WO2017057109A1 - 樹脂組成物、微多孔膜、セパレータ、及び二次電池 - Google Patents
樹脂組成物、微多孔膜、セパレータ、及び二次電池 Download PDFInfo
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- WO2017057109A1 WO2017057109A1 PCT/JP2016/077741 JP2016077741W WO2017057109A1 WO 2017057109 A1 WO2017057109 A1 WO 2017057109A1 JP 2016077741 W JP2016077741 W JP 2016077741W WO 2017057109 A1 WO2017057109 A1 WO 2017057109A1
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- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/78—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from chromium, molybdenum or tungsten
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- 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
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- 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
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Definitions
- the present invention relates to a resin composition suitably used as a raw material for a separator of a secondary battery having excellent safety, a microporous film obtained by molding this resin composition, a separator comprising this microporous film, and this separator.
- the present invention relates to a secondary battery provided.
- a secondary battery such as a lithium ion battery generally includes members such as a positive electrode, a negative electrode, and a separator.
- the separator is usually made of a resin microporous film and is disposed between the positive electrode and the negative electrode.
- the separator has a role of separating the positive electrode and the negative electrode and preventing an internal short circuit due to contact of both electrodes, and a role of allowing charging / discharging of the secondary battery by passing ions such as lithium ions. .
- Patent Document 1 A microporous membrane obtained using a polyethylene composition containing ultrahigh molecular weight polyethylene and low density polyethylene, and a separator made of this microporous membrane (Patent Document 2) are known.
- the separators described in these documents contain two or more polymer components.
- the polymer having a lower heat deformation temperature melts and closes the micropores, and the polymer having a higher heat deformation temperature maintains the structure of the entire separator.
- meltdown temperature the temperature at which the entire separator melts and deforms.
- JP 10-298324 A Japanese Patent Laid-Open No. 2001-200081
- Patent Documents 1 and 2 disclose a microporous membrane having a high meltdown temperature and a low shutdown temperature.
- a separator having a higher meltdown temperature and a desired shutdown temperature (a temperature at which micropores are blocked) in order to further increase the safety and practicality of secondary batteries. Yes.
- the present invention has been made in view of the above circumstances, a resin composition suitably used as a raw material for a secondary battery separator excellent in safety, a microporous film obtained by molding this resin composition, It aims at providing the separator which consists of this microporous film, and a secondary battery provided with this separator.
- the present inventors have intensively studied a microporous membrane and a resin composition used as a raw material thereof. As a result, it contains a specific alicyclic structure-containing polymer hydrogenated product and a specific polymer that is incompatible with this alicyclic structure polymer, and contains the alicyclic structure-containing polymer hydrogenated product. It has been found that a resin composition whose amount is in a specific range is suitable as a raw material for producing a separator having a high meltdown temperature and a desired shutdown temperature, and has completed the present invention.
- a resin composition suitably used as a raw material for a separator of a secondary battery having excellent safety, a microporous film obtained by molding this resin composition, a separator comprising this microporous film, and this A secondary battery comprising a separator is provided.
- the resin composition of the present invention is a resin composition containing the following polymer (A) and polymer (B), and the content of the polymer (A) is the polymer (A). And 1 to 80% by weight based on the total of the polymer (B).
- the polymer (A) used in the present invention is an alicyclic structure-containing polymer hydrogenated product having a heat distortion temperature of 170 ° C. or higher.
- the alicyclic structure-containing polymer hydrogenated product is a polymer having an alicyclic structure in the molecule, and is a hydride of a polymer obtained by performing a polymerization reaction using a cyclic olefin as a monomer.
- Examples of the alicyclic structure that the polymer (A) has include a cycloalkane structure and a cycloalkene structure. Among these, a cycloalkane structure is preferable because a resin composition excellent in heat resistance and the like is easily obtained.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15. When the number of carbon atoms constituting the alicyclic structure is within the above range, the properties of mechanical strength, heat resistance, and moldability are highly balanced, which is preferable.
- the proportion of the repeating unit having an alicyclic structure relative to all repeating units in the polymer (A) may be appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more, more preferably. Is 70% by weight or more.
- the ratio of the repeating unit having an alicyclic structure in the polymer (A) is excessively small, the polymer (A) tends to be inferior in heat resistance.
- the remainder other than the repeating unit having an alicyclic structure in the polymer (A) is appropriately selected without any particular limitation.
- the heat distortion temperature of the polymer (A) is 170 ° C. or higher, preferably 200 ° C. or higher, more preferably 230 ° C. or higher.
- the heat distortion temperature is a value measured according to JIS K7206.
- the heat distortion temperature of the alicyclic structure-containing polymer hydrogenated product can be increased, for example, by increasing its stereoregularity.
- the weight average molecular weight (Mw) of the polymer (A) is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 500,000. When the weight average molecular weight of the polymer (A) is within the above range, an excellent resin composition can be easily obtained due to the balance between molding processability and heat resistance.
- the molecular weight distribution (Mw / Mn) of a polymer (A) is not specifically limited, Usually, it is 4.0 or less, Preferably it is 3.5 or less. A polymer having such a molecular weight distribution is more excellent in moldability.
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer (A) are polystyrene conversion values measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.
- the polymer (A) can be produced by performing a ring-opening polymerization reaction or an addition polymerization reaction using a cyclic olefin as a monomer, and subjecting the obtained polymer to a hydrogenation reaction.
