WO2011046066A1 - リチウム二次電池用基材及びリチウム二次電池用セパレータ - Google Patents

リチウム二次電池用基材及びリチウム二次電池用セパレータ Download PDF

Info

Publication number
WO2011046066A1
WO2011046066A1 PCT/JP2010/067702 JP2010067702W WO2011046066A1 WO 2011046066 A1 WO2011046066 A1 WO 2011046066A1 JP 2010067702 W JP2010067702 W JP 2010067702W WO 2011046066 A1 WO2011046066 A1 WO 2011046066A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
lithium secondary
base material
secondary battery
fibers
Prior art date
Application number
PCT/JP2010/067702
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
兵頭　建二
宏明 渡邉
緑川　正敏
佃　貴裕
友洋 佐藤
山本　浩和
加寿美 加藤
克彦 川崎
真一 江角
松岡　昌伸
Original Assignee
三菱製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱製紙株式会社 filed Critical 三菱製紙株式会社
Priority to CN201080046394.4A priority Critical patent/CN102549805B/zh
Priority to KR1020127008642A priority patent/KR101702693B1/ko
Priority to JP2011536114A priority patent/JP5651120B2/ja
Publication of WO2011046066A1 publication Critical patent/WO2011046066A1/ja

Links

Images

Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/411—Organic 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • 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
    • H01M50/44—Fibrous 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium secondary battery substrate and a lithium secondary battery separator that can be suitably used for lithium secondary batteries such as lithium ion secondary batteries and lithium ion polymer secondary batteries.
  • a lithium secondary battery using an organic electrolyte (non-aqueous electrolyte) has attracted attention.
  • This lithium secondary battery has a high energy density because an average voltage of about 3.7 V, which is about three times that of an alkaline secondary battery, which is a conventional secondary battery, can be obtained.
  • an aqueous electrolyte solution cannot be used, a non-aqueous electrolyte solution having sufficient oxidation-reduction resistance is used.
  • non-aqueous electrolytes are flammable, there is a risk of ignition and the like, and careful attention is paid to safety in their use. There are several possible cases of exposure to fire and other hazards, but overcharging is particularly dangerous.
  • the current non-aqueous secondary battery has a safety circuit / PTC element equipped and a separator with a thermal fuse function for the purpose of destroying the battery safely when overcharged. Has been made. However, even if equipped with the above-mentioned means, depending on the overcharge conditions, the safety during overcharge is not guaranteed, and in fact, non-aqueous secondary battery ignition accidents Is still happening.
  • a film-like porous film made of polyolefin such as polyethylene is often used, and when the temperature inside the battery is around 130 ° C., it melts and closes the micropores.
  • a thermal fuse function shutdown function
  • the polyolefin itself may melt and short-circuit, suggesting the possibility of thermal runaway Has been. Therefore, there is a need for a heat-resistant separator that does not melt and shrink even at temperatures close to 200 ° C.
  • a nonwoven fabric mainly composed of ultrafine fibers composed of a low melting point resin component and a high melting point resin component as a separator, when the temperature inside the battery rises, the low melting point resin component melts and pores between the fibers are formed.
  • a shut-down characteristic is expressed by blocking (see, for example, Patent Document 6).
  • the nonwoven fabric in order to express the strength of the nonwoven fabric, it is necessary to melt the low melting point resin component and bond the fibers sufficiently, but the difference between the heating temperature and the shutdown temperature required for strength development is small, while maintaining the strength, it is very difficult to control the pore diameter and the number of pores between the fibers.
  • the shutdown characteristic when the shutdown characteristic is not sufficiently developed, the nonwoven fabric itself may melt and shrink and may cause a short circuit.
  • a non-woven fabric, a woven fabric or the like is not used as a separator as it is, but is used as a base material, and various materials are combined with the base material to provide heat resistance and a shutdown function.
  • a separator that has been combined with a porous film on a base material, and a separator that has been composited by impregnating and surface coating filler particles, resin, gel electrolyte, solid electrolyte, etc. on the base material have been reported. (For example, see Patent Documents 8 to 10).
  • composite materials such as filler particles, resins, and porous films, but they are used as substrates.
  • the base material that has been used so far has large pores, so that the surface smoothness when composited by bonding, surface coating, impregnation, etc. is poor, and the composite is easy to peel off or fall off was there.
  • the composite material is filled in the base material and the pores inside the base material are closed, the electrolyte solution retainability is deteriorated and the internal resistance of the separator is increased.
  • JP 2003-323878 A JP 2003-123728 A JP 2007-317675 A (Pamphlet of International Publication No. 2001/67536, US Patent Application Publication No. 2003/0003363) JP 2006-19191 A JP-A-60-52 JP 2004-115980 A JP 2004-214066 A JP 2005-293891 A JP 2005-536857 A (Pamphlet of International Publication No. 2004/021476, US Patent Application Publication No. 2006/0024569) JP 2007-157723 A (International Publication No. 2006/062153, US Patent Application Publication No. 2007/0264577)
  • An object of the present invention is to provide a lithium secondary battery substrate that is used to form a composite for a lithium secondary battery by combining with a composite such as a porous film, filler particles, a resin, a gel electrolyte, and a solid electrolyte.
  • a composite such as a porous film, filler particles, a resin, a gel electrolyte, and a solid electrolyte.
  • a base material for a lithium secondary battery that has a small variation in the surface when composited and can reduce peeling and dropping of the composite, and a separator for a lithium secondary battery using the base material for the lithium secondary battery Is to provide.
  • the present invention for solving the above problems comprises the following base materials (1) to (22) for lithium secondary batteries and a separator (23) for lithium secondary batteries.
  • a base material for a lithium secondary battery comprising a nonwoven fabric containing, as essential components, synthetic resin short fibers and fibrillated lyocell fibers
  • the base material for a lithium secondary battery according to the above (1) wherein the fibrillated lyocell fiber content is 5 to 80% by mass of the nonwoven fabric.
  • a base material for a lithium secondary battery according to the above (1) or (2) (7) In the fiber length distribution histogram of the fibrillated lyocell fiber, the lithium secondary battery substrate according to (6) above having a peak between 1.50 and 3.50 mm in addition to the maximum frequency peak, (8) The base material for a lithium secondary battery according to the above (1) or (2), wherein the synthetic resin constituting the synthetic resin short fiber is at least one selected from polyester resins, acrylic resins, and polyolefin resins. , (9) The above-mentioned (1) or (2), which comprises a nonwoven fabric containing core-sheath-type heat-fusible short fibers composed of a heat-fusion component and a non-heat-fusion component as at least one kind of synthetic resin short fibers.
  • Base material for lithium secondary battery (10) The base for a lithium secondary battery according to (9), wherein the core of the core-sheath type heat-fusible short fiber is polyethylene terephthalate and the sheath is a polyester copolymer, (11) The base material for a lithium secondary battery according to (9) or (10), which is heat-treated, (12) The base material for a lithium secondary battery according to (1) or (2), further comprising a nonwoven fabric containing a paper strength enhancer as an essential component, (13) The base material for a lithium secondary battery according to (12), wherein the paper strength enhancer is at least one selected from a synthetic polymer, a semi-synthetic polymer, a vegetable gum, and starch, (14) The base material for a lithium ion battery according to the above (12), wherein the paper strength enhancer is at least one selected from amphoteric or cationic polyacrylamide resins.
  • Base material for lithium secondary battery (22) A heat-resistant layer (A) containing synthetic resin short fibers and fibrillated lyocell fibers as essential components, and a heat-melting layer (B) containing synthetic resin short fibers and polyethylene synthetic pulp as essential components
  • the separator for lithium secondary batteries which performs at least 1 process chosen from the process to carry out, the process which laminates and integrates a porous film, the process which impregnates or coats a solid electrolyte or a gel electrolyte.
  • the base material for a lithium secondary battery of the present invention is composed of a nonwoven fabric containing, as essential components, synthetic resin short fibers and fibrillated lyocell fibers.
  • the fibrillated lyocell fiber is entangled with the synthetic resin short fiber, so that the surface is highly smooth and excellent in denseness.
  • the lithium secondary battery separator of the present invention obtained by bonding to the lithium secondary battery base material of the present invention, combining with impregnation, surface coating, etc. has reduced surface variation. , The composite is less likely to be peeled off or dropped off. Further, the fibrillated lyocell fiber present on the surface of the base material for the lithium secondary battery is firmly bound to the composite, whereby the composite can be further prevented from being peeled off or dropped off.
  • FIG. 1 is a graph showing the relationship between Canadian standard freeness of fibrillated lyocell fibers and modified freeness (freeness measured in accordance with JIS P8121 except that the sample concentration is 0.03%). It is.
  • Fig. 2 shows the modified drainage of fibrillated lyocell fiber (according to JIS P8121 except that an 80-mesh wire mesh with a wire diameter of 0.14 mm and an aperture of 0.18 mm is used as the sieve plate, and the sample concentration is 0.1%) It is an example of the graph showing the modified drainage degree measured in this way.
  • FIG. 1 is a graph showing the relationship between Canadian standard freeness of fibrillated lyocell fibers and modified freeness (freeness measured in accordance with JIS P8121 except that the sample concentration is 0.03%). It is.
  • Fig. 2 shows the modified drainage of fibrillated lyocell fiber (according to JIS P8121 except that an 80-mesh wire mesh with a wire diameter of 0.14 mm and an aperture of 0.18
  • FIG. 3 shows a modified drainage degree of fibrillated lyocell fibers used in the examples of the present invention (80 mesh wire mesh having a wire diameter of 0.14 mm and openings of 0.18 mm was used as a sieve plate, and the sample concentration was 0.1%. It is the graph showing the modified drainage degree measured based on JIS P8121 except having made it.
  • FIG. 4 is a fiber length distribution histogram of fibrillated lyocell fiber [I].
  • FIG. 5 is a fiber length distribution histogram of fibrillated lyocell fiber [II].
  • FIG. 6 shows a graph of the ratio of fibers having a fiber length of every 0.05 mm between 1.0 and 2.0 mm and an approximate straight line in a fiber length distribution histogram of fibrillated lyocell fibers [I] and [II].
  • FIG. 7 is an example of a fiber length distribution histogram of fibrillated lyocell fiber [i] having a maximum frequency peak between 0.00 and 1.00 mm.
  • FIG. 8 is an example of a fiber length distribution histogram of fibrillated lyocell fiber [ii] having a peak between 1.50 and 3.50 mm in addition to the maximum frequency peak.
  • the base material for a lithium secondary battery of the present invention (hereinafter sometimes referred to as “base material”) is a base material for impregnating or coating a slurry containing filler particles, and a slurry containing a resin.
  • the filler may be either inorganic or organic.
  • Inorganic fillers include alumina, gibbsite, boehmite, magnesium oxide, magnesium hydroxide, silica, titanium oxide, barium titanate, zirconium oxide and other inorganic oxides, aluminum nitride and silicon nitride inorganic nitrides, aluminum compounds, zeolites And mica.
  • Examples of the organic filler include polyethylene, polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polystyrene, polyvinylidene fluoride, ethylene-vinyl monomer copolymer, polyolefin wax, and the like.
  • the porous film is not particularly limited as long as it is a resin capable of forming a film, but is preferably a polyolefin resin such as a polyethylene resin and a polypropylene resin.
  • Polyethylene resins include not only ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, or ultra high density polyethylene alone, but also ethylene propylene copolymers. Or a mixture of a polyethylene-based resin and another polyolefin-based resin.
  • Polypropylene resins include homopropylene (propylene homopolymer), or ⁇ -, such as propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene or 1-decene. Examples thereof include random copolymers with olefins and block copolymers.
  • the lithium secondary battery in the present invention means a lithium ion battery, a lithium ion polymer battery, or the like.
  • the negative electrode active material of the lithium secondary battery include carbon materials such as graphite and coke, metallic lithium, aluminum, silica, tin, nickel, and an alloy of lithium and lithium, SiO, SnO, Fe Metal oxides such as 2 O 3 , WO 2 , Nb 2 O 5 , Li 4/3 Ti 5/3 O 4 , and nitrides such as Li 0.4 CoN are used.
  • the positive electrode active material lithium cobaltate, lithium manganate, lithium nickelate, lithium titanate, lithium nickel manganese oxide, or lithium iron phosphate is used.
  • the lithium iron phosphate may be a composite with one or more metals selected from manganese, chromium, cobalt, copper, nickel, vanadium, molybdenum, titanium, zinc, aluminum, gallium, magnesium, boron, and niobium.
  • an electrolytic solution for a lithium secondary battery a solution obtained by dissolving a lithium salt in an organic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, dimethoxymethane, or a mixed solvent thereof is used.
  • the lithium salt include lithium hexafluorophosphate and lithium tetrafluoroborate.
  • solid electrolyte what melt
  • the base material for a lithium secondary battery of the present invention is composed of a nonwoven fabric containing, as essential components, synthetic resin short fibers and fibrillated lyocell fibers.
  • “Lyocell” of fibrillated lyocell fiber is a term defined in ISO standards and Japanese JIS standards, and refers to “cellulose fibers obtained by spinning directly in an organic solvent without spinning through cellulose derivatives”. is there.
  • Lyocell fibers are beater and dispersion equipment such as beaters, PFI mills, single disc refiners (SDR), double disc refiners (DDR), ball mills and dyno mills used to disperse and pulverize pigments, etc. Can be fibrillated.
  • SDR single disc refiners
  • DDR double disc refiners
  • the desired optimally fibrillated lyocell fiber fiber length, fiber length distribution, variant freeness
  • the modified freeness of the fibrillated lyocell fiber is 0 to 250 ml, and the length weighted average fiber length is 0.20 to 2.00 mm. It is preferable that the pores of the substrate are formed relatively uniformly. As a result, the back-through of the coating liquid containing the composite such as filler particles and resin is suppressed, and the composite is concentrated on the surface of the base material, so that the surface smoothness after coating is excellent, Unnecessary gaps are unlikely to occur between the two. In addition, since the back-through of the coating liquid is suppressed, there is no problem that pores inside the base material are blocked by the composite material filled inside the base material, and a separator with a high electrolyte retention rate is obtained. Can do.
  • the modified freeness in the present invention means that either the sample concentration or the sieve plate, or both the sample concentration and the sieve plate are changed with respect to the Canadian standard freeness measurement method stipulated in JIS P8121. Means the freeness measured. So far, the relationship between Canadian standard freeness and modified freeness of natural cellulose fibers such as conifer wood pulp, hardwood wood pulp, hemp pulp and esparto pulp has been reported, but fibrillated lyocell fiber. the relationship between the Canadian standard freeness and modified freeness of, were not revealed.
  • the refiner was used to refine the lyocell fiber, and as a result of measuring the Canadian standard freeness and modified freeness for each degree of refinement, the drainage behavior of the lyocell fiber was It has been found that it is different from the drainage behavior of natural cellulose fiber disclosed in Japanese Patent No. 2000-331663.