- the reaction conditions for the ring-opening polymerization reaction, the addition polymerization reaction, and the hydrogenation reaction are not particularly limited, and known methods can be used.
- the polymer (A) preferably has crystallinity. “Crystallinity” refers to the property that the melting point can be observed with a differential scanning calorimeter (DSC) by optimizing the measurement conditions and the like, and is determined by the stereoregularity of the polymer chain.
- DSC differential scanning calorimeter
- the melting point thereof is preferably 180 to 350 ° C., more preferably 200 to 320 ° C., particularly preferably 220 to 300 ° C.
- polymer (A) having crystallinity examples include dicyclopentadiene having syndiotactic stereoregularity described in International Publication No. 2012/033076.
- Hydrogenated ring-opening polymer, hydrogenated dicyclopentadiene ring-opening polymer having isotactic stereoregularity described in JP-A-2002-249553, norbornene ring-opening described in JP-A-2007-16102 A well-known thing, such as a polymer hydrogenated substance, can be used.
- the polymer ( ⁇ ) is preferably a dicyclopentadiene ring-opened polymer hydrogenated product (hereinafter sometimes referred to as “polymer ( ⁇ 1)”) having syndiotactic stereoregularity.
- polymer ( ⁇ 1) a dicyclopentadiene ring-opened polymer hydrogenated product
- the polymer (B) can be selected from various known polymers by using the polymer ( ⁇ 1) as the polymer (A).
- the degree of stereoregularity of the polymer ( ⁇ 1) is not particularly limited, but it is preferable that the degree of stereoregularity is higher because a resin composition excellent in heat resistance and the like can be easily obtained.
- the ratio of the racemo dyad to the repeating unit obtained by ring-opening polymerization of dicyclopentadiene and then hydrogenating is preferably 51% or more, more preferably 60% or more. It is preferably 70% or more.
- the ratio of racemo dyad can be measured and quantified by 13 C-NMR spectrum analysis. Specifically, by applying an inverted-gate decoupling method at 200 ° C. using a mixed solvent of 1,3,5-trichlorobenzene-d3 / orthodichlorobenzene-d4 (volume ratio: 2/1) as a solvent, 13 C -NMR measurement was performed, and the intensity ratio of the 43.35 ppm signal derived from meso-dyad and the 43.43 ppm signal derived from racemo-dyad from the 127.5 ppm peak of orthodichlorobenzene-d4 as a reference shift. The proportion of dyads can be determined.
- the polymer ( ⁇ 1) undergoes ring-opening polymerization using dicyclopentadiene as the main monomer, and hydrogenates (hydrogenates) at least part of the carbon-carbon double bonds present in the resulting ring-opened polymer. Can be obtained.
- Dicyclopentadiene has stereoisomers of endo and exo, both of which can be used as monomers in the present invention. Moreover, only one isomer may be used alone, or an isomer mixture in which an endo isomer and an exo isomer are present in an arbitrary ratio may be used.
- the crystallinity of the polymer ( ⁇ 1) is increased, and a resin composition that is superior in heat resistance is easily obtained. Therefore, it is preferable to increase the ratio of one stereoisomer.
- the ratio of endo-form or exo-form is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.
- combination is easy, it is preferable that the ratio of an end body is high.
- dicyclopentadiene When producing the polymer ( ⁇ 1), only dicyclopentadiene may be used as the monomer, or another monomer copolymerizable with dicyclopentadiene may be used.
- examples of other monomers include norbornenes other than dicyclopentadiene, cyclic olefins, and dienes.
- the amount used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of monomers.
- the ring-opening polymerization catalyst used when synthesizing the polymer ( ⁇ 1) is not particularly limited as long as ring-opening polymerization of dicyclopentadiene and a ring-opening polymer having syndiotactic stereoregularity can be obtained.
- Preferred examples of the ring-opening polymerization catalyst include those containing a metal compound represented by the following formula (1).
- M is a metal atom selected from group 6 transition metal atoms in the periodic table, and R 1 may have a substituent at at least one of the 3, 4, and 5 positions.
- a good phenyl group, or —CH 2 R 3 (R 3 is a group selected from a hydrogen atom, an alkyl group which may have a substituent and an aryl group which may have a substituent).
- R 2 is a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent, and X has a halogen atom and a substituent.
- L is a group selected from an optionally substituted alkyl group, an optionally substituted aryl group and an alkylsilyl group, and L is an electron-donating neutral ligand.
- a is 0 or 1
- b is an integer of 0-2.
- M is a transition metal atom (Chromium, Molybdenum, Tungsten) of Group 6 of the Periodic Table, preferably Molybdenum or Tungsten, more preferably Tungsten.
- the number of carbon atoms of the phenyl group which may have a substituent at at least one of the positions 3, 4, and 5 of R 1 is not particularly limited, but is usually 6 to 20, preferably 6 to 15. .
- substituents include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group;
- substituents present in at least two positions of the 3, 4, and 5 positions may be bonded to each other to form a ring structure.
- Examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group; a 4-methylphenyl group, a 4-chlorophenyl group, a 3-methoxyphenyl group, 4- Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group; disubstituted groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group and 3,5-dimethoxyphenyl group Phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group and 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl And 2-naphthyl group which may have a substituent such as a group
- R 3 is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.
- the carbon number of the alkyl group which may have a substituent of R 3 is not particularly limited, but is usually 1 to 20, preferably 1 to 10. This alkyl group may be linear or branched.
- the substituent include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; and the like.
- alkyl group which may have a substituent for R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, And neophyll groups.
- the carbon number of the aryl group which may have a substituent of R 3 is not particularly limited, but is usually 6 to 20, preferably 6 to 15.
- substituents include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group;
- the aryl group of R 3 which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-methylphenyl group, and a 2,6-dimethylphenyl group.
- the group represented by R 3 is preferably an alkyl group having 1 to 20 carbon atoms.
- Examples of the halogen atom for X include a chlorine atom, a bromine atom, and an iodine atom.
- the alkyl group which may have a substituent of X and the aryl group which may have a substituent the alkyl group which may have a substituent and the substituent of R 3 respectively.
- the thing similar to what was shown as an aryl group which may have is mentioned.
- the alkylsilyl group of X include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.
- the metal compound shown by Formula (1) has two or more X, these may couple
- alkyl group which may have a substituent of R 2 and the aryl group which may have a substituent an alkyl group which may have a substituent and a substituent of R 3 respectively.
- the thing similar to what was shown as an aryl group which may have this is mentioned.
- Examples of the electron-donating neutral ligand of L include an electron-donating compound containing an atom of Group 14 or Group 15 of the Periodic Table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, Amines such as lutidine; and the like. Among these, ethers are preferable.
- a tungsten compound having a phenylimide group (a compound in which M in the formula (1) is a tungsten atom and R 1 is a phenyl group) is preferable, and tetrachlorotungsten phenylimide ( Tetrahydrofuran) complexes are more preferred.
- the method for synthesizing the metal compound represented by the formula (1) is not particularly limited.
- a conventionally known production method such as the method described in JP-A-5-345817 can be employed.
- the reaction solution may be used as it is as a catalyst solution for the ring-opening polymerization reaction, or after isolation and purification of the metal compound by a known purification treatment such as crystallization, You may use for ring-opening polymerization reaction.
- the ring-opening polymerization catalyst may be composed only of the metal compound represented by the formula (1), or may be a combination of the metal compound represented by the formula (1) and an organometallic reducing agent.
- an organometallic reducing agent By using a combination of the metal compound represented by the formula (1) and the organometallic reducing agent, the polymerization activity is improved.
- the organometallic reducing agent include organometallic compounds of Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms.
- organometallic compound examples include organic lithium such as methyl lithium, n-butyl lithium, and phenyl lithium; organic magnesium such as butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, and allyl magnesium bromide.
- organic lithium such as methyl lithium, n-butyl lithium, and phenyl lithium
- organic magnesium such as butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, and allyl magnesium bromide.
- Organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum ethoxide, diisobutyl aluminum isobutoxide, ethyl aluminum di Organic aluminum such as ethoxide, isobutylaluminum diisobutoxide Um; tetramethyl tin, tetra (n- butyl) tin, organic tin such as tetraphenyl tin; and the like. Among these, organoaluminum or organotin is preferable.
- the ring-opening polymerization reaction is usually performed in an organic solvent.
- the organic solvent to be used is not particularly limited as long as it can dissolve or disperse the ring-opening polymer or its hydrogenated product under predetermined conditions and does not inhibit the ring-opening polymerization reaction or the hydrogenation reaction. Not.
- organic solvent examples include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexa Alicyclic hydrocarbons such as hydroindene and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Chlorobenzene and dichlorobenzene Halogenated aromatic hydrocarbons such as: Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile;
- the ring-opening polymerization reaction can be started by mixing a monomer, a metal compound represented by the formula (1), and, if necessary, an organometallic reducing agent in an organic solvent.
- the amount of the metal compound represented by the formula (1) used for the ring-opening polymerization reaction is such that the molar ratio of (metal compound: monomer) is usually from 1: 100 to 1: 2,000,000, preferably 1: 500.
- the amount is from 1,000 to 1,000,000, more preferably from 1: 1,000 to 1: 500,000. If the amount of the metal compound is too large, it may be difficult to remove the metal compound after the reaction. If the amount is too small, sufficient polymerization activity may not be obtained.
- the amount used is preferably 0.1 to 100 mol, more preferably 0.2 to 50 mol, based on 1 mol of the metal compound represented by the formula (1), 0.5 ⁇ 20 mol is particularly preferred. If the amount of the organometallic reducing agent used is too small, the polymerization activity may not be sufficiently improved, and if it is too much, side reactions may easily occur.
- An activity regulator may be added to the polymerization reaction system.
- the activity regulator By using the activity regulator, the ring-opening polymerization catalyst can be stabilized, the reaction rate of the ring-opening polymerization reaction, and the molecular weight distribution of the polymer can be adjusted.
- the activity regulator is not particularly limited as long as it is an organic compound having a functional group. Examples of the activity regulator include conventionally known activity regulators such as oxygen-containing compounds, nitrogen-containing compounds, and phosphorus-containing organic compounds.
- An activity regulator can be used individually by 1 type or in combination of 2 or more types.
- the amount of the activity regulator to be added is not particularly limited, but it may be generally selected from 0.01 to 100 mol% with respect to the metal compound represented by the formula (1).
- a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer.