  • Fig. 1 shows the relationship between Canadian standard freeness and modified freeness of fibrillated lyocell fiber.
  • the standard freeness means the Canadian standard freeness of JIS P8121.
  • the modified freeness means the freeness measured according to JIS P8121, except that the sample concentration is 0.03%.
  • the horizontal axis in FIG. 1 indicates the length-weighted average fiber length, and the degree of miniaturization progresses toward the right.
  • the Canadian standard freeness is 0.5 ml with a length-weighted average fiber length of 0.72 mm, but the shorter the length-weighted average fiber length is 0.55 mm or less, the greater the freeness. Yes.
  • variations freeness according proceeds the degree of miniaturization, freeness is increased.
  • This drainage behavior is the drainage behavior of natural cellulose fibers disclosed in JP 2000-331663 A, that is, the Canadian standard freeness and modified freeness decrease as the degree of refinement progresses. The drainage behavior is quite different.
  • the reason why the degree of freezing increases as the degree of refinement progresses is that the length-weighted average fiber length of the fibrillated lyocell fiber becomes shorter as the refinement progresses, especially when the sample concentration is thin, This is because the entanglement between the fibers decreases and the fiber network is hardly formed, so that the fibrillated lyocell fibers themselves pass through the holes in the sieve plate. That is, in the case of refined lyocell fiber, an accurate freeness cannot be measured by the measuring method of JIS P8121.
  • FIG. 2 shows an example of modified freeness measured by changing both the sample concentration and the sieve plate. That is, this is a modified freeness measured by using an 80-mesh wire net instead of the sieve plate specified in JIS P8121, and setting the sample concentration to 0.1%.
  • the wire diameter of 80 mesh was 0.14 mm in diameter, and a wire mesh (PULP AND PAPER RESEARCH INSTITUTE OF CANADA) having an opening of 0.18 mm was used.
  • PULP AND PAPER RESEARCH INSTITUTE OF CANADA wire mesh having an opening of 0.18 mm was used.
  • the modified freeness in the present invention is based on JIS P8121, except that an 80 mesh wire net having a wire diameter of 0.14 mm and an aperture of 0.18 mm is used as a sieve plate, and the sample concentration is 0.1%. It means the measured modified freeness, and is simply expressed as “modified dryness” unless otherwise specified.
  • the fiber length and fiber length distribution histogram of the fibrillated lyocell fiber can be obtained by utilizing the deflection characteristics obtained by applying laser light to the fiber, and can be measured using a commercially available fiber length measuring instrument.
  • the “fiber length”, “average fiber length” and “fiber length distribution” of the fibrillated lyocell fiber are “length-weighted fiber length”, “length-weighted average fiber length” and “ It means “length-weighted fiber length distribution”.
  • the lyocell short fibers are mixed with water at an appropriate concentration.
  • rotary blade homogenizer that applies shearing force with a high-speed rotary blade, cylindrical inner blade that rotates at high speed, and fixed outer blade Double-cylindrical high-speed homogenizer that generates shearing force
  • ultrasonic crusher that is refined by impact by ultrasonic waves, high-pressure homogenizer, etc., and conditions such as blade shape, flow rate, processing frequency, processing speed, processing concentration, etc.
  • the lyocell fiber is divided parallel to the fiber long axis and the fiber length is shortened. Therefore, the pores of the base material are formed relatively uniformly, preventing the back-through of the coating liquid during coating, and improving the surface smoothness of the coating layer. Further, since the back-through of the coating liquid is suppressed, the filler particles do not block the pores inside the substrate, and a separator having excellent electrolyte solution retention can be obtained.
  • the length-weighted average fiber length can be adjusted in various ways within the range of 0 to 250 ml of modified freeness by changing the conditions of refinement. Even so, fibrillated lyocell fibers having different length-weighted average fiber lengths can be produced.
  • FIG. 3 shows the modified freeness of the fibrillated lyocell fiber used in Examples 14 to 36 of the present invention.
  • the modified freeness of the fibrillated lyocell fiber is more preferably 0 to 200 ml, further preferably 0 to 160 ml.
  • the modified freeness exceeds 250 ml, the refinement process is insufficient, the fiber division does not proceed sufficiently, and the ratio of the fiber diameter remaining large increases, so that a large through hole is formed in the base material. , The coating liquid will be broken through during coating.
  • the length weighted average fiber length of the fibrillated lyocell fiber used in the present invention is more preferably 0.30 to 1.80 mm, and further preferably 0.40 to 1.60 mm.
  • fibrillated lyocell fibers may fall off from the base material during wet papermaking or after wet papermaking or may be broken during coating due to fluffing. If it is longer than 2.00 mm, the fibers are easily entangled, resulting in unevenness in the formation and unevenness in thickness.
  • the fiber length distribution histogram of fibrillated lyocell fibers as in the lithium secondary battery substrate (4) of the present invention has a maximum frequency peak between 0.00 and 1.00 mm, and is 1.00 mm or more. It is preferable that the ratio of the fibers having a fiber length of 10% or more.
  • Such fibrillated lyocell fibers are well entangled with the synthetic resin short fibers, the surface smoothness of the base material is increased, the denseness is excellent, and the surface variation when combined by surface coating is reduced. , It becomes difficult for the composite to fall off. Moreover, the fibrillated lyocell fiber present on the surface of the base material is firmly bound to the composite, whereby the composite can be further prevented from falling off.
  • the slope of the ratio of fibers having a fiber length of every 0.05 mm between 1.00 and 2.00 mm is more preferable because the denseness required for the substrate and the coating property of the substrate are more excellent.
  • the fiber length distribution histograms of fibrillated lyocell fibers with a maximum frequency peak between 0.00 and 1.00 mm, and the proportion of fibers having a fiber length of 1.00 mm or more. 10% or more. More preferably, the fiber length distribution histogram has a maximum frequency peak between 0.30 and 0.70 mm in terms of the smoothness of the surface when complexed by surface coating such as filler particles or resin.
  • the ratio of the fibers having a fiber length of 1.00 mm or more is 12% or more.
  • the proportion of fibers having a fiber length of 1.00 mm or more is preferably higher, but about 50% is sufficient.
  • the slope of the ratio of fibers having a fiber length of every 0.05 mm between 1.00 and 2.00 mm is ⁇ 3.0 or more and ⁇ 0.5 or less. -2.5 or more and -0.8 or less are more preferable, and -2.0 or more and -1.0 or less are still more preferable. It is preferable to use fibrillated lyocell fibers having an inclination in this range because the coating property of the substrate is improved. When the inclination is smaller than ⁇ 3.0, the base material may be damaged during the composite process, or the composite product may fall off. On the other hand, if the inclination exceeds ⁇ 0.5, the denseness and the coating property of the substrate may not be improved.
  • “large inclination” means a state in which the fiber length distribution of the fibrillated lyocell fiber is wide.
  • “Slight inclination” is a state in which the fiber length distribution of fibrillated lyocell fibers is narrow and the fiber lengths are more uniform.
  • the slope of the fibrillated lyocell fiber [I] in FIG. 4 is ⁇ 2.9, and the slope of the fibrillated lyocell fiber [II] in FIG. 5 is ⁇ 0.6.
  • the “inclination of the proportion of fibers having a fiber length of every 0.05 mm between 1.00 and 2.00 mm” is 0. 1 between 1.00 and 2.00 mm, as shown in FIG.
  • an approximate straight line is calculated by the method of least squares, and the inclination of the obtained approximate straight line is meant.
  • the fiber length distribution histogram of the fibrillated lyocell fiber as in the lithium secondary battery substrate (6) of the present invention has a maximum frequency peak between 0.00 and 1.00 mm, and is 1.00 mm or more. It is preferable that the ratio of the fibers having a fiber length of 50% or more.
  • Such fibrillated lyocell fibers are well entangled with the synthetic resin short fibers, the surface smoothness of the base material is increased, the denseness is excellent, and the surface variation when combined by surface coating is reduced. , It becomes difficult for the composite to fall off. Moreover, the fibrillated lyocell fiber present on the surface of the base material is firmly bound to the composite, whereby the composite can be further prevented from falling off.
  • a base for lithium secondary battery having a peak between 1.50 and 3.50 mm in addition to the maximum frequency peak The material (7) is more preferable because it is more excellent in the denseness required for the base material and the coatability of the base material.
  • FIG. 7 is a fiber length distribution histogram of fibrillated lyocell fibers.
  • the maximum frequency peak is between 0.00 and 1.00 mm, and the proportion of fibers having a fiber length of 1.00 mm or more is 50% or more. It is.
  • the fiber length distribution histogram has a maximum frequency peak between 0.30 and 0.70 mm in terms of the smoothness of the surface when complexed by surface coating such as filler particles or resin, and is 1.00 mm. More preferably, the proportion of fibers having the above fiber length is 55% or more. A higher proportion of fibers having a fiber length of 1.00 mm or more is desirable, but about 75% is sufficient.
  • the fiber length distribution histogram of fibrillated lyocell fibers it is more preferable to have a peak between 1.50 and 3.50 mm in addition to the maximum frequency peak described above. More preferably, it has a peak between 3.25 mm, and particularly preferably has a peak between 2.00 and 3.00 mm. By having a peak in this range, it is preferable because both the coatability of the substrate and the prevention of the composite from falling off can be achieved.
  • the fiber length of the peak is shorter than 1.50 mm, the base material may be damaged during composite formation, or the composite product may fall off. On the other hand, if it exceeds 3.50 mm, the denseness and the coating property of the substrate are not improved, and the composite product may fall off.
  • the resins constituting the synthetic resin short fibers include polyolefin resins, polyester resins, polyvinyl acetate resins, ethylene-vinyl acetate copolymer resins, polyamide resins, acrylic resins, polyvinyl chloride resins, and polychlorinated resins.
  • Vinylidene resins polyvinyl ether resins, polyvinyl ketone resins, polyether resins, polyvinyl alcohol resins, diene resins, polyurethane resins, phenol resins, melamine resins, furan resins, urea resins, aniline resins
  • Examples include resins, unsaturated polyester resins, alkyd resins, fluorine resins, silicone resins, polyamideimide resins, polyphenylene sulfide resins, polyimide resins, and derivatives of these resins.
  • a polyester resin, an acrylic resin, or a polyolefin resin is used, a lithium secondary battery substrate having higher surface smoothness and excellent denseness can be obtained.
  • polyester resin the acrylic resin, the polyolefin resin, and the fibrillated lyocell fiber are intertwined more uniformly than other synthetic resins. Further, with these resins, it is possible to obtain a base material for a lithium secondary battery that is more effective in suppressing damage to the base material and suppressing wrinkles and is excellent in denseness. If a polyester resin, acrylic resin, or polyamide resin is used, the heat resistance of the substrate can be improved.
  • polyester resin examples include polyethylene terephthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polyethylene isophthalate resin, and derivatives thereof. Can be mentioned. Among these, when used for a base material for a lithium secondary battery, a polyethylene terephthalate resin having excellent heat resistance and electrolytic solution resistance is preferable.
  • Acrylic resin is made of 100% acrylonitrile polymer, and acrylonitrile is copolymerized with (meth) acrylic acid derivatives such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, vinyl acetate, etc. And the like.
  • polystyrene resin examples include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl alcohol copolymer, olefin copolymer, and the like. From the viewpoint of heat resistance, polypropylene, polymethylpentene, ethylene-vinyl alcohol copolymer, olefin copolymer and the like can be mentioned.
  • Polyamide resins include aliphatic polyamides such as nylon, poly-p-phenylene terephthalamide, poly-p-phenylene terephthalamide-3,4-diphenyl ether terephthalamide, and poly-m-phenylene isophthalamide.
  • An aromatic polyamide having, for example, a fatty chain as a part of the main chain can be mentioned.
  • the synthetic resin short fiber may be a fiber (single fiber) made of a single resin, or may be a fiber (composite fiber) made of two or more kinds of resins.
  • the synthetic resin short fiber contained in the base material for lithium secondary batteries of the present invention may be one kind or a combination of two or more kinds.
  • the composite fiber include a core-sheath type, an eccentric type, a side-by-side type, a sea-island type, an orange type, and a multiple bimetal type.
  • the fineness of the synthetic resin short fiber is preferably 0.004 to 1.3 dtex, more preferably 0.007 to 0.8 dtex, further preferably 0.02 to 0.6 dtex, and particularly preferably 0.04 to 0.3 dtex. .
  • the fineness of the synthetic resin short fibers exceeds 1.3 dtex, the number of fibers in the thickness direction decreases, so that the required denseness cannot be ensured, the coating liquid is exposed, or the thickness is reduced. It may be difficult. Moreover, the unevenness
  • the fiber length of the synthetic resin short fiber is preferably 0.4 to 10 mm, more preferably 1 to 7 mm, further preferably 1 to 6 mm, and particularly preferably 1 to 5 mm. If the fiber length exceeds 10 mm, formation may be poor. On the other hand, when the fiber length is less than 0.4 mm, the mechanical strength of the base material becomes low, and the base material may be damaged during the composite.
  • a heat-fusible short fiber that functions as a binder may be used.
  • the heat-fusible short fiber include a core-sheath type, an eccentric type, a side-by-side type, a sea-island type, an orange type, a multi-bimetal type composite fiber, or a single fiber.
  • Unstretched polyester short fibers are suitable in terms of improving uniformity, and the core-sheath type heat-fusible short fibers are softened, melted or melted by wet heat while maintaining the fiber shape of the core. Since the fibers are thermally bonded to each other, it is suitable for bonding the fibers without impairing the dense structure of the base material. Moreover, you may use the wet heat adhesive fiber which functions as a binder.
  • the wet heat adhesive fiber refers to a fiber that exhibits an adhesive function by flowing or easily deforming from a fiber state at a certain temperature in a wet state.
  • thermoplastic fiber that is softened with hot water (for example, about 80 to 120 ° C.) and can be self-adhered or bonded to other fibers, such as polyvinyl fibers (polyvinyl pyrrolidone, polyvinyl ether, vinyl alcohol).
  • cellulose fibers C1-3 alkyl cellulose such as methyl cellulose, hydroxy C1-3 alkyl cellulose such as hydroxymethyl cellulose, carboxy C1-3 alkyl cellulose such as carboxymethyl cellulose or salts thereof
  • modified Fibers made of vinyl copolymers copolymers or salts of vinyl monomers such as isobutylene, styrene, ethylene, vinyl ether and unsaturated carboxylic acids such as maleic anhydride or anhydrides thereof
  • vinyl copolymers or salts of vinyl monomers such as isobutylene, styrene, ethylene, vinyl ether and unsaturated carboxylic acids such as maleic anhydride or anhydrides thereof
  • wet heat adhesive fibers it is necessary to control the blending amount and the degree of melting and not to form a film, but to melt only at the intersection between other fibers to act as a binder.
  • the core-sheath type short heat-sealable material comprising a heat-seal component and a non-heat-seal component as the base material is at least one kind of synthetic resin short fiber
  • the core-sheath-type heat-fusible short fibers maintain the fiber shape of the core part, and only the sheath part is softened, melted or wet-heat-dissolved to thermally bond the fibers together, without compromising dense structure of the substrate, thereby bonding the fibers together.
  • the sheath portion of the core-sheath type heat-fusible short fiber is softened, melted or melted by wet heat, and the fibers are thermally bonded to each other. Since falling off and fluffing can be prevented, the variation in the surface when combined by surface coating can be reduced.