- the molecular weight modifier include ⁇ -olefins, aromatic vinyl compounds, oxygen-containing vinyl compounds, halogen-containing vinyl compounds, nitrogen-containing vinyl compounds, non-conjugated dienes, and conjugated dienes.
- Molecular weight regulators can be used alone or in combination of two or more.
- the amount of the molecular weight modifier to be added may be appropriately determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to dicyclopentadiene.
- the polymerization temperature is not particularly limited, but is usually in the range of ⁇ 78 to + 200 ° C., and preferably in the range of ⁇ 30 to + 180 ° C.
- the polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.
- a dicyclopentadiene ring-opening polymer having syndiotactic stereoregularity By the ring-opening polymerization reaction, a dicyclopentadiene ring-opening polymer having syndiotactic stereoregularity can be obtained.
- the target polymer ( ⁇ 1) can be obtained by subjecting the dicyclopentadiene ring-opening polymer to a hydrogenation reaction.
- the degree of syndiotactic stereoregularity of the ring-opening polymer can be adjusted by selecting the kind of the ring-opening polymerization catalyst.
- the hydrogenation reaction of the ring-opening polymer can be performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst.
- a hydrogenation catalyst a well-known homogeneous catalyst and a heterogeneous catalyst can be used as a hydrogenation catalyst of an olefin compound.
- Homogeneous catalysts include transition metal compounds such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc.
- Catalyst comprising a combination of alkali metal compounds; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV ) Noble metal complex catalysts such as dichloride and chlorotris (triphenylphosphine) rhodium; .
- metal catalysts such as nickel, palladium, platinum, rhodium, ruthenium; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, etc.
- a solid catalyst in which the metal is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide.
- the hydrogenation reaction is usually performed in an inert organic solvent.
- the inert organic solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like.
- the inert organic solvent may be the same as or different from the solvent used in the ring-opening polymerization reaction.
- the hydrogenation catalyst may be added as it is to the ring-opening polymerization reaction solution to carry out the hydrogenation reaction.
- the reaction conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst used, but the reaction temperature is usually ⁇ 20 to + 250 ° C., preferably ⁇ 10 to + 220 ° C., more preferably 0 to + 200 ° C. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, side reactions may occur.
- the hydrogen pressure is usually from 0.01 to 20 MPa, preferably from 0.05 to 15 MPa, more preferably from 0.1 to 10 MPa. If the hydrogen pressure is too low, the reaction rate may be too slow. If the hydrogen pressure is too high, a special device such as a high pressure reactor is required.
- the reaction time is not particularly limited as long as the desired hydrogenation rate is achieved, but is usually 0.1 to 10 hours. After the hydrogenation reaction, the target polymer ( ⁇ 1) may be recovered according to a conventional method.
- the hydrogenation rate in the hydrogenation reaction (the ratio of hydrogenated main chain double bonds) is not particularly limited, but is preferably 98% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the resulting polymer ( ⁇ 1).
- the polymer (A) can be used alone or in combination of two or more.
- the polymer (B) used in the present invention is a polymer that is incompatible with the polymer (A) and has a heat distortion temperature of less than 170 ° C.
- incompatible means the property of forming a sea-island structure when mixed with a certain polymer to form a resin composition or resin molded body. Since the polymer (B) is a polymer that is incompatible with the polymer (A), the excellent heat resistance of the polymer (A) in the microporous membrane (having a high heat distortion temperature) And the characteristics of the polymer (B) that flow at a relatively low temperature are fully utilized. As a result, the separator made of the obtained microporous membrane has a high meltdown temperature and a low shutdown temperature.
- the polymer (B) used is incompatible with the polymer (A), and the surface tension of the polymer (A) with respect to water and the surface tension of the polymer (B) with respect to water.
- the difference [(surface tension of polymer (A) with respect to water) ⁇ (surface tension of polymer (B) with respect to water)] is preferably 2 mN / m or more, more preferably 3 mN / m or more. .
- the difference in surface tension is 2 mN / m or more, the polymer mixture is more likely to have a sea-island structure.
- the heat distortion temperature of the polymer (B) is less than 170 ° C., preferably 165 ° C. or less, more preferably 160 ° C. or less.
- a microporous film having a lower shutdown temperature can be easily obtained.
- a polymer having a low heat distortion temperature can be efficiently obtained by lowering the molecular weight or lowering its stereoregularity.
- the weight average molecular weight (Mw) of the polymer (B) is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 500,000. Although the molecular weight distribution (Mw / Mn) of a polymer (B) is not specifically limited, Usually, it is 4.0 or less, Preferably it is 3.5 or less.
- the polymer (B) is not particularly limited as long as it is an incompatible polymer with respect to the polymer (A) and has a heat distortion temperature of less than 170 ° C.
- the polymer (B) include polyolefin polymers such as homopolymers and copolymers of monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Coalescence is mentioned.
- Specific examples of the polymer (B) include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultrahigh molecular weight polyethylene, polypropylene, ethylene-propylene random copolymer, polybutene and the like. Among these, high density polyethylene or polypropylene is preferable.
- a polymer (B) can be used individually by 1 type or in combination of 2 or more types.
- the content of the polymer (A) is 1 to 80% by weight based on the total of the polymer (A) and the polymer (B).
- the meltdown temperature becomes low
- the microporous membrane is When used as a separator, the shutdown temperature increases.