  • the resin component constituting the core and sheath of the core-sheath-type heat-fusible short fiber is not particularly limited, and any resin having fiber-forming ability may be used.
  • the core / sheath combination includes polyethylene terephthalate / polyester copolymer, polyethylene terephthalate / polyethylene, polyethylene terephthalate / polypropylene, polyethylene terephthalate / ethylene-propylene copolymer, polyethylene terephthalate / ethylene-vinyl alcohol copolymer. , polypropylene / polyethylene, high melting point polylactic acid / low melting point polylactic acid.
  • the melting point, softening point or wet heat melting temperature of the resin component in the core part is preferably 20 ° C. or more higher than the melting point or softening point of the resin component in the sheath part from the viewpoint of easy production of the nonwoven fabric.
  • the thermal dimensional stability of the base material is improved. It is preferable because the property can be improved.
  • a polyester copolymer for the sheath because the mechanical strength of the base material is improved.
  • the polyester copolymer used for the sheath is a copolymer of polyethylene terephthalate and one or more compounds selected from isophthalic acid, sebacic acid, adipic acid, diethyl glycol, 1,4-butadiol and the like. preferable.
  • the content of the heat-fusible short fibers is preferably 5 to 40% by mass, more preferably 8 to 35% by mass with respect to the nonwoven fabric. More preferably, it is 10 to 30% by mass. If the content is less than 5% by mass, the mechanical strength of the substrate may be reduced, and if it exceeds 40% by mass, the thermal dimensional stability may be reduced.
  • the total content of the fibrillated lyocell fiber and the synthetic resin short fiber is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and 80 to 100% by mass. % Is more preferable. If the total content is less than 50% by mass, the coating liquid may be broken through.
  • the base material for a lithium secondary battery of the present invention may contain fibers other than the synthetic resin short fibers and the fibrillated lyocell fibers.
  • fibers other than the synthetic resin short fibers and the fibrillated lyocell fibers examples include natural cellulose fibers, pulped and fibrillated natural cellulose fibers, short fibers of regenerated fibers or semi-synthetic fibers, fibrils made of synthetic resins, pulped products, fibrillated products, inorganic fibers, and the like.
  • the modified freeness of the natural cellulose fiber pulped product or fibrillated product is preferably 0 to 400 ml.
  • the inorganic fiber include glass, alumina, silica, ceramics, and rock wool. When inorganic fiber is contained, the heat-resistant dimensional stability and puncture strength of the substrate may be improved, which is preferable.
  • the mass ratio of the synthetic resin short fiber and the fibrillated lyocell fiber is preferably 95/5 to 20/80, more preferably 90/10 to 30/70, 70/30 to 40/60 is more preferable.
  • the base material for a lithium secondary battery in which the content of the fibrillated lyocell fiber is 5 to 80% by mass of the total content of the synthetic resin short fiber and the fibrillated lyocell fiber is required to be dense and uniform as a base material. The property is better.
  • the content ratio of the fibrillated lyocell fiber is less than 5% by mass, the denseness and uniformity may not be improved, or the coating liquid may be broken through.
  • the content ratio of the fibrillated lyocell fiber exceeds 80% by mass the substrate may be damaged when the substrate is handled or combined.
  • the fibrillated lyocell fiber and the synthetic resin short fiber are the paper strength enhancer.
  • surface smoothness is high, density is excellent, and variation in the surface when combined by surface coating is reduced.
  • the composite not only does the composite fall off easily, but also prevents the fibers from falling off and fluffing when composited, can provide a uniform surface, can improve the coating suitability, Dirt etc. can also be controlled.
  • the base material for a lithium secondary battery (13) in which the paper strength enhancer is at least one selected from synthetic polymers, semi-synthetic polymers, vegetable gums and starches is more excellent in coating suitability.
  • the synthetic polymer include polyacrylamide resin, polyethyleneimine resin, urea resin, polyethylene oxide (PEO), polyvinyl alcohol (PVA), and the like.
  • the semi-synthetic polymer include dialdehyde starch, cationic starch, methyl cellulose, carboxymethyl cellulose, and hydroxymethyl cellulose.
  • examples of vegetable gums include guar gum, locust bean gum, chili pepper gum and the like.
  • the starch include corn starch, potato starch, wheat starch, tapioca starch and the like.
  • the cationic portion of the paper strength enhancer and the fibrillated lyocell fiber The anion part adsorbs and strengthens the bond between fibers.
  • the amphoteric or cationic polyacrylamide is present between the fibers constituting the nonwoven fabric in a state where the polyacrylamide portion is self-adhered, so that a network having a moderate space is formed without the fibers being aggregated too much. . For this reason, it is possible to further prevent the surface from becoming uneven when it is combined, and to prevent the fine fibers such as the fibrillated lyocell fibers from falling off and the fluffing of the fibers constituting the nonwoven fabric.
  • the amphoteric or cationic polyacrylamide-based resin linear, can be used in branched both.
  • the cation portion is adsorbed on the fibrillated lyocell fiber, and the anion portion is self-bonded with each other and bonded more firmly.
  • an amphoteric polyacrylamide type resin is more preferable.
  • the polyacrylamide-based resin is preferably a mass average molecular weight of 10,000 to 6,000,000.
  • the mass average molecular weight is less than 10,000, the required strength cannot be obtained.
  • the mass average molecular weight is more than 6 million, the viscosity becomes high, and it may be difficult to produce and apply a nonwoven fabric by a wet method.
  • the mass average molecular weight here refers to the molecular weight measured by gel permeation chromatography.
  • Polyacrylamide-based resin according to the present invention can be manufactured as follows.
  • the polyacrylamide resin is obtained, for example, by copolymerizing (a) (meth) acrylamide and (b) a cationic vinyl monomer and / or (c) an anionic vinyl monomer. That is, the cationic polyacrylamide resin can be obtained by copolymerizing (a) (meth) acrylamide and (b) a cationic vinyl monomer.
  • the amphoteric polyacrylamide resin is obtained by copolymerizing (a) (meth) acrylamide, (b) a cationic vinyl monomer, and (c) an anionic vinyl monomer.
  • Component (a) is preferably used in an amount of 50 to 98.9 mol%, more preferably 50 to 96.5 mol%, based on the total molar amount of monomers constituting the cationic or amphoteric polyacrylamide resin. When the component (a) is less than 50 mol%, it may be difficult to obtain sufficient coating suitability.
  • Examples of cationic vinyl monomers include vinyls having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and the like.
  • vinyls having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and the like.
  • the amount of the (b) cationic vinyl monomer used is such that the equivalent ratio of the cationic group / anionic group is 2 or less.
  • the means for imparting a cationic group to an amphoteric polyacrylamide resin includes (b) Mannich modification in which formalin and a secondary amine are reacted with anionic acrylamide in addition to the method of copolymerizing a cationic vinyl monomer.
  • a cationic group can also be introduced by a Hofmann reaction in which a hypohalite is reacted. Even when a cationic group is introduced by such modification, the equivalent ratio of the cationic group / anionic group in the amphoteric polyacrylamide resin is preferably 2 or less.
  • anionic vinyl monomer examples include ⁇ , ⁇ -unsaturated monobasic acids such as (meth) acrylic acid, crotonic acid, and (meth) allylcarboxylic acid; maleic acid, fumaric acid, itaconic acid, muconic acid, etc. ⁇ , ⁇ -unsaturated dibasic acids of the above; organic sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, (meth) allyl sulfonic acid; or sodium salts of these various organic acids , Alkali metal salts such as potassium salts, ammonium salts and the like.
  • monobasic acids such as (meth) acrylic acid, crotonic acid, and (meth) allylcarboxylic acid
  • anionic vinyl monomers can be used alone or in combination of two or more.
  • the use of a monomer having a (meth) allyl group, particularly (meth) allylsulfonic acid or a salt thereof, as one kind of anionic vinyl monomer is preferable in terms of increasing the molecular weight of the polyacrylamide resin.
  • the amount of the (b) cationic vinyl monomer and (c) anionic vinyl monomer used is usually preferably 1 to 40 mol%, preferably 3 to 40 mol based on the total molar amount of monomers constituting the amphoteric polyacrylamide resin. % Is more preferable, and 3 to 30 mol% is more preferable.
  • N-substituted (meth) acrylamides represented by the general formula (1) a methyl group or a methylene group in an N-alkyl group acts as a chain transfer point, and many branched structures are introduced into the polymer. A branched polymer without conversion is obtained.
  • Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R2 or R3 in the general formula (1) include a methyl group, an ethyl group, an isopropyl group, and a t-butyl group.
  • N-substituted (meth) acrylamides include N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- Examples include isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide and the like. Of these, copolymerizable, in terms of the chain transfer N, N-dimethylacrylamide are preferred.
  • a cross-linked structure can be imparted to the amphoteric or cationic polyacrylamide resin by using a polyfunctional monomer.
  • Multifunctional monomers include di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, methylene bis (meth) acrylamide, ethylene bis (meth) Bis (meth) acrylamides such as acrylamide and hexamethylenebis (meth) acrylamide, divinyl esters such as divinyl adipate and divinyl sebacate, allyl methacrylate, diallylamine, diallyldimethylammonium, diallyl phthalate, diallyl chlorendate, divinylbenzene Bifunctional vinyl monomers such as N, N-diallylacrylamide; 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate Trifunctional vinyl mono
  • the amount of N-substituted (meth) acrylamides and / or polyfunctional monomers represented by the general formula (1) is 10 with respect to the total moles of monomers constituting the cationic or amphoteric polyacrylamide resin. It is preferably about mol% or less, more preferably 5 mol% or less. In order to exhibit the function of the N-substituted (meth) acrylamides represented by the general formula (1), it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. .
  • the alkyl ester of the anionic vinyl monomer (alkyl group having 1 to 8 carbon atoms), acrylonitrile, styrenes, vinyl acetate, methyl vinyl ether.
  • Nonionic vinyl monomers such as can also be used.
  • the amount used is preferably about 30 mol% or less, preferably 20 mol% or less, based on the total molar amount of monomers constituting the cationic or amphoteric polyacrylamide resin. More preferably.
  • Polymerization of amphoteric or cationic polyacrylamide resins can be performed by various methods. For example, it can be obtained by charging the above-mentioned various monomers and water in a predetermined reaction vessel, adding a radical polymerization initiator, and heating with stirring.
  • the reaction temperature is preferably about 50 ⁇ 100 ° C.
  • the reaction time is preferably about 1 to 5 hours.
  • the reaction concentration (monomer concentration) is usually preferably about 10 to 40% by mass, but the polymerization can be performed even at a higher concentration.
  • Other charged method monomers simultaneous polymerization can be carried out by various methods such as continuous dropping polymerization.
  • radical polymerization initiator a radical polymerization initiator such as a persulfate such as potassium persulfate or ammonium persulfate or a combination of these with a reducing agent such as sodium bisulfite can be used.
  • An azo initiator may be used as the radical polymerization initiator.
  • the use amount of the radical polymerization initiator is preferably 0.05 to 2% by mass, more preferably 0.1 to 0.5% by mass, based on the total mass of the monomers.
  • Mannich organization, Hoffmann reaction, etc. are performed after manufacturing polyacrylamide or anionic polyacrylamide.
  • the content of the paper strength enhancer is 0.01 to 20 in terms of solid content with respect to 100 parts by mass of the fibrillated lyocell fiber in order to provide the coating suitability of the lithium ion battery substrate.
  • the amount is preferably mass parts, more preferably 0.1 to 5 mass parts.
  • the base material for a lithium secondary battery (15) in which the paper strength enhancer is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the fibrillated lyocell fiber has the required strength and uniformity as a base material. A surface is obtained, and it becomes a base material for a lithium ion battery in which the occurrence of paper breakage and wrinkles at the time of coating is suppressed and the coating suitability is improved.
  • the content of the paper strength enhancer is less than 0.01 parts by mass with respect to 100 parts by mass of the fibrillated lyocell fiber, the effect of improving the coating suitability may not be obtained. Moreover, when larger than 20 mass parts, uniformity may be lost by aggregation and coating suitability may fall. In addition, an increase in viscosity may impair manufacturing stability.
  • the paper strength enhancer can be added by a method of adding a nonwoven fabric (internal addition method) or a method of impregnating or coating a nonwoven fabric (external addition method). . Since the paper strength enhancer is uniformly mixed and the network of polymer chains can be stretched uniformly, it is easy to suppress the dropping of fibers and the like, and it is an internal addition method that can improve the uniformity of the entire substrate. Is preferred.
  • the substrate When the fibrillated heat-resistant fiber is further contained as an essential component as in the lithium secondary battery substrate (16) of the present invention, the substrate has small pores and is formed relatively uniformly. Therefore, the back-through of the coating liquid containing the filler particles is suppressed, and the filler particles are intensively laminated on the surface of the base material. Therefore, the surface smoothness of the coated surface is excellent, and an unnecessary gap is generated between the electrodes. Hateful. Further, since the back-through of the coating liquid is suppressed, the filler particles are not filled inside the base material and do not block the pores inside the base material, so that a separator having a high electrolytic solution retention rate can be obtained. it can. Since it contains fibrillated heat-resistant fibers, it has excellent heat resistance, the lithium secondary battery is internally short-circuited and generates heat, and even if the temperature rises, the separator does not melt or shrink.
  • lithium dendrite a phenomenon occurs in which metallic lithium is deposited on the surface of the negative electrode, and this deposit is called “lithium dendrite”. Lithium dendrite grows gradually, penetrates the separator and reaches the positive electrode, which may cause internal short circuit, but the separator and composite base material that have been used conventionally have large pores in the nonwoven fabric, There was also a problem that this internal short circuit was likely to occur.
  • the fibrillated heat-resistant fiber is rigid, so that penetration of lithium dendrite can be suppressed.
  • the fibrillated heat-resistant fiber which is an essential component constituting the base material for the lithium secondary battery of the present invention, includes wholly aromatic polyamide, wholly aromatic polyester, polyimide, polyamideimide, polyetheretherketone, polyphenylene sulfide, polybenzoe.
  • a fibrillated heat-resistant fiber made of imidazole, poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole, polytetrafluoroethylene, acrylic resin or the like is used.
  • para-type wholly aromatic polyamides and acrylic resins are particularly preferred because of their high thermal decomposition temperature, excellent heat resistance, and excellent compatibility with the electrolyte.
  • Acrylic resin is made of 100% acrylonitrile polymer, and acrylonitrile is copolymerized with (meth) acrylic acid derivatives such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, vinyl acetate, etc. And the like.
  • the mass% (acrylonitrile ratio) of acrylonitrile with respect to the polymerizable component in the acrylonitrile-based polymer constituting the fiber is preferably 40% by mass or more, and more preferably 50% by mass or more. More preferably, it is 88 mass% or more.
  • the fibrils of the fibrillated acrylonitrile fiber may become too thick, and it may be difficult to achieve the target degree of fibrillation.
  • the degree of fibrillation is preferably 0 to 500 ml, more preferably 0 to 400 ml, and even more preferably 0 to 300 ml in Canadian standard freeness as defined in JIS P8121. If it exceeds 500 ml, the fiber diameter distribution becomes wide, and there are cases where it becomes a textured spot or a thick spot, or there is a case where the coating liquid is breached.
  • the length weighted average fiber length of the fibrillated heat resistant fiber is preferably 0.2 to 2.0 mm, more preferably 0.3 to 1.5 mm, and further preferably 0.5 to 1.2 mm. If it is less than 0.2 mm, it may fall off from the substrate or the substrate may become fluffy, and if it is longer than 2.0 mm, it may become lumpy.
  • the fibrillated heat-resistant fiber not only improves the heat resistance of the substrate, but is more rigid than cellulose and other synthetic fibers, and therefore can suppress penetration of the substrate even when lithium dendrite is generated.
  • Heat-resistant fiber fibrillation consists of a heat-resistant fiber that is fixed to a refiner, beater, mill, milling device, rotary homogenizer that applies shearing force with a high-speed rotating blade, and circular-shaped inner blade that rotates at high speed.
  • Double-cylindrical high-speed homogenizer that generates shearing force between the blades, ultrasonic crusher that is refined by ultrasonic impact, and a pressure difference of at least 3000 psi is applied to the fiber suspension to pass through a small-diameter orifice. It is obtained by processing using a high-pressure homogenizer or the like that applies a shearing force or a cutting force to the fiber by causing a high speed and colliding with this to rapidly decelerate.
  • the content of the fibrillated heat-resistant fiber is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass.
  • the content of the fibrillated heat-resistant fiber is less than 5% by mass, the heat resistance and dendrite resistance of the substrate may be insufficient.
  • the content is more than 60% by mass, the substrate is likely to become fluffy. Occasionally, the fibers may fall off, fouling the rolls and hindering the coatability.
  • the nonwoven fabric may have a multilayer structure.
  • the fiber composition of each layer may be the same or different.
  • the basis weight of each layer can be lowered, so that the fiber concentration of the slurry can be lowered, so that the nonwoven fabric is better formed.
  • the synthetic resin short fibers and fibrillated lyocell
  • the entanglement with the fiber becomes complicated and uniform, and the denseness and uniformity of the base material are improved.
  • the paper making speed can be increased, and the operability is improved.
  • At least one layer may be a layer containing a synthetic resin short fiber and a fibrillated lyocell fiber as essential components.
  • the function can be separated by changing the fiber composition of each layer.
  • (A) it has a heat-resistant layer containing synthetic resin short fibers and fibrillated lyocell fibers as essential components, and a heat melting layer (B) containing synthetic resin short fibers and polyethylene synthetic pulp as essential components.
  • the fibrillated lyocell fiber is entangled with the synthetic resin short fiber
  • the polyethylene synthetic pulp is the synthetic resin short fiber.
  • the smoothness of both the front and back surfaces is high, the denseness is excellent, the variation of the surface when combined by surface coating is small, and it has sufficient surface strength, so the composite will fall off It becomes difficult.
  • the heat-melting layer (B) when the temperature inside the battery becomes around 130 ° C., it melts and closes the micropores, exhibits shutdown characteristics, and further rises in temperature due to some malfunction. Even when the temperature is close to 170 ° C., the separator does not shrink due to the effect of the heat-resistant layer (A). That is, the base material for a lithium ion secondary battery of the present invention has characteristics that the surface smoothness is higher, the denseness and uniformity are excellent, and the shutdown characteristics can be expressed while having heat resistance.
  • the mass ratio of the synthetic resin short fiber and the fibrillated lyocell fiber is preferably 95/5 to 20/80, and 90/10 to 30. / 70 is more preferable, and 70/30 to 40/60 is more preferable.
  • the content ratio of the fibrillated lyocell fiber is less than 5% by mass, sufficient heat resistance may not be obtained or the denseness and uniformity may not be improved.
  • the content ratio of the fibrillated lyocell fiber exceeds 80% by mass, the base material may be damaged during the formation of the composite.
  • the polyethylene-based synthetic pulp of the present invention refers to a pulp-like product produced from polyethylene as a raw material. Among them, a solution at a temperature higher than that of the raw material hydrocarbon solvent disclosed in Japanese Patent Publication No. 55-10683 is depressurized.
  • the surface of the synthetic pulp may be treated with polyvinyl alcohol.
  • Treatment with polyvinyl alcohol is preferably 0.5 to 3.0 mass% with respect to the emulsion solution of synthetic pulp, preferably is preferably carried out by adding 1.0 to 2.0 mass%, it added in other steps You may do it.
  • Polyvinyl alcohol hydrophilizes the polyethylene-based synthetic pulp and prevents the synthetic pulp from flocking during wet papermaking.
  • the content mass ratio of the synthetic resin short fiber and the polyethylene synthetic pulp is preferably 60/40 to 10/90, and 50/50 to 20 / 80 is more preferable, and 40/60 to 20/80 is more preferable.
  • the content ratio of the polyethylene-based synthetic pulp is less than 40% by mass, sufficient shutdown characteristics may not be exhibited, and the denseness and uniformity may not be improved. The substrate may be damaged.
  • the ratio of the heat-resistant layer of the lithium ion battery substrate of the present invention (A) and hot-melt layer (B) is preferably 20 / 80-80 / 20, more preferably 30 / 70-70 / 30, 40 / More preferably, it is 60-60 / 40.
  • the ratio of the heat-resistant layer (A) is less than 20% by mass, the heat resistance may be inferior.
  • the ratio of the heat-melted layer (B) is less than 20% by mass, a good shutdown may not occur. .
  • the minimum pore diameter is 0.10 ⁇ m or more and the maximum pore diameter is 20 ⁇ m or less.
  • the fibrillated lyocell fiber is entangled with the synthetic resin short fiber, this pore diameter can be achieved, it is excellent in denseness, and it is possible to suppress the exfoliation / dropping of composites such as filler particles and resin and the generation of pinholes.
  • the minimum pore diameter is more preferably 0.20 ⁇ m or more and the maximum pore diameter is more preferably 15 ⁇ m or less.
  • the ratio dmax / dave between the maximum pore diameter dmax ( ⁇ m) and the average pore diameter dave ( ⁇ m) is preferably 10 or less.
  • dmax / dave is 10 or less, the denseness and uniformity are excellent, and more excellent in the prevention of dropping off of composites and pinholes when composited by surface coating such as filler particles or resin. ing.
  • it is 8.0 or less.
  • dmax / dave is closer to 1.0, the variation in the pore diameter of the base material is less likely to vary, but a lower limit of dmax / dave is preferably about 2.0.
  • the minimum pore diameter, the maximum pore diameter, and the average pore diameter are specified in JIS K 3832, ASTM F316-86, and ASTM E1294-89.
  • a lyocell fiber with an increased fibrillation degree For example, in a double disc refiner (DDR), it is preferable to use one that has been beaten 50 times or more. It is also effective to set the content ratio of the fibrillated lyocell fiber to 5% by mass or more with respect to the total content of the synthetic resin short fiber and the fibrillated lyocell fiber.
  • the fineness of the synthetic resin short fiber is preferably 0.004 to 1.3 dtex. When the fineness of the synthetic resin short fiber exceeds 1.3 dtex, the maximum pore diameter may increase.
  • the center line average roughness Ra in the flow direction and the width direction is preferably 3.0 or less, and the variation in the surface when combined is reduced.
  • the value of Ra is more preferably 2.6 or less, and even more preferably 2.3 or less. Most preferably, it is 2.0 or less.
  • the same direction as the direction which a fiber web advances at the time of paper making with a paper machine be a flow direction, and let a perpendicular direction to a flow direction be a width direction.
  • the center line average roughness Ra was measured based on the method defined in JIS B 0601-1982.
  • the fineness of the synthetic resin short fiber is 1.3 dtex or less and the fiber length is 7 mm or less.
  • the content ratio of the fibrillated lyocell fiber is set to 5% by mass or more with respect to the total content of the synthetic resin short fiber and the fibrillated lyocell fiber.
  • the fineness of the synthetic resin short fiber exceeds 1.3 dtex, the unevenness becomes large, and the value of the center line average roughness Ra falls outside the preferable numerical range, and the surface when combined by surface coating is large.
  • it is also effective to set the fiber length of the synthetic resin short fibers to 10 mm or less.
  • the ratio of the tensile strength (MDs) in the flow direction to the tensile strength (CDs) in the width direction is not particularly limited, but is 0.5-8. It is preferably within the range of 0, and when (MDs / CDs) is within this range, the generation of wrinkles when combined with surface coating of filler particles, resin, etc., and the accompanying dropout of the composite are suppressed. can do.
  • (MDs / CDs) is more preferably 1.0 to 5.5, and still more preferably 1.0 to 3.0. Particularly preferred is 1.0 to 2.0.
  • (MDs / CDs) In order to set (MDs / CDs) to 0.5 to 8.0, for example, heat-fusible short fibers may be contained. High mechanical strength can be obtained by softening, melting or wet-heat-dissolving the heat-fusible short fibers by heating or wet heat heating, and heat-bonding the fibers to each other. Therefore, the value of (MDs / CDs) is 0. It tends to be 5 to 8.0, and the generation of wrinkles when combined by surface coating can be reduced. Moreover, since the value of (MDs / CDs) may become larger than 8.0 when the fiber length of the synthetic resin short fiber exceeds 7 mm, the fiber length of the synthetic resin short fiber is preferably 7 mm or less. .
  • the tensile strength is measured based on the method specified in JIS P 8113, and the ratio (MDs / CDs) of the tensile strength (MDs) in the flow direction and the tensile strength (CDs) in the width direction is based on the measurement result. Calculated.
  • the content ratio of the fibrillated lyocell fiber to the total content of the synthetic resin short fiber and the fibrillated lyocell fiber should be 5% by mass or more. It is valid. It is also effective to set the fiber length of the synthetic resin short fibers to 10 mm or less.
  • a paper strength enhancer not only can the tensile strength in the flow direction be improved, but also the tensile strength in the width direction can be greatly improved, and (MDs / CDs) can easily be kept within the preferred numerical range. Become.
  • Basis weight of the lithium secondary battery substrate is 3.0 preferably ⁇ 30.0 g / m 2, more preferably 6.0 ⁇ 20.0g / m 2, 8.0 ⁇ 12.0g / m 2 and more preferable.
  • the basis weight means a basis weight based on a method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
  • the thickness of the base material for a lithium secondary battery of the present invention is preferably 4 to 45 ⁇ m, more preferably 6 to 40 ⁇ m, and still more preferably 8 to 30 ⁇ m. If it exceeds 45 ⁇ m, the base material alone occupies the majority of the separator, and it becomes difficult to obtain the effect of the composite. If the thickness is less than 4 ⁇ m, the strength of the base material becomes too low, and the base material may be damaged when the base material is handled or combined, or the pore diameter may not be within the preferred range. In some cases, pinholes are likely to occur.
  • thickness means the value measured by the method prescribed
  • the density of the lithium secondary battery base material of the present invention is preferably 0.250 ⁇ 1.000g / cm 3, more preferably 0.400 ⁇ 0.800g / cm 3.
  • the coating liquid may be seen through, and when it exceeds 1.000 g / cm 3 , the resistance value of the separator may be increased.
  • the base material for a lithium secondary battery of the present invention as a method for producing a nonwoven fabric, a method of forming a fiber web and bonding, fusing, and entanglement of fibers in the fiber web can be used.
  • the obtained nonwoven fabric may be used as it is or may be used as a laminate comprising a plurality of sheets.
  • the method for producing the fiber web include a dry method such as a card method and an air array method, a wet method such as a papermaking method, a spunbond method, and a melt blow method.
  • the web obtained by a wet method is uniform and dense, and can be suitably used as a base material for a lithium secondary battery.
  • the fibers are uniformly dispersed in water to obtain a uniform papermaking slurry, and then passed through steps such as screen (removal of foreign matter, lump, etc.), and the final fiber concentration is 0.01 to 0.50% by weight. Adjusted to paper.
  • chemicals such as a dispersion aid, an antifoaming agent, a hydrophilic agent, and an antistatic agent may be added during the process.
  • a paper machine having at least one of a wire such as a circular net, a long net, and an inclined type can be used for the papermaking slurry.
  • a hydroentanglement method a needle punch method, a binder adhesion method, or the like can be used.
  • the wet method when used with emphasis on uniformity, it is preferable to include a heat-fusible short fiber and bond the heat-fusible short fiber by a binder bonding method.
  • a uniform nonwoven fabric is formed from a uniform web by the binder bonding method.
  • the wet nonwoven fabric thus manufactured may be subjected to heat treatment, calendar treatment, thermal calendar treatment, and the like. By these treatments, effects such as adjustment of thickness, uniformization, and strength improvement are obtained, and the value of Ra is easily kept within a preferable numerical range.
  • the maximum pore diameter and the average pore diameter can be controlled by a process such as a calendar, and as a result, dmax / dave can be easily kept within a preferable numerical range.
  • the pressure It is preferable to apply pressure.
  • the tension of the calendar it is possible to control the ratio of the tensile strength and keep (MDs / CDs) within a preferable numerical range.
  • the mechanical strength is preferably increased by heat treatment.
  • the heat treatment method include a heat treatment method using a heating device such as a hot air dryer, a heating roll, an infrared (IR) heater, or the like while continuously performing the heat treatment or pressurizing.
  • the heat treatment temperature is equal to or higher than the temperature at which the sheath portion of the core-sheath type heat-fusible short fiber melts or softens, and the core portion of the core-sheath type heat-fusible short fiber and other contained fibers melt, soften, or decompose. It is preferable that the temperature be less than the temperature.
  • wet-making method is a papermaking slurry in which fibers are dispersed in water to form a uniform papermaking slurry, and this papermaking slurry is made using a papermaking machine having at least two wires such as a circular net, a long net, and an inclined type. This is a method for obtaining a fibrous web.
  • a drying step is required to remove moisture, but when the base material for the lithium secondary battery has a hot melt layer (B), the polyethylene synthetic pulp is It is preferable to dry at a temperature at which the film is not completely formed (a temperature lower by 20 ° C. or more than the melting point) and a treatment time. When over-drying is performed, film formation of the polyethylene-based synthetic pulp is promoted too much, and an optimal void may not be obtained.
  • Non-fibrillar lyocell fiber (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) was repeatedly treated 50 times using a double disc refiner to produce fibrillated lyocell fiber 1.
  • the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This slurry for paper making is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 130 ° C., and unstretched polyethylene terephthalate (PET) heat-fusible short fibers are bonded to express nonwoven fabric strength. A 50 cm wide nonwoven fabric was produced.
  • PET polyethylene terephthalate
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • the base material for a lithium secondary battery obtained in the examples is composed of a nonwoven fabric containing synthetic resin short fibers and fibrillated lyocell fibers, and thus has a dense structure and is composited by surface coating. A good result was obtained that the variation of the surface was small.