- the resin composition of the present invention When the resin composition of the present invention is used as a molding material for a microporous film, the resin composition usually contains a solvent (hereinafter sometimes referred to as “a pore-forming solvent”).
- a pore-forming solvent is used to form micropores.
- the pore-forming solvent in the resin sheet is removed to form micropores in the resin sheet.
- the boiling point of the pore-forming solvent is usually 120 to 600 ° C., preferably 150 to 500 ° C.
- the pore-forming solvent examples include hydrocarbon solvents such as nonane, decane, undecane, dodecane, and liquid paraffin.
- the content of the pore-forming solvent is usually 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 60% by weight, based on the entire resin composition.
- the resin composition of the present invention may contain a compatibilizing agent as long as the polymer (A) and the polymer (B) are in a separated state.
- a compatibilizing agent such as rubber polymers such as styrene / butadiene rubber, isoprene rubber, chloroprene rubber, and hydrogenated products thereof.
- the content is usually 0.1 to 10% by weight with respect to the total of the polymer (A) and the polymer (B).
- the resin composition of the present invention may contain an inorganic filler.
- an inorganic filler By using a resin composition containing an inorganic filler, a separator having a high shutdown temperature can be easily obtained.
- the inorganic filler include silica, alumina, zeolite, magnesia, titania and the like.
- the content is usually 1 to 50% by weight with respect to the total of the polymer (A) and the polymer (B).
- the resin composition of the present invention may further contain other additives.
- the additive include antioxidants, crystal nucleating agents, flame retardants, flame retardant aids, colorants, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, lubricants, and the like. These contents can be appropriately determined according to the purpose, but are usually less than 20% by weight, preferably 10% by weight or less based on the entire resin composition.
- the resin composition of the present invention can be obtained by melt-kneading the polymer (A), the polymer (B), and, if necessary, a solvent and additives.
- the method of melt kneading is not particularly limited.
- kneading can be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll, or a feeder ruder.
- the kneading temperature is preferably 200 to 400 ° C, more preferably 240 to 320 ° C.
- each component may be added and kneaded at once, or may be kneaded while adding in several times.
- microporous membrane of the present invention is formed using the resin composition of the present invention, and is a sea-island structure in which the polymer (A) is dispersed in the polymer (B). It is what has.
- the sea-island structure in the microporous membrane of the present invention is formed by using a combination of the polymer (A) and the polymer (B) which is a polymer incompatible with the polymer (A). Since the sea-island structure is easily formed, the polymer (A1) is preferably the polymer ( ⁇ 1).
- the shape of the island part which consists of a polymer (A) is not specifically limited, Usually, it is circular or elliptical.
- the average diameter of the island part is usually 0.05 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m.
- the average diameter of the island is calculated by observing the microporous membrane with an electron microscope, replacing each arbitrarily selected island with a circle of the same area, measuring the diameter of the circle, and taking the average of those circles. can do.
- the microporous shape is not particularly limited, but is usually circular or elliptical.
- the average microporous diameter is usually from 0.01 to 1 ⁇ m, preferably from 0.05 to 0.3 ⁇ m.
- the average microporous diameter is calculated by observing the microporous membrane with an electron microscope, replacing each arbitrarily selected hole with a circle of the same area, measuring the diameter of the circle, and taking the average value thereof. Can do.
- the film thickness of the microporous film is not particularly limited.
- the film thickness of the microporous membrane is usually 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m.
- the method for producing the microporous membrane of the present invention is not particularly limited.
- a resin composition containing a hole-forming solvent is used as a molding material, and after molding into a sheet by a film extruder, the resulting resin sheet is brought into contact with a volatile solvent and contained in the resin composition.
- a microporous film having micropores formed in the resin sheet can be obtained.
- the shape of the resin (molding material) before molding is not particularly limited as long as a microporous film can be produced.
- a pellet, powder, etc. are mentioned.
- the volatile solvent is not particularly limited as long as it is a volatile solvent and is miscible with the pore-forming solvent at 30 ° C. at an arbitrary ratio and does not dissolve the polymer (A) and the polymer (B). Not.
- the boiling point of the volatile solvent is preferably 100 ° C. or lower, and more preferably 80 ° C. or lower.
- examples of the volatile solvent include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, and 2-methylpentane. It is done.
- the treatment method for extracting and removing the hole forming solvent is not particularly limited.
- the hole forming solvent can be extracted and removed by immersing the resin sheet in a volatile solvent.
- the temperature of the volatile solvent at the time of this immersion treatment is not particularly limited, but is usually 10 to 80 ° C., preferably 20 to 60 ° C.
- the time for the immersion treatment is not particularly limited, but is usually 30 seconds to 1 hour, preferably 1 to 30 minutes.
- the method for volatilizing and removing the volatile solvent is not particularly limited.
- the volatile solvent can be volatilized and removed by heating the resin sheet under normal pressure or reduced pressure.
- the heating conditions for the resin sheet are not particularly limited, but are, for example, 20 to 150 ° C. and 30 seconds to 24 hours.
- resin sheet referred to before volatile solvent removal
- microporous membrane referred to after removal of volatile solvent
- a stretching process or a heat setting process may be performed.
- the stretching treatment refers to a treatment in which an unoriented long-chain polymer is stretched in a uniaxial or biaxial direction and molecules are oriented in the stretched direction. By performing the stretching treatment, a microporous film having higher strength can be obtained.