  • Example 5 content of lyocell fibers to fibrillate is less than 5 wt%, Baratsuki surface, shedding was observed slightly larger tendency.
  • Example 12 in which the content of fibrillated lyocell fiber exceeded 80% by mass the strength tended to decrease slightly.
  • Examples 14-17, 28, Comparative Examples 7-9, Examples 32-36 According to the number of blending parts shown in Table 3, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, both surfaces were brought into contact with a metal roll heated to 210 ° C. and heat-treated, and further, supercalendering was performed to obtain a lithium secondary battery substrate.
  • Examples 18-27, 29-31, Comparative Example 10 According to the number of blending parts shown in Table 3, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • Basis material density The basis weight was measured according to JIS P 8124, and the density was determined by dividing by the thickness measured by the above method.
  • the coating rate (%). The greater the area that could not be coated due to cutting or tearing of the substrate, the smaller the coating rate.
  • the separator was cut to 100 mm width ⁇ 100 mm, immersed in the electrolyte solution for 1 minute, suspended for 1 minute to cut off the excess electrolyte solution, and the mass W1 of the separator was measured. The value obtained by subtracting the mass W0 of the separator before holding the electrolytic solution from W1 and dividing the value W2 by W0 and multiplying by 100 was defined as the electrolytic solution retention rate (%).
  • the electrolytic solution a mixed solution in which 1 mol / l of LiPF 6 was dissolved was used as the electrolytic solution. The mixed solution is ethylene carbonate and diethyl carbonate in a mass ratio of 3: 7.
  • the base materials for lithium secondary batteries of Examples 14 to 31 are fibrillated lyocell fibers having a modified freeness of 0 to 250 ml and a length weighted average fiber length of 0.20 to 2.00 mm. Since it consists of a wet nonwoven fabric containing synthetic resin short fibers, the back-through of the coating liquid containing filler particles is suppressed, the surface smoothness of the coated surface is good, and the electrolyte solution retention is high.
  • the base materials for lithium secondary batteries of Comparative Examples 7 to 9 are fibrillated lyocell having a modified freeness of 0 to 250 ml and a length-weighted average fiber length of 0.20 to 2.00 mm. Since it is composed only of synthetic resin short fibers without containing fibers, the coating liquid containing filler particles is broken through, causing problems in the coating operation, and the surface smoothness of the coated surface is poor. Further, the filler particles were filled in the base material, and the pores inside the base material were closed, so that the electrolyte solution retention rate was poor.
  • the base material for the lithium secondary battery of Example 32 contains fibrillated lyocell fiber having a modified freeness of 0 to 250 ml and a length-weighted average fiber length of 0.20 to 2.00 mm.
  • the modified freeness is 33 ml and the weight-weighted average fiber length is 0.17 mm, the fibrillated lyocell fiber tends to fall off.
  • Some penetration of the liquid occurred, and the surface smoothness of the coated surface was slightly inferior to Examples 14 to 31.
  • the filler particles are filled in the substrate, since the pores of the inner substrate becomes closed slightly, as compared with Examples 14-31, the electrolyte solution retention was slightly low.
  • the base material for the lithium secondary battery of Example 33 contains fibrillated lyocell fiber having a modified freeness of 0 to 250 ml and a length-weighted average fiber length of 0.20 to 2.00 mm.
  • fibrillated lyocell fibers having a modified freeness of 45 ml and a length-weighted average fiber length of 2.16 mm uneven formation occurs, which is compared with Examples 14 to 31.
  • the surface smoothness of the coated surface was poor.
  • the base material for the lithium secondary battery of Example 34 does not contain fibrillated lyocell fibers having a modified freeness of 0 to 250 ml and a length-weighted average fiber length of 0.20 to 2.00 mm. Since the modified lyocell fiber has a modified freeness of 255 ml and a weight-weighted average fiber length of 0.19 mm, it contains 90% by mass of the fibrillated lyocell fiber. Cutting and tearing occurred during the work, and compared with Examples 14 to 31, the coating rate was poor.
  • the base material for a lithium secondary battery of Example 35 does not contain fibrillated lyocell fibers having a modified freeness of 0 to 250 ml and a length-weighted average fiber length of 0.20 to 2.00 mm. Since the modified freeness is 257 ml and 90% by mass of the fibrillated lyocell fiber having a length-weighted average fiber length of 1.63 mm is contained, uneven formation occurs, and the modified freeness is 0 to The surface smoothness of the coated surface is worse than in Examples 26 and 27 containing 90% by mass of fibrillated lyocell fiber having a weight weighted average fiber length of 0.20 to 2.00 mm at 250 ml, and the electrolyte solution The retention rate was low.
  • the base material for a lithium secondary battery of Example 36 does not contain fibrillated lyocell fibers having a modified freeness of 0 to 250 ml and a length-weighted average fiber length of 0.20 to 2.00 mm.
  • the modified freeness is 260 ml and 90% by mass of the fibrillated lyocell fiber having a length weighted average fiber length of 2.11 mm is contained, the formation unevenness is further increased than in Examples 34 and 35. The surface smoothness of the coated surface was worse.
  • the base material for a lithium secondary battery of Comparative Example 10 is a fibrillated lyocell fiber having no synthetic resin short fiber, a modified freeness of 107 ml, and a length-weighted average fiber length of 1.22 mm. Since the piercing strength was weak and it was torn during coating, the coating rate was poor.
  • fibrillated lyocell fibers 1A to 1L were prepared by processing fibrillar lyocell single fibers (fiber diameter: 12 ⁇ m, fiber length: 6 mm, manufactured by Coatles) using a double disc refiner.
  • Examples 37-52, Comparative Example 11 According to the number of parts shown in Table 6, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 130 ° C., unstretched PET-based heat-fusible short fibers are bonded to develop a nonwoven fabric strength, and the width is 50 cm. A non-woven fabric was prepared. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Comparative Example 12 According to the number of parts shown in Table 6, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • the base materials for lithium secondary batteries obtained in Examples 37 to 50 are composed of a nonwoven fabric containing synthetic resin short fibers and fibrillated lyocell fibers.
  • the fiber length distribution histogram of fibrillated lyocell fibers 0.
  • the ratio of fibers having a maximum frequency peak between 00 and 1.00 mm and having a fiber length of 1.00 mm or more is 10% or more, it has a dense structure and is combined by surface coating. A good result was obtained that the variation of the surface of the film was small.
  • Example 47 when the content of the fibrillated lyocell fiber is 5 to 80% by mass, the surface variation when combined by surface coating is small, the strength is high, and the porosity is No membrane loss was observed.
  • Example 47 in which the content of the fibrillated lyocell fiber was 5% by mass, the surface variation tended to be slightly increased.
  • Example 50 the content of lyocell fibers fibrillated exceeds 80 wt%, a strength tends to decrease slightly observed.
  • the base material for a lithium secondary battery obtained in Comparative Example 12 does not contain synthetic resin short fibers, the strength is low, and the degree of dropout of the porous film is larger than that in Examples 37 to 50. .
  • the maximum frequency peak in the fiber length distribution histogram is out of the range of 0.0 to 1.0 mm.
  • the degree of dropping off of the membrane was also greater than in Examples 37-50.
  • the base material for a lithium secondary battery obtained in Example 52 has a low strength because the proportion of fibers having a fiber length of 1.0 mm or more is less than 10%, and the degree of dropping of the porous membrane is also carried out. Results were greater than Examples 37-50.
  • the fibrillated lyocell fibers 2A to 2K were prepared by treating unfibrillated lyocell single fibers (fiber diameter: 12 ⁇ m, fiber length: 6 mm, manufactured by Coatles Co., Ltd.) using a double disc refiner.
  • Examples 53 to 67, Comparative Example 13 According to the number of parts shown in Table 9, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 130 ° C., unstretched PET-based heat-fusible short fibers are bonded to develop a nonwoven fabric strength, and the width is 50 cm. A non-woven fabric was prepared.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Comparative Example 14 According to the number of parts shown in Table 9, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • the base materials for lithium secondary batteries obtained in Examples 53 to 65 have a maximum frequency peak between 0.00 and 1.00 mm in the fiber length distribution histogram, and have a fiber length of 1.00 mm or more. Since the ratio of the fibers was 50% or more, a good result was obtained that the structure had a dense structure and the surface variation when combined by surface coating was small.
  • Example 62 when the content of the fibrillated lyocell fiber was 5 to 80% by mass, the strength was high and the removal of the porous membrane was not confirmed.
  • Example 62 in which the content of fibrillated lyocell fiber was 5% by mass, the tendency of the porous membrane to drop off was slightly deteriorated.
  • Example 65 the content of lyocell fibers fibrillated exceeds 80 wt%, a strength tends to decrease slightly observed.
  • the base material for a lithium secondary battery obtained in Comparative Example 14 did not contain synthetic resin short fibers, so the strength was low, and the degree of dropout of the porous membrane was greater than that in Examples 53 to 65. .
  • Example 66 since the maximum frequency peak in the fiber length distribution histogram deviates from between 0.00 to 1.00 mm, surface variation occurs, and the porous The degree of dropping off of the membrane was also greater than in Examples 53-65.
  • the base material for a lithium secondary battery obtained in Example 67 has a low strength because the proportion of fibers having a fiber length of 1.00 mm or more is less than 50%, and the degree of dropping of the porous membrane is also carried out. Results were greater than Examples 53-65.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 60 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC1”.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 75 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC2”.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 110 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC3”.
  • Examples 68, 70, 72, 73, 76-81, Comparative Example 15 In accordance with the number of parts shown in Table 11, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 120 ° C., and heat-bondable short fibers are bonded by heat or wet heat to develop non-woven fabric strength. A non-woven fabric was prepared. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 69 In accordance with the number of parts shown in Table 11, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 120 ° C., heat-bondable short fibers are thermally bonded to develop a nonwoven fabric strength, and a 50 cm wide nonwoven fabric is produced. Produced.
  • the nonwoven fabric was brought into contact with a heat roll having a diameter of 1.2 m heated to 200 ° C. at a speed of 20 m / min and heat-treated.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 71 In accordance with the number of parts shown in Table 11, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 120 ° C., heat-bondable short fibers are thermally bonded to develop a nonwoven fabric strength, and a 50 cm wide nonwoven fabric is produced. Produced.
  • a heat roll having a diameter of 1.2 m heated to 75 ° C. was subjected to pressure heat treatment at a pressure of 196 N / cm 2 and a speed of 10 m / min to obtain a base material for a lithium secondary battery.
  • Examples 74, 75, 84, 85, Comparative Example 18 In accordance with the number of parts shown in Table 11, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry is made up by a wet method using a circular paper machine, dried by a cylinder dryer at 140 ° C., heat-bondable short fibers are thermally bonded to develop a nonwoven fabric strength, and a 50 cm wide nonwoven fabric is produced. Produced. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 82 Comparative Examples 16 and 19
  • the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry was made up by a wet method using a circular paper machine and dried by a cylinder dryer at 110 ° C. without thermally bonding the heat-fusible short fibers to produce a 50 cm wide nonwoven fabric.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 83 Comparative Example 17
  • the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry was made up by a wet method using a circular paper machine and dried by a cylinder dryer at 110 ° C. without thermally bonding the heat-fusible short fibers to produce a 50 cm wide nonwoven fabric.
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • Test strength of substrate Five or more substrates were cut and arranged in a strip shape having a width of 50 mm and a length of 200 mm. The test piece is sandwiched at 100 mm intervals between sample ends with a sample knob of a desktop material testing machine (trade name: STA-1150, manufactured by Orientec Co., Ltd.), and the upper end is cut at a constant speed of 100 mm / min. The maximum load at this time was measured, this was taken as the tensile strength, and evaluated according to the following criteria.
  • thickness means the value measured by the method prescribed
  • the base materials for lithium secondary batteries prepared in Examples 68 to 81 contain the synthetic resin short fibers and the fibrillated lyocell fibers as essential components, and as at least one kind of the synthetic resin short fibers, a heat fusion component and Because it consists of a non-woven fabric containing core-sheath-type heat-fusible short fibers made of non-heat-sealing components, it forms a dense structure and the fibers are thermally bonded without damaging the structure. Good results were obtained in that the surface variation when composited by surface coating was small. Moreover, the mechanical strength was high, the heat shrinkage was small at 150 ° C., and the thermal dimensional stability was excellent.
  • the base material for a lithium secondary battery produced in Example 82 and Comparative Example 19 was somewhat inferior in the result of the friction test as compared with Examples 68 to 81 because the fibers were not thermally bonded. It was. Therefore, the surface coating of when fibers fall off or of the fuzz is generated, rose with the surface has become to become a result larger. Also, the mechanical strength was low.
  • the base materials for lithium secondary batteries of Examples 83 to 85 manufactured using unstretched polyethylene terephthalate short fibers or polyolefin-based split composite fibers as the heat-fusible short fibers were heat-fusible during heat-sealing. Loss of the fiber shape of the short fibers resulted in a decrease in the density of the base material, resulting in a slightly larger variation in the surface when combined by surface coating than in Examples 68-81. .
  • Non-fibrillar lyocell fiber (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) was repeatedly treated 75 times using a double disc refiner to produce fibrillated lyocell fiber 2.
  • Example 86 Add a paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin to the pulper to add 2 parts to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • a paper strength enhancer made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250
  • Example 87 A paper strength enhancer of cationic polyacrylamide resin (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 705) is added to the pulper so that it becomes 2 parts per 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Polystron registered trademark
  • Example 88 After adding and dispersing a cationic starch-based paper strength enhancer (trade name: DD4280, manufactured by Seiko PMC Co., Ltd.) to pulper so as to be 2 parts with respect to 100 parts of fibrillated lyocell fiber, Table 13 shows. According to the number of blending parts, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. The papermaking slurry was made up using a wet method using a circular paper machine and dried with a cylinder dryer at 120 ° C. to produce a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • a cationic starch-based paper strength enhancer trade name: DD4280, manufactured by Seiko PMC Co., Ltd.
  • Example 89 The composition shown in Table 13 was added to the pulper after adding and dispersing the guar gum paper strength enhancer (trade name: Mayproid 2066, manufactured by Mayhall Chemical Co., Ltd.) to 100 parts of fibrillated lyocell fiber. According to the number of parts, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • the guar gum paper strength enhancer trade name: Mayproid 2066, manufactured by Mayhall Chemical Co., Ltd.