- the stretching method is not particularly limited. Examples thereof include a uniaxial stretching method, a biaxial stretching method, and an oblique stretching method.
- the temperature of the resin sheet or the like during the stretching treatment is usually 100 to 140 ° C., preferably 110 to 120 ° C.
- the draw ratio is preferably 10 times or more, more preferably 15 to 400 times in terms of surface magnification.
- the heat setting process refers to a process of applying predetermined heat in a state where a film is stretched by applying tension in the longitudinal direction and the width direction. By performing the heat setting treatment, a microporous film having a small heat shrinkage rate can be obtained.
- the temperature of the resin sheet or the like in the heat setting treatment is usually 100 to 140 ° C., preferably 110 to 120 ° C.
- the heat setting time is usually 1 to 60 seconds.
- the microporous membrane of the present invention is formed using the resin composition of the present invention, and is suitably used as a separator for a secondary battery.
- the separator of the present invention comprises the microporous membrane of the present invention. Accordingly, the separator of the present invention has a high meltdown temperature and a desired shutdown temperature.
- the meltdown temperature of the separator of the present invention is usually over 260 ° C., and the shutdown temperature is usually 170 ° C. or lower.
- the meltdown temperature and the shutdown temperature can be measured by the methods described in the examples.
- the polymer (A) (alicyclic structure-containing polymer hydrogenated product) constituting the separator of the present invention is excellent in electrical insulation and chemical resistance. For this reason, the separator of the present invention is less likely to cause a short circuit and is less likely to deteriorate due to a chemical reaction. Furthermore, the separator of the present invention has a high meltdown temperature and a desired shutdown temperature as described above. Because of the above characteristics, the separator of the present invention is extremely safe and practical.
- the secondary battery of the present invention includes the separator of the present invention. Moreover, the secondary battery of the present invention usually has a positive electrode, a negative electrode, and an electrolyte component.
- the secondary battery of the present invention includes, for example, a positive electrode and a negative electrode that are stacked with a separator interposed therebetween, and are wound into a battery container according to the battery shape as necessary. It can be manufactured by injecting and sealing the liquid. In order to prevent an increase in pressure inside the secondary battery, overcharge / discharge, and the like, a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, and the like may be provided as necessary.
- the shape of the secondary battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
- Ratio of racemo dyad of hydrogenated polymer containing alicyclic structure 200% mixed solvent (volume ratio: 2/1) of 1,3,5-trichlorobenzene-d3 / orthodichlorobenzene-d4 The 13 C-NMR measurement was performed at 0 ° C., and based on the intensity ratio of the 43.35 ppm signal derived from meso-dyad and the 43.43 ppm signal derived from racemo-dyad, racemo of the alicyclic structure-containing polymer hydrogenated product • Determined the proportion of dyads.
- total addition amount of dicyclopentadiene 270 parts (total addition amount of dicyclopentadiene 270 parts), and further at 50 ° C. The reaction was continued for 2 hours. Next, a small amount of isopropanol was added to the reaction solution to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to precipitate a ring-opening polymer. The precipitated polymer was collected by filtration. The obtained ring-opening polymer was dried at 40 ° C. under reduced pressure for 20 hours. The yield of the polymer was 296 parts (99% yield).
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) of this polymer were 14,200 and 27,000, respectively, and the molecular weight distribution (Mw / Mn) calculated
- the precipitate was collected by filtration, washed with isopropyl alcohol, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 27.2 parts (yield 98%) of a hydrogenated dicyclopentadiene ring-opening polymer.
- the hydrogenation rate of the obtained dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the ratio of racemo dyad was 85%, and the melting point was 265 ° C.
- Example 1 Using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM-37BS), 60 parts of COP and 40 parts of HDPE were kneaded at a resin temperature of 270 ° C. At that time, liquid paraffin was supplied from the side feeder so that the amount thereof was 50% of the entire resin composition. The obtained resin composition was put into a film extruder (manufactured by GSI Creos), which was passed through a gear pump and a T die, and formed into a resin sheet having a thickness of 50 ⁇ m. The obtained sheet was immersed in an n-hexane solution for 3 minutes to remove liquid paraffin. Thereafter, the sheet was heated and fixed at 120 ° C. for 30 seconds while the four sides of the sheet were fixed to obtain a microporous film. Using this as a test piece, the shutdown temperature and the meltdown temperature were measured.
- a twin-screw extruder Toshiba Machine Co., Ltd., TEM-37
- Example 2 Comparative Examples 1 to 4
- Example 1 except that the resin component was changed to that shown in Table 1, a resin composition and a microporous film were obtained in the same manner as in Example 1, and the shutdown temperature and meltdown temperature were measured. .
- the microporous membranes obtained in Examples 1 to 5 have a low shutdown temperature and a high meltdown temperature. Therefore, the separator made of this microporous membrane is excellent in safety.
- the microporous membranes obtained in Comparative Examples 1 and 3 had low meltdown temperatures, and the microporous membranes obtained in Comparative Examples 2 and 4 had high shutdown temperatures. Therefore, a separator made of these microporous membranes is inferior in safety.
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Abstract
Description
セパレータは、通常、樹脂製の微多孔膜からなり、正極と負極との間に配置される。セパレータには、正極と負極とを分離し、両極の接触による内部短絡を防止するという役割や、リチウムイオン等のイオンを通過させることで、二次電池の充放電を可能にするという役割がある。
しかしながら、近年においては、二次電池の安全性と実用性をより高めるために、メルトダウン温度がより高く、かつ、所望のシャットダウン温度(微孔が塞がれる温度)を有するセパレータが要望されている。
〔1〕下記重合体(A)及び重合体(B)を含有する樹脂組成物であって、重合体(A)の含有量が、重合体(A)と重合体(B)の合計に対して1~80重量%である樹脂組成物。
重合体(A):熱変形温度が170℃以上の脂環構造含有重合体水素添加物
重合体(B):重合体(A)に対して非相溶性の重合体であって、熱変形温度が170℃未満の重合体
〔2〕重合体(A)の水に対する表面張力と、重合体(B)の水に対する表面張力の差が2mN/m以上である、〔1〕に記載の樹脂組成物。
〔3〕前記〔1〕又は〔2〕に記載の樹脂組成物を用いて形成された微多孔膜であって、重合体(B)中に、重合体(A)が分散してなる海島構造を有する微多孔膜。
〔4〕前記〔3〕に記載の微多孔膜からなるセパレータ。
〔5〕前記〔4〕に記載のセパレータを備える二次電池。
本発明の樹脂組成物は、下記重合体(A)及び重合体(B)を含有する樹脂組成物であって、重合体(A)の含有量が、重合体(A)と重合体(B)の合計に対して1~80重量%のものである。
重合体(A):熱変形温度が170℃以上の脂環構造含有重合体水素添加物
重合体(B):重合体(A)に対して非相溶性の重合体であって、熱変形温度が170℃未満の重合体
本発明に用いる重合体(A)は、熱変形温度が170℃以上の脂環構造含有重合体水素添加物である。
脂環構造含有重合体水素添加物は、分子内に、脂環構造を有する重合体であって、環状オレフィンを単量体として用いて重合反応を行って得られた重合体の水素化物である。
重合体(A)が有する脂環構造としては、シクロアルカン構造やシクロアルケン構造が挙げられる。これらの中でも、耐熱性等に優れる樹脂組成物が得られ易いことから、シクロアルカン構造が好ましい。脂環構造を構成する炭素原子の数は、特に制限はないが、通常4~30個、好ましくは5~20個、より好ましくは5~15個である。脂環構造を構成する炭素原子の数が上記範囲内にあることで、機械的強度、耐熱性、及び成形性の特性が高度にバランスされ好適である。
重合体(A)中の脂環構造を有する繰り返し単位以外の残部は、格別な限定はなく、適宜選択される。
熱変形温度は、JIS K7206に準拠して測定した値である。
重合体(A)の熱変形温度が170℃以上であることで、メルトダウン温度がより高い微多孔膜が得られ易くなる。
脂環構造含有重合体水素添加物の熱変形温度は、例えばその立体規則性を高めることにより高くすることができる。
重合体(A)の分子量分布(Mw/Mn)は、特に限定されないが、通常4.0以下であり、好ましくは3.5以下である。このような分子量分布を有する重合体は、成形加工性により優れる。
重合体(A)の重量平均分子量(Mw)や分子量分布(Mw/Mn)は、テトラヒドロフランを展開溶媒とするゲル・パーミエーション・クロマトグラフィー(GPC)により測定されるポリスチレン換算値である。
開環重合反応、付加重合反応、水素添加反応の反応条件等は特に限定されず、公知の方法を使用することができる。
重合体(A)が結晶性を有するとき、その融点は、好ましくは180~350℃、より好ましくは200~320℃、特に好ましくは220~300℃である。
具体的には、ジシクロペンタジエンを開環重合して、次いで、水素化して得られる繰り返し単位についてのラセモ・ダイアッドの割合が、51%以上であることが好ましく、60%以上であることがより好ましく、70%以上であることが特に好ましい。
ラセモ・ダイアッドの割合が高いものほど、すなわち、シンジオタクチック立体規則性の高いものほど、高い融点を有するジシクロペンタジエン開環重合体水素添加物となる。
ラセモ・ダイアッドの割合は、13C-NMRスペクトル分析で測定し、定量することができる。具体的には、1,3,5-トリクロロベンゼン-d3/オルトジクロロベンゼン-d4の混合溶媒(体積比:2/1)を溶媒として、200℃でinverse-gated decoupling法を適用して13C-NMR測定を行い、オルトジクロロベンゼン-d4の127.5ppmのピークを基準シフトとして、メソ・ダイアッド由来の43.35ppmのシグナルと、ラセモ・ダイアッド由来の43.43ppmのシグナルの強度比からラセモ・ダイアッドの割合を決定することができる。
他の単量体を用いる場合、その使用量は、単量体全量中、好ましくは10重量%以下、より好ましくは5重量%以下である。
前記置換基としては、メチル基、エチル基等のアルキル基;フッ素原子、塩素原子、臭素原子等のハロゲン原子;メトキシ基、エトキシ基、イソプロポキシ基等のアルコキシ基;等が挙げられる。
また、3,4,5位の少なくとも2つの位置に存在する置換基が互いに結合し、環構造を形成していてもよい。