  • Example 90 Alpha pulped potato starch strength enhancer (manufactured by Shikishima Starch Co., Ltd., trade name: Mermaid (registered trademark) M-300) was added to the pulper and dispersed to 100 parts of fibrillated lyocell fiber. Thereafter, the raw materials were mixed together in accordance with the number of blending parts shown in Table 13, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Mermaid registered trademark
  • Example 91 An acrylic ester latex paper strength enhancer (manufactured by Nippon Zeon Co., Ltd., trade name: Nipol (registered trademark) Lx854E) was added to the pulper so as to be 2 parts per 100 parts of fibrillated lyocell fiber and dispersed. Thereafter, the raw materials were mixed together in accordance with the number of blending parts shown in Table 13, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. The papermaking slurry was made up using a wet method using a circular paper machine and dried with a cylinder dryer at 120 ° C. to produce a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Nipol registered trademark
  • Example 92 Paper strength enhancer of amphoteric polyacrylamide resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1810) is added to the pulper so as to be 1.5 parts with respect to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. 0.5 parts relative to 100 parts of lyocell fiber fibrillated with amphoteric polyacrylamide resin paper strength enhancer (trade name: Polystron (registered trademark) 1280) in the pipe before the circular net It added so that it might become.
  • Polystron registered trademark
  • This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 93 After adding and dispersing a cation starch (trade name: DD4280 manufactured by Seiko PMC Co., Ltd.) to the pulper so as to be 1.5 parts with respect to 100 parts of the fibrillated lyocell fiber, according to the number of parts shown in Table 13, The raw materials were mixed together and disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. 0.5 parts relative to 100 parts of lyocell fiber fibrillated with amphoteric polyacrylamide resin paper strength enhancer (trade name: Polystron (registered trademark) 1280) in the pipe before the circular net It added so that it might become.
  • amphoteric polyacrylamide resin paper strength enhancer trade name: Polystron (registered trademark) 1280
  • the papermaking slurry was made up using a wet method using a circular paper machine and dried with a cylinder dryer at 120 ° C. to produce a nonwoven fabric.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 94 A paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) made of amphoteric polyacrylamide resin is added to the pulper so as to be 0.01 part with respect to 100 parts of lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Polystron registered trademark
  • Example 95 Paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin is added to the pulper so that it becomes 0.1 part with respect to 100 parts of lyocell fiber.
  • the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • the papermaking slurry was made up using a wet method using a circular paper machine and dried with a cylinder dryer at 120 ° C. to produce a nonwoven fabric.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 96 A paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin is added to the pulper so that it becomes 1 part with respect to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Polystron registered trademark
  • Example 97 A paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin is added to the pulper so that it becomes 5 parts with respect to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Polystron registered trademark
  • Example 98 A paper strength enhancer of an amphoteric polyacrylamide resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) is added to the pulper so as to be 10 parts with respect to 100 parts of the fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • an amphoteric polyacrylamide resin manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250
  • Example 99 A paper strength enhancer of an amphoteric polyacrylamide resin (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) is added to the pulper so that it becomes 20 parts with respect to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • an amphoteric polyacrylamide resin made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250
  • Example 100 A paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin is added to the pulper so that it becomes 25 parts with respect to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Polystron registered trademark
  • Example 101 According to the number of parts shown in Table 13, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. After making this papermaking slurry by a wet method using a circular paper machine, an amphoteric polyacrylamide resin paper strength enhancer (trade name: Polystron (registered trademark) 1250, manufactured by Arakawa Chemical Industries, Ltd.) A diluted solution prepared so as to be 2 parts per 100 parts of fibrillated lyocell fiber was sprayed and dried by a cylinder dryer at 120 ° C. to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • an amphoteric polyacrylamide resin paper strength enhancer trade name: Polystron (registered trademark) 1250, manufactured by Arakawa Chemical Industries, Ltd.
  • a diluted solution prepared so as to be 2 parts per 100 parts of fibrillated lyocell fiber was sprayed and dried
  • Examples 102-104 Add a paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin to the pulper to add 2 parts to 100 parts of fibrillated lyocell fiber. After the dispersion, the raw materials were mixed together according to the number of blending parts shown in Table 13, disintegrated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. The papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • a paper strength enhancer made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250
  • Examples 105 to 108, Comparative Example 20 According to the number of parts shown in Table 13, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • the papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to prepare a nonwoven fabric.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Comparative Example 21 100 parts of fibrillated lyocell fiber 2 was disaggregated in pulper water, and a uniform papermaking slurry (2% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried with a cylinder dryer at 110 ° C. to produce a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Comparative Example 22 A paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of an amphoteric polyacrylamide resin is added to the pulper so as to be 2 parts with respect to 100 parts by mass of the PET fiber. After that, according to the number of blending parts shown in Table 13, the raw materials were mixed together, disaggregated in the pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to prepare a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • a paper strength enhancer made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250
  • Comparative Example 23 Add a paper strength enhancer (made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250) of amphoteric polyacrylamide resin to the pulper to add 2 parts to 100 parts of fibrillated lyocell fiber. After dispersion, 100 parts of fibrillated lyocell fiber 2 was disaggregated in pulper water, and a uniform papermaking slurry (2% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried with a cylinder dryer at 110 ° C. to produce a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • a paper strength enhancer made by Arakawa Chemical Industry Co., Ltd., trade name: Polystron (registered trademark) 1250
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • Test strength of substrate Five or more substrates were cut and arranged in a strip shape having a width of 50 mm and a length of 200 mm. The test piece is sandwiched at 100 mm intervals between sample ends with a sample knob of a desktop material testing machine (trade name: STA-1150, manufactured by Orientec Co., Ltd.), and the upper end is cut at a constant speed of 100 mm / min. The maximum load at this time was measured, this was taken as the tensile strength, and evaluated according to the following criteria.
  • the base materials for lithium secondary batteries obtained in Examples 86 to 104 are composed of a nonwoven fabric containing synthetic resin short fibers, fibrillated lyocell fibers, and a paper strength enhancer. It is possible to suppress fuzz and fiber dropping due to friction during coating. For this reason, it has become possible to obtain a highly uniform separator that is excellent in surface smoothness and that does not easily cause the porous film to fall off. In addition to improving the coating suitability, the tensile strength was also improved. From Examples 86 to 91, those using synthetic polymers, semi-synthetic polymers, vegetable gums, and starches as paper strength enhancers have coating suitability such as coating smoothness, removal of porous membranes and wear resistance. Although improvement and improvement in tensile strength were observed, more favorable results were obtained when amphoteric or cationic polyacrylamide resins were used.
  • Example 86 and Examples 94 to 100 when the content of the paper strength enhancer is 0.01 to 20 parts by mass with respect to 100 parts of the fibrillated lyocell fiber, fiber aggregation hardly occurs, and the paper strength Since the network between fibers by the enhancer is sufficiently widened, fiber dropping and fluffing are suppressed, and a highly uniform surface can be obtained when combined. Also, the tensile strength was improved. From Example 86 and Examples 95 to 97, when 0.1 to 5 parts by mass of a paper strength enhancer was added to 100 parts of fibrillated lyocell fiber, the tensile strength was further strong and the wear resistance was excellent. A substrate could be obtained.
  • Comparative Examples 21 and 23 do not contain synthetic resin short fibers, the fibrillated lyocell fibers are partially taken up by the net, and the surface smoothness is low.
  • Comparative Examples 20 and 22 did not contain fibrillated lyocell fiber, the denseness was low and the surface smoothness was low, so the surface variation when combined was large. Further, in Comparative Example 20 which did not contain fibrillated lyocell fiber, the paper strength enhancer could not adsorb with fibrillated lyocell fiber, and no increase in tensile strength was observed as compared with Comparative Example 22.
  • Examples 105 to 108 did not contain a paper strength enhancer, the degree of suppression of fiber dropout and fluffing was slightly inferior, and fiber dropout seemed to occur during compounding. Examples 105 to 108 were slightly inferior in tensile strength and wear resistance as compared with Examples 86 and 102 to 104.
  • Examples 109-116, 119-127, 129-140, Comparative Examples 24, 28, 32 According to the number of blending parts shown in Table 15, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, both surfaces were brought into contact with a metal roll heated to 210 ° C., heat-treated, and further subjected to supercalendering to obtain a lithium secondary battery substrate.
  • Examples 117, 118, 128, Comparative Examples 25, 26, 29, 30, 33-36 According to the number of blending parts shown in Table 15, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 120 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Comparative Example 27 According to the number of parts shown in Table 15, the raw material was disaggregated in the water of a pulper, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. The papermaking slurry was made by a wet method using a circular paper machine, but the base material could not be prepared because the fibrillated wholly aromatic polyamide fiber had no binding force.
  • Comparative Example 31 According to the number of parts shown in Table 15, the raw material was disaggregated in the water of a pulper, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. The papermaking slurry was made by a wet method using a circular paper machine, but the base material could not be produced because the fibrillated acrylamide fiber had no binding force.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • the base material was cut into 200 mm width ⁇ 200 mm length, and allowed to stand in a constant temperature dryer at 200 ° C. for 3 hours, the shrinkage in the width direction and the length direction was calculated, and the average value was shown.
  • the positive electrode used was an aluminum current collector coated with a slurry prepared by mixing lithium cobaltate as an active material, acetylene black as a conductive additive, and polyvinylidene fluoride as a binder at a mass ratio of 90: 5: 5. .
  • a mixed solution in which 1 mol / l of LiPF 6 was dissolved was used as the electrolytic solution.
  • the mixed solution is ethylene carbonate and diethyl carbonate in a mass ratio of 3: 7.
  • the separator was cut to 100 mm width ⁇ 100 mm, immersed in the electrolyte solution for 1 minute, suspended for 1 minute to cut off the excess electrolyte solution, and the mass W1 of the separator was measured. The value obtained by subtracting the mass W0 of the separator before holding the electrolytic solution from W1 and dividing the value W2 by W0 and multiplying by 100 was defined as the electrolytic solution retention rate (%).
  • the electrolytic solution a mixed solution in which 1 mol / l of LiPF 6 was dissolved was used as the electrolytic solution. The mixed solution is ethylene carbonate and diethyl carbonate in a mass ratio of 3: 7.
  • the base materials for lithium secondary batteries of Examples 109 to 127 and 130 to 140 are made of wet nonwoven fabric containing fibrillated heat resistant fibers, synthetic resin short fibers, and fibrillated lyocell fibers, heat resistance and dendrite resistance
  • the coating solution containing the filler particles was prevented from seeping through, the surface smoothness of the coated surface was good, and the electrolyte solution retention rate was high.
  • the base materials for lithium secondary batteries of Examples 113 and 134 are fibrillated heat-resistant fibers that are fibrillated wholly aromatic polyamide fibers or fibrillated acrylic fibers. The heat resistance was superior to the base materials for lithium secondary batteries of Examples 114 to 116 using the above fibrillated heat resistant fiber.
  • the base materials for lithium secondary batteries of Comparative Examples 24 and 28 do not contain fibrillated lyocell fibers, and are composed only of fibrillated heat-resistant fibers and synthetic resin short fibers, and thus have good heat resistance and dendrite resistance.
  • the surface of the substrate was fuzzy, which hindered coating properties. The smoothness of the coated surface was poor due to the fuzz of the surface.
  • the base materials for lithium secondary batteries of Comparative Examples 25 and 29 do not contain synthetic resin short fibers and consist only of fibrillated heat-resistant fibers and fibrillated lyocell fibers, heat resistance, electrolyte solution retention, and dendrite resistance Although its properties were good, it was easy to break during coating, which hindered coating properties.
  • the base materials for lithium secondary batteries of Comparative Examples 26 and 30 do not contain synthetic resin short fibers and fibrillated lyocell fibers, and consist only of fibrillated heat resistant fibers and natural pulp, they have good dendrite resistance, It was easy to break at the time of coating, and it hindered coating properties. Since natural pulp proportion of thick fibers diameter is large, it is uneven on the substrate surface, resulting in poor surface smoothness of the coated surface.
  • Comparative Examples 27 and 31 attempted to produce a base material for a lithium secondary battery using only fibrillated heat-resistant fibers. However, since the fibers do not have a binding force, a base material for a lithium secondary battery cannot be produced. There wasn't.
  • the base materials for lithium secondary batteries of Comparative Examples 32 and 33 do not contain fibrillated heat-resistant fibers and fibrillated lyocell fibers, and are composed of only synthetic resin short fibers, they have heat resistance and dendrite resistance. was inferior, strike the coating liquid containing the filler particles is caused, resulting in poor surface smoothness of the coated surface. Further, the filler particles were filled in the base material, and the pores inside the base material were closed, so that the electrolyte solution retention rate was extremely poor.
  • the base material for a lithium secondary battery of Example 128 does not contain fibrillated heat-resistant fibers and consists only of synthetic resin short fibers and fibrillated lyocell fibers, it is compared with Examples 109 to 127 and 130 to 140.
  • the heat resistance and dendrite resistance were slightly inferior, and there was a case where the coating was broken at the time of coating, and the coating property was slightly inferior.
  • the base material for the lithium secondary battery of Comparative Example 34 does not contain fibrillated heat-resistant fibers and fibrillated lyocell fibers, and is composed only of synthetic resin short fibers and natural pulp, and therefore has poor heat resistance and dendrite resistance. It was. Since natural pulp has a large proportion of thick fiber diameters, the substrate has irregularities, the surface smoothness of the coated surface is poor, and the electrolyte retention rate is poor.
  • the base material for a lithium secondary battery of Comparative Example 35 does not contain fibrillated heat-resistant fibers and synthetic resin short fibers, and consists only of fibrillated lyocell fibers, and therefore has poor heat resistance and dendrite resistance. It was easy to break at the time of construction, and it hindered coating properties.
  • the base material for the lithium secondary battery of Comparative Example 36 does not contain fibrillated heat-resistant fibers and synthetic resin short fibers, and consists of fibrillated lyocell fibers and natural pulp, so that heat resistance and dendrite resistance are inferior. It was easy to break at the time of coating, and the coating property was hindered. Since natural pulp has a large proportion of thick fiber diameters, the substrate was uneven, and the surface smoothness of the coated surface was poor.
  • the modified freeness of the fibrillated lyocell fiber exceeded 250 ml, so that the beating was insufficient and many thick fibers remained, and the thickness unevenness The surface smoothness of the coated surface was poor.
  • Non-fibrillated lyocell fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 110 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC4”.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 60 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC5”.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 75 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC6”.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 50 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC7”.
  • Non-fibrillar lyocell single fibers (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) were repeatedly treated 40 times using a double disc refiner to produce fibrillated lyocell fibers. This is expressed as “FBC8”.
  • Examples 141-143, 145-147, 149-153, Comparative Examples 37, 39-42 In accordance with the number of parts shown in Table 17, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This papermaking slurry is made up by a wet method using a circular paper machine, and unstretched PET-based heat-fusible short fibers are adhered by a cylinder dryer at 130 ° C. to develop a nonwoven fabric strength, and a nonwoven fabric having a width of 50 cm. Was made.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Examples 144 and 148, Comparative Example 38 In accordance with the number of parts shown in Table 17, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • the base materials for lithium secondary batteries obtained in Examples 141 to 151 are made of a nonwoven fabric containing synthetic resin short fibers and fibrillated lyocell fibers, have a minimum pore diameter of 0.10 ⁇ m or more, and a maximum Since the pore diameter was 20 ⁇ m or less, a good result was obtained that the structure had a dense structure and the surface variation when combined by surface coating was small.
  • Example 141, 144, 145, 147, and 148 when the content of the fibrillated lyocell fiber is 5 to 80% by mass, the surface variation when combined by surface coating is small and the strength is high. Also, no loss of the porous membrane was confirmed. In Example 147 in which the content of the fibrillated lyocell fiber is less than 5% by mass, the surface variation tends to increase. In Example 148 in which the content of the fibrillated lyocell fiber exceeded 80% by mass, the strength tended to decrease slightly.
  • the resin constituting the synthetic resin short fiber was a polyester resin, an acrylic resin, or a polyolefin resin.
  • the variation was small, the strength was high, and no loss of the porous membrane was confirmed.
  • the base material for lithium secondary battery obtained in Comparative Example 38 does not contain synthetic resin short fibers, and the minimum pore diameter is smaller than 0.10 ⁇ m, so that the strength is low and the degree of dropping of the porous film is also low.
  • the results were larger than those of Examples 141 to 153.
  • Example 153 contains synthetic resin short fibers and fibrillated lyocell fibers, the minimum pore diameter is smaller than 0.10 ⁇ m. Also, the degree of dropout was larger than that of Examples 141-151.
  • the base materials for lithium secondary batteries obtained in Comparative Example 37, Example 152, and Comparative Examples 40 to 42 have a maximum pore diameter larger than 20 ⁇ m, so that surface variation occurs and the strength is low.
  • the degree of dropout and the occurrence of pinholes were also larger than those of Examples 141-151.
  • Non-fibrillated lyocell single fiber (fiber diameter 15 ⁇ m, fiber length 4 mm, manufactured by Coatles Co., Ltd.) was repeatedly treated 50 times using a double disc refiner to produce fibrillated lyocell fiber 3.
  • Examples 154 to 159, 161 to 165, Comparative Examples 43, 45 to 48 According to the number of blending parts shown in Table 19, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry is made up by a wet method using a circular paper machine, and unstretched PET-based heat-fusible short fibers are adhered by a cylinder dryer at 130 ° C. to develop a nonwoven fabric strength, and a nonwoven fabric having a width of 50 cm. Was made. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Comparative Example 44 According to the number of blending parts shown in Table 19, the raw materials were mixed, disaggregated in the pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. This papermaking slurry was made up by a wet method using a circular paper machine and dried by a 130 ° C. cylinder dryer to produce a 50 cm wide nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Example 160 According to the number of blending parts shown in Table 19, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator.
  • This slurry for paper making is made up using a wet method using a circular paper machine, dried by a cylinder dryer at 120 ° C., the PET core-sheath type heat-fusible short fibers are thermally bonded, and the nonwoven fabric strength is expressed.
  • a nonwoven fabric having a width of 50 cm was produced.
  • the nonwoven fabric was brought into contact with a heat roll having a diameter of 1.2 m heated to 200 ° C. at a speed of 20 m / min and heat-treated.
  • a super calendar process was performed to obtain a base material for a lithium secondary battery.
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • the base materials for lithium secondary batteries obtained in Examples 154 to 163 are composed of a nonwoven fabric containing synthetic resin short fibers and fibrillated lyocell fibers, and have a centerline roughness Ra of 3. Since it was 0 or less, it had a dense structure, and a good result was obtained that the variation in the surface when composited by surface coating was small.
  • Example 159 when the content of the fibrillated lyocell fiber is 5 to 80% by mass, the surface variation when combined by surface coating is small, the strength is high, and the porous membrane No dropout was confirmed.
  • Example 159 in which the content of the fibrillated lyocell fiber was less than 5% by mass, there was a tendency for the surface variation to increase and the loss of the porous membrane.
  • Example 158 in which the content of the fibrillated lyocell fiber exceeded 80% by mass, the strength tended to decrease slightly.
  • the base materials for lithium secondary batteries obtained in Comparative Examples 43 and 45 to 47 do not contain fibrillated lyocell fibers, and the center line average roughness Ra is larger than 3.0, so the surface variation is large. There occurs, the strength is low, dropping degree of the porous membrane also became examples 154-163 larger results.
  • the base materials for lithium secondary batteries obtained in Examples 164 and 165 contain synthetic resin short fibers and fibrillated lyocell fibers, the center line average roughness Ra is larger than 3.0. dropping the degree of variation or a porous film on the surface becomes examples 154-163 larger results.
  • the base material for lithium secondary batteries obtained in Comparative Example 48 has a center line average roughness Ra of 3.0 or less in the flow direction and the width direction, it does not contain fibrillated lyocell fibers, The degree of dropout of the porous membrane was also higher than that of Examples 154 to 165.
  • a fibrillated lyocell fiber 4 was obtained by repeatedly treating a fibrillated lyocell single fiber (fiber diameter: 15 ⁇ m, fiber length: 4 mm, manufactured by Coatles Co., Ltd.) 50 times using a double disc refiner.
  • a fibrous material obtained by flash spinning from polyethylene is dispersed at a concentration of 2% by mass, and the obtained dispersion is charged into a homogenizer (trade name: 15M-8TA, manufactured by Gaulin) at room temperature.
  • a homogenizer (trade name: 15M-8TA, manufactured by Gaulin) at room temperature.
  • a polyethylene standard synthetic pulp having a Canadian standard freeness of 200 ml and a fiber length of 0.7 mm was obtained by passing 30 times under a pressure of 5 MPa. The average fiber diameter was measured by microscopic observation, and the average fiber length was measured according to TAPPI T232hm-85.
  • Examples 166 to 179, 184, Comparative Examples 49 to 53 For heat-resistant layer (A), according to the number of parts shown in Table 21, the raw materials are mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) is prepared under stirring by an agitator. did.
  • each layer is adjusted to 6.0 g / m 2 , the two slurries are combined using a circular two-layer paper machine, and a drying cylinder dryer (surface temperature 130 ° C.) is used. Then, the layers were heated and joined, and unstretched PET-based heat-fusible short fibers and polyethylene-based synthetic pulp were adhered to develop the strength of the nonwoven fabric to produce a nonwoven fabric having a width of 50 cm. Next, a super calendar process was performed to obtain a base material for a lithium ion secondary battery.
  • Example 180 According to the number of blending parts shown in Table 22, the raw materials were mixed together, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. The slurry was made using a circular mesh single layer paper machine, adjusted to a basis weight of 12.0 g / m 2 , and then dried using a drying cylinder dryer (surface temperature 130 ° C.). Stretched PET-based heat-fusible short fibers were bonded to develop the strength of the nonwoven fabric, thereby producing a nonwoven fabric. Next, a super calendar process was performed to obtain a base material for a lithium ion secondary battery.
  • Examples 181 to 183, 185 to 187 For layer (I), the raw materials were mixed together according to the number of blending parts shown in Table 22, disaggregated in pulper water, and a uniform papermaking slurry (1% concentration) was prepared under stirring by an agitator. .
  • the layers are heated and bonded together, and the heat-fusible short fibers are bonded to develop the strength of the nonwoven fabric, and the nonwoven fabric has a width of 50 cm.
  • a super calendar process was performed to obtain a base material for a lithium ion secondary battery.
  • Basis weight of base material was measured according to JIS P 8124.
  • the thickness was measured by a method defined in JIS B 7502, that is, by an outer micrometer at 5N load.
  • thickness means the value measured by the method prescribed
  • the produced separator was put into a 170 degreeC thermostat, heat-processed for 40 minutes, the shrinkage rate of each separator was measured, and heat resistance was evaluated.
  • the shrinkage rate was measured as follows. A sheet sample of 50 mm x 50 mm is cut out, the CD side of the sample is fixed with a clip and sandwiched between heat-resistant glass plates, stored in a thermostatic bath at 170 ° C for 30 minutes, taken out, and the length of the sheet sample is measured and tested. Compared with the previous length, when the percentage of reduction in length is the shrinkage, the value is less than 2%, ⁇ 2% or more and less than 5%, or 5% or more and less than 8%.
  • the heat resistance was evaluated as “ ⁇ ”, and “ ⁇ ” as 8% or more.
  • the heat resistance of a 20 ⁇ m thick polyethylene microporous membrane which is a conventionally known lithium ion secondary battery separator, was evaluated, the polyethylene microporous membrane melted and contracted, and the shrinkage rate was 30% or more. Met.
  • the base materials for lithium ion secondary batteries obtained in Examples 166 to 179 are composed of a heat resistant layer (A) containing synthetic resin short fibers and fibrillated lyocell fibers, synthetic resin short fibers and polyethylene synthetic pulp. Since it is made of a nonwoven fabric having a heat-melting layer (B) to be contained, it has a dense structure and has a good result that the variation of the surface when combined by surface coating is small, and 170 ° C. not only excellent in heat resistance in, it was obtained good results expressed shutdown characteristics at 130 ° C..
  • A heat resistant layer
  • B heat-melting layer
  • Example 166 and Examples 167 to 170 From the comparison between Example 166 and Examples 167 to 170, when the content of the polyethylene synthetic pulp as the component of the hot melt layer (B) is 40 to 90% by mass, The variation was small, the strength was high, the drop-off of the porous film was not confirmed, and not only the heat resistance at 170 ° C. was excellent, but also a shutdown characteristic at 130 ° C. was exhibited. From a comparison between Example 166 and Examples 171 and 172, when the resin constituting the synthetic resin short fiber which is a component of the hot melt layer (B) is a polyester resin or an acrylic resin, the heat resistance at 170 ° C. is extremely high. Excellent results were obtained.
  • Example 166 and 173 and Example 174 when the resin constituting the synthetic resin short fiber, which is a component of the heat-resistant layer (A), is a polyester resin or an acrylic resin, it is combined by surface coating. The surface variation of the film was small, the strength was high, and the removal of the porous film was not confirmed. From the comparison between Example 166 and Examples 175 to 178, when the content of the fibrillated lyocell fiber as the component of the heat-resistant layer (A) is 10 to 80% by mass, The variation was small, the strength was high, and no loss of the porous membrane was confirmed. In Example 175 in which the content of the fibrillated lyocell fiber is less than 10% by mass, the surface variation tends to increase. In Example 178 in which the content of fibrillated lyocell fiber exceeded 80% by mass, the strength tended to decrease slightly.
  • the base materials for lithium ion secondary batteries obtained in Comparative Examples 49-53 do not contain fibrillated lyocell fibers in the heat-resistant layer (A), so that surface variation occurs and the strength is low.
  • the degree of removal of the porous film was also larger than that of the example.
  • the base material for lithium ion secondary batteries obtained in Examples 180 to 183 and 185 to 187 does not contain a polyethylene-based synthetic pulp in the hot melt layer (B), a shutdown characteristic at 130 ° C. is exhibited. The result was not.
  • Example 184 Since the base material for a lithium ion secondary battery obtained in Example 184 does not contain synthetic resin short fibers in the hot melt layer (B), there is no entanglement between the polyethylene synthetic pulp and the synthetic resin short fibers. As a result, the surface strength was weakened, resulting in poor removal of the porous membrane.
  • Example 185 since the base material for lithium ion secondary batteries obtained in Example 185 is a two-layer structure nonwoven fabric of the same composition and does not contain polyethylene-based synthetic pulp in the hot melt layer (B), at 130 ° C. Although the shutdown characteristic was not exhibited, the coating property, the puncture strength, the drop-off, and the heat resistance were the same as those obtained in Example 180, which is a single-layered nonwoven fabric. In addition, in the case of a two-layer structure nonwoven fabric, when making a nonwoven fabric having the same basis weight, the basis weight per net (one layer) can be reduced, so that there is an advantage that the paper making speed can be increased.
  • the base material for lithium secondary battery and the separator for lithium secondary battery of the present invention can be suitably used for lithium ion secondary batteries such as lithium ion secondary batteries and lithium ion polymer secondary batteries.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)
PCT/JP2010/067702 2009-10-15 2010-10-01 リチウム二次電池用基材及びリチウム二次電池用セパレータ WO2011046066A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201080046394.4A CN102549805B (zh) 2009-10-15 2010-10-01 锂二次电池用基材和锂二次电池用隔板
KR1020127008642A KR101702693B1 (ko) 2009-10-15 2010-10-01 리튬 ２ 차 전지용 기재 및 리튬 ２ 차 전지용 세퍼레이터
JP2011536114A JP5651120B2 (ja) 2009-10-15 2010-10-01 リチウム二次電池用基材及びリチウム二次電池用セパレータ

Applications Claiming Priority (20)

Application Number Priority Date Filing Date Title
JP2009238198 2009-10-15
JP2009-238198 2009-10-15
JP2010-039538 2010-02-25
JP2010039538 2010-02-25
JP2010-041424 2010-02-26
JP2010041424 2010-02-26
JP2010-047270 2010-03-04
JP2010047270 2010-03-04
JP2010050272 2010-03-08
JP2010-050272 2010-03-08
JP2010-065433 2010-03-23
JP2010065433 2010-03-23
JP2010-097195 2010-04-20
JP2010097195 2010-04-20
JP2010119008 2010-05-25
JP2010-119008 2010-05-25
JP2010120001 2010-05-26
JP2010-120001 2010-05-26
JP2010-156494 2010-07-09
JP2010156494 2010-07-09

Publications (1)

Publication Number Publication Date
WO2011046066A1 true WO2011046066A1 (ja) 2011-04-21

Family

ID=43876117

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/067702 WO2011046066A1 (ja) 2009-10-15 2010-10-01 リチウム二次電池用基材及びリチウム二次電池用セパレータ

Country Status (4)

Country Link
JP (1) JP5651120B2 (zh)
KR (1) KR101702693B1 (zh)
CN (1) CN102549805B (zh)
WO (1) WO2011046066A1 (zh)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012008559A1 (ja) * 2010-07-14 2012-01-19 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
JP2012124029A (ja) * 2010-12-08 2012-06-28 Sony Corp 積層型微多孔膜、電池用セパレータおよび非水電解質電池
JP2012232518A (ja) * 2011-05-02 2012-11-29 Daicel Corp 不織繊維積層体及びその製造方法並びにセパレータ
JP2013105578A (ja) * 2011-11-11 2013-05-30 Ube Ind Ltd 電池用セパレータ
WO2013118639A1 (ja) 2012-02-09 2013-08-15 三菱製紙株式会社 リチウムイオン二次電池セパレータ用基材、リチウムイオン二次電池セパレータ用基材の製造方法及びリチウムイオン二次電池セパレータ
JP2013254677A (ja) * 2012-06-08 2013-12-19 Mitsubishi Paper Mills Ltd 金属イオン二次電池セパレータ
JP2015060702A (ja) * 2013-09-18 2015-03-30 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
JP2015088460A (ja) * 2013-09-26 2015-05-07 三菱製紙株式会社 リチウム二次電池用セパレータ用基材及びリチウム二次電池用セパレータ
JP2015162281A (ja) * 2014-02-26 2015-09-07 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
WO2018074442A1 (ja) * 2016-10-17 2018-04-26 三菱製紙株式会社 電気化学素子用セパレータ及びそれを含む電気化学素子
JP2018067458A (ja) * 2016-10-19 2018-04-26 三菱製紙株式会社 リチウムイオン二次電池用セパレータ用基材、リチウムイオン二次電池用セパレータ、リチウムイオン二次電池用セパレータ用基材の製造方法、及びリチウムイオン二次電池用セパレータの製造方法
WO2018123689A1 (ja) * 2016-12-27 2018-07-05 三菱製紙株式会社 リチウムイオン電池セパレータ及びリチウムイオン電池
WO2019006765A1 (zh) * 2017-07-07 2019-01-10 老虎表面技术新材料（苏州）有限公司 光伏组件用复合封装材料及该复合封装材料的制备方法
JP2020024860A (ja) * 2018-08-08 2020-02-13 三菱製紙株式会社 固体電解質担持用不織布及び固体電解質シート
JP2020098721A (ja) * 2018-12-18 2020-06-25 住友化学株式会社 多孔質層の製造方法、積層体、非水電解液二次電池用セパレータおよび非水電解液二次電池
KR20200087206A (ko) * 2017-12-26 2020-07-20 피브르웨이 메텔리얼 사이언스 & 테크놀로지 디벨롭먼트 컴퍼니., 리미티드. 리튬이온 배터리 격막 기재와 그 제조방법 및 응용
CN113493958A (zh) * 2020-04-05 2021-10-12 北京化工大学 一种同轴包覆勃姆石的聚酰亚胺纳米纤维膜及其制备方法
CN115191059A (zh) * 2020-01-23 2022-10-14 日本高度纸工业株式会社 锂离子二次电池用隔膜及锂离子二次电池
EP3899113B1 (en) 2018-12-17 2023-01-18 Lenzing Aktiengesellschaft Process for the treatment of lyocell fibres
US11637349B2 (en) 2016-09-08 2023-04-25 Mitsubishi Paper Mills Limited Substrate for lithium ion battery separators and lithium ion battery separator

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6359676B2 (ja) * 2014-09-26 2018-07-18 旭化成株式会社 セルロース微細繊維層を含む薄膜シート
JP6412805B2 (ja) * 2015-01-16 2018-10-24 ニッポン高度紙工業株式会社 セパレータ及びアルミニウム電解コンデンサ
CN108028132B (zh) * 2015-09-17 2019-11-05 日本高度纸工业株式会社 电化学元件用分隔件和电化学元件
CN109328408B (zh) * 2016-06-27 2021-06-29 日本高度纸工业株式会社 电化学元件用分隔件和电化学元件、汽车、电子设备
CN110892551B (zh) * 2017-07-18 2022-11-25 日本宝翎株式会社 电化学元件用隔膜
CN107631129A (zh) * 2017-10-31 2018-01-26 湖南国盛石墨科技有限公司 一种连续式石墨石棉板材生产用物料混碾输送系统
WO2019131588A1 (ja) 2017-12-26 2019-07-04 株式会社クラレ セパレータおよび該セパレータからなるアルカリマンガン乾電池用セパレータ
JP6506448B1 (ja) * 2018-05-25 2019-04-24 日本板硝子株式会社 鉛蓄電池用セパレータ
CN112996958A (zh) * 2018-11-13 2021-06-18 日本宝翎株式会社 无纺布以及电化学元件用隔膜
CN112585796B (zh) * 2019-05-03 2024-04-12 株式会社Lg新能源 固体电解质膜、其制造方法以及包含其的固态电池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH117936A (ja) * 1997-06-16 1999-01-12 Mitsubishi Paper Mills Ltd 電池用セパレータおよび電池
JP2005183161A (ja) * 2003-12-19 2005-07-07 Mitsubishi Paper Mills Ltd 電池用セパレータ
JP2007067389A (ja) * 2005-08-03 2007-03-15 Mitsubishi Paper Mills Ltd 電気化学素子用セパレータ
WO2007061108A1 (ja) * 2005-11-28 2007-05-31 Mitsubishi Paper Mills Limited 電気二重層キャパシタ用セパレータ

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5171150B2 (ja) 2000-03-07 2013-03-27 帝人株式会社 リチウムイオン二次電池用セパレータ
JP2003123728A (ja) 2001-10-17 2003-04-25 Oji Paper Co Ltd 非水系二次電池用セパレータ
JP2003323878A (ja) 2002-04-26 2003-11-14 Japan Storage Battery Co Ltd 複合シート、その製造方法、及びその複合シートを用いた非水電解質二次電池
DE10238944A1 (de) 2002-08-24 2004-03-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separator zur Verwendung in Hochenergiebatterien sowie Verfahren zu dessen Herstellung
JP4185748B2 (ja) 2002-09-30 2008-11-26 日本バイリーン株式会社 不織布及びリチウムイオン二次電池用セパレータ
JP4350953B2 (ja) 2003-01-07 2009-10-28 日本バイリーン株式会社 リチウム二次電池用セパレータ及びリチウム二次電池
JP2005293891A (ja) 2004-03-31 2005-10-20 Teijin Ltd リチウムイオン二次電池
JP2006019191A (ja) 2004-07-02 2006-01-19 Japan Vilene Co Ltd リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
JP4184404B2 (ja) 2005-12-08 2008-11-19 日立マクセル株式会社 電気化学素子用セパレータおよび電気化学素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH117936A (ja) * 1997-06-16 1999-01-12 Mitsubishi Paper Mills Ltd 電池用セパレータおよび電池
JP2005183161A (ja) * 2003-12-19 2005-07-07 Mitsubishi Paper Mills Ltd 電池用セパレータ
JP2007067389A (ja) * 2005-08-03 2007-03-15 Mitsubishi Paper Mills Ltd 電気化学素子用セパレータ
WO2007061108A1 (ja) * 2005-11-28 2007-05-31 Mitsubishi Paper Mills Limited 電気二重層キャパシタ用セパレータ

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2012008559A1 (ja) * 2010-07-14 2013-09-09 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
WO2012008559A1 (ja) * 2010-07-14 2012-01-19 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
JP5767222B2 (ja) * 2010-07-14 2015-08-19 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
JP2012124029A (ja) * 2010-12-08 2012-06-28 Sony Corp 積層型微多孔膜、電池用セパレータおよび非水電解質電池
JP2012232518A (ja) * 2011-05-02 2012-11-29 Daicel Corp 不織繊維積層体及びその製造方法並びにセパレータ
JP2013105578A (ja) * 2011-11-11 2013-05-30 Ube Ind Ltd 電池用セパレータ
US9570726B2 (en) 2012-02-09 2017-02-14 Mitsubishi Paper Mills Limited Base for lithium ion secondary battery separators, method for producing base for lithium ion secondary battery separators, and lithium ion secondary battery separator
WO2013118639A1 (ja) 2012-02-09 2013-08-15 三菱製紙株式会社 リチウムイオン二次電池セパレータ用基材、リチウムイオン二次電池セパレータ用基材の製造方法及びリチウムイオン二次電池セパレータ
JP2013254677A (ja) * 2012-06-08 2013-12-19 Mitsubishi Paper Mills Ltd 金属イオン二次電池セパレータ
JP2015060702A (ja) * 2013-09-18 2015-03-30 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
JP2015088460A (ja) * 2013-09-26 2015-05-07 三菱製紙株式会社 リチウム二次電池用セパレータ用基材及びリチウム二次電池用セパレータ
JP2015162281A (ja) * 2014-02-26 2015-09-07 三菱製紙株式会社 リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
US11637349B2 (en) 2016-09-08 2023-04-25 Mitsubishi Paper Mills Limited Substrate for lithium ion battery separators and lithium ion battery separator
WO2018074442A1 (ja) * 2016-10-17 2018-04-26 三菱製紙株式会社 電気化学素子用セパレータ及びそれを含む電気化学素子
JP6349021B1 (ja) * 2016-10-17 2018-06-27 三菱製紙株式会社 電気化学素子用セパレータ及びそれを含む電気化学素子
JP2019046776A (ja) * 2016-10-17 2019-03-22 三菱製紙株式会社 電気化学素子用セパレータ及びそれを含む電気化学素子
US10964986B2 (en) 2016-10-17 2021-03-30 Mitsubishi Paper Mills Limited Separator for electrochemical elements, and electrochemical element comprising same
JP2018067458A (ja) * 2016-10-19 2018-04-26 三菱製紙株式会社 リチウムイオン二次電池用セパレータ用基材、リチウムイオン二次電池用セパレータ、リチウムイオン二次電池用セパレータ用基材の製造方法、及びリチウムイオン二次電池用セパレータの製造方法
JPWO2018123689A1 (ja) * 2016-12-27 2018-12-27 三菱製紙株式会社 リチウムイオン電池セパレータ及びリチウムイオン電池
US11335972B2 (en) 2016-12-27 2022-05-17 Mitsubishi Paper Mills Limited Lithium ion battery separator and lithium ion battery
WO2018123689A1 (ja) * 2016-12-27 2018-07-05 三菱製紙株式会社 リチウムイオン電池セパレータ及びリチウムイオン電池
WO2019006765A1 (zh) * 2017-07-07 2019-01-10 老虎表面技术新材料（苏州）有限公司 光伏组件用复合封装材料及该复合封装材料的制备方法
KR20200087206A (ko) * 2017-12-26 2020-07-20 피브르웨이 메텔리얼 사이언스 & 테크놀로지 디벨롭먼트 컴퍼니., 리미티드. 리튬이온 배터리 격막 기재와 그 제조방법 및 응용
KR102452483B1 (ko) * 2017-12-26 2022-10-06 피브르웨이 메텔리얼 사이언스 & 테크놀로지 디벨롭먼트 컴퍼니., 리미티드. 리튬이온 배터리 격막 기재와 그 제조방법 및 응용
US11616272B2 (en) 2017-12-26 2023-03-28 Fibrway Material Science & Technology Development Co., Ltd. Battery separator substrate including dense layer formed on support layer, and method for preparing the same
JP2020024860A (ja) * 2018-08-08 2020-02-13 三菱製紙株式会社 固体電解質担持用不織布及び固体電解質シート
JP7019531B2 (ja) 2018-08-08 2022-02-15 三菱製紙株式会社 固体電解質担持用不織布及び固体電解質シート
EP3899113B1 (en) 2018-12-17 2023-01-18 Lenzing Aktiengesellschaft Process for the treatment of lyocell fibres
JP2020098721A (ja) * 2018-12-18 2020-06-25 住友化学株式会社 多孔質層の製造方法、積層体、非水電解液二次電池用セパレータおよび非水電解液二次電池
JP7289194B2 (ja) 2018-12-18 2023-06-09 住友化学株式会社 多孔質層の製造方法、積層体、非水電解液二次電池用セパレータおよび非水電解液二次電池
CN115191059A (zh) * 2020-01-23 2022-10-14 日本高度纸工业株式会社 锂离子二次电池用隔膜及锂离子二次电池
CN115191059B (zh) * 2020-01-23 2023-09-29 日本高度纸工业株式会社 锂离子二次电池用隔膜及锂离子二次电池
CN113493958A (zh) * 2020-04-05 2021-10-12 北京化工大学 一种同轴包覆勃姆石的聚酰亚胺纳米纤维膜及其制备方法

Also Published As

Publication number Publication date
CN102549805B (zh) 2015-08-05
JPWO2011046066A1 (ja) 2013-03-07
KR101702693B1 (ko) 2017-02-06
JP5651120B2 (ja) 2015-01-07
KR20120101341A (ko) 2012-09-13
CN102549805A (zh) 2012-07-04

Similar Documents

Publication Publication Date Title
JP5651120B2 (ja) リチウム二次電池用基材及びリチウム二次電池用セパレータ
JP5552040B2 (ja) リチウム二次電池用セパレータ
JP5613063B2 (ja) リチウム二次電池用セパレータ
JP5767222B2 (ja) リチウムイオン二次電池用セパレータ及びそれを用いてなるリチウムイオン二次電池
JP5613069B2 (ja) リチウム二次電池用セパレータ
KR101606157B1 (ko) 리튬 이온 이차 전지용 기재 및 리튬 이온 이차 전지용 세퍼레이터
JP6292626B2 (ja) リチウムイオン二次電池セパレータ用不織布基材及びリチウムイオン二次電池セパレータ
JP6953413B2 (ja) リチウムイオン電池セパレータ用基材及びリチウムイオン電池セパレータ
TW201211331A (en) Non-woven farbric comprising cellulose fiber, production method thereof and separator
JP2011249008A (ja) リチウムイオン二次電池用セパレータ
US20220158299A1 (en) Lithium ion battery separator and lithium ion battery
JP6408810B2 (ja) リチウム二次電池用セパレータ及びリチウム二次電池用セパレータの製造方法
JP2012123957A (ja) リチウム二次電池用基材及びリチウム二次電池用セパレータ
JP2012003873A (ja) リチウム二次電池用基材
JP2011187346A (ja) リチウムイオン二次電池用基材
JP2012195162A (ja) リチウム二次電池用基材及びリチウム二次電池用セパレータ
JP2019200943A (ja) リチウムイオン電池セパレータ用基材及びリチウムイオン電池セパレータ
JP2012190622A (ja) 電気化学素子用セパレータ及びそれを用いた電気化学素子
JP2012134097A (ja) リチウム二次電池用セパレータ
JP2018206671A (ja) リチウムイオン電池セパレータ用基材及びリチウムイオン電池セパレータ
JP2012227115A (ja) リチウム二次電池用基材及びリチウム二次電池用セパレータ
JP2019212436A (ja) リチウムイオン電池セパレータ用基材及びリチウムイオン電池セパレータ
JP2019212403A (ja) リチウムイオン電池セパレータ用基材及びリチウムイオン電池セパレータ
JP2017168743A (ja) 電気二重層コンデンサ用セパレータおよびそれを用いてなる電気二重層コンデンサ
JP2012221818A (ja) リチウム二次電池用基材及びリチウム二次電池用セパレータ

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080046394.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10823334

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011536114

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20127008642

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10823334

Country of ref document: EP

Kind code of ref document: A1