3,4,5位の少なくとも1つの位置に置換基を有していてもよいフェニル基としては、無置換フェニル基;4-メチルフェニル基、4-クロロフェニル基、3-メトキシフェニル基、4-シクロヘキシルフェニル基、4-メトキシフェニル基等の一置換フェニル基;3,5-ジメチルフェニル基、3,5-ジクロロフェニル基、3,4-ジメチルフェニル基、3,5-ジメトキシフェニル基等の二置換フェニル基;3,4,5-トリメチルフェニル基、3,4,5-トリクロロフェニル基等の三置換フェニル基;2-ナフチル基、3-メチル-2-ナフチル基、4-メチル-2-ナフチル基等の置換基を有していてもよい2-ナフチル基;等が挙げられる。
R3の、置換基を有していてもよいアルキル基の炭素数は、特に限定されないが、通常1~20、好ましくは1~10である。このアルキル基は直鎖状であっても分岐状であってもよい。
前記置換基としては、フェニル基、4-メチルフェニル基等の置換基を有していてもよいフェニル基;メトキシ基、エトキシ基等のアルコキシル基;等が挙げられる。
R3の、置換基を有していてもよいアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t-ブチル基、ペンチル基、ネオペンチル基、ベンジル基、ネオフィル基等が挙げられる。
前記置換基としては、メチル基、エチル基等のアルキル基;フッ素原子、塩素原子、臭素原子等のハロゲン原子;メトキシ基、エトキシ基、イソプロポキシ基等のアルコキシ基;等が挙げられる。
R3の、置換基を有していてもよいアリール基としては、フェニル基、1-ナフチル基、2-ナフチル基、4-メチルフェニル基、2,6-ジメチルフェニル基等が挙げられる。
これらの中でも、R3で表される基としては、炭素数が1~20のアルキル基が好ましい。
Xの、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基としては、それぞれ、R3の、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基として示したものと同様のものが挙げられる。
Xのアルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、t-ブチルジメチルシリル基等が挙げられる。
また、式(1)で示される金属化合物が、2以上のXを有するとき、これらは互いに結合し、環構造を形成していてもよい。
金属化合物の合成後、反応液をそのまま開環重合反応の触媒液として用いてもよいし、結晶化等の公知の精製処理により、金属化合物を単離、精製した後、得られた金属化合物を開環重合反応に供してもよい。
有機金属還元剤としては、炭素数1~20の炭化水素基を有する周期律表第1、2、12、13、14族の有機金属化合物が挙げられる。
前記有機金属化合物としては、メチルリチウム、n-ブチルリチウム、フェニルリチウム等の有機リチウム;ブチルエチルマグネシウム、ブチルオクチルマグネシウム、ジヘキシルマグネシウム、エチルマグネシウムクロリド、n-ブチルマグネシウムクロリド、アリルマグネシウムブロミド等の有機マグネシウム;ジメチル亜鉛、ジエチル亜鉛、ジフェニル亜鉛等の有機亜鉛;トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、ジエチルアルミニウムクロリド、エチルアルミニウムセスキクロリド、エチルアルミニウムジクロリド、ジエチルアルミニウムエトキシド、ジイソブチルアルミニウムイソブトキシド、エチルアルミニウムジエトキシド、イソブチルアルミニウムジイソブトキシド等の有機アルミニウム;テトラメチルスズ、テトラ(n-ブチル)スズ、テトラフェニルスズ等の有機スズ;等が挙げられる。
これらの中でも、有機アルミニウム又は有機スズが好ましい。
有機溶媒としては、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素類;シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ビシクロヘプタン、トリシクロデカン、ヘキサヒドロインデン、シクロオクタン等の脂環族炭化水素類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類;ジクロロメタン、クロロホルム、1,2-ジクロロエタン等のハロゲン系脂肪族炭化水素類;クロロベンゼン、ジクロロベンゼン等のハロゲン系芳香族炭化水素類;ニトロメタン、ニトロベンゼン、アセトニトリル等の含窒素炭化水素類;ジエチルエ-テル、テトラヒドロフラン等のエ-テル類;これらを組み合わせた混合溶媒;等が挙げられる。
これらの中でも、有機溶媒としては、芳香族炭化水素類、脂肪族炭化水素類、脂環族炭化水素類、エーテル類が好ましい。
活性調整剤は、官能基を有する有機化合物であれば特に制限されない。活性調整剤としては、含酸素化合物、含窒素化合物、含リン有機化合物等の従来公知の活性調整剤が挙げられる。
活性調整剤は1種単独で、あるいは2種以上を組み合わせて用いることができる。添加する活性調整剤の量は、特に限定されないが、通常、式(1)で示される金属化合物に対して0.01~100モル%の間で選択すればよい。
分子量調整剤は1種単独で、あるいは2種以上を組み合わせて用いることができる。添加する分子量調整剤の量は目的とする分子量に応じて適宜決定すればよいが、通常、ジシクロペンタジエンに対して、0.1~50モル%の範囲で選択すればよい。
不活性有機溶媒は、開環重合反応に用いた溶媒と同じものであってもよいし、異なるものであってもよい。また、開環重合反応液にそのまま水素化触媒を添加して、水素添加反応を行ってもよい。
水素圧力は、通常0.01~20MPa、好ましくは0.05~15MPa、より好ましくは0.1~10MPaである。水素圧力が低すぎると反応速度が遅くなりすぎる場合があり、水素圧力が高すぎると高耐圧反応装置等の特別な装置が必要になる。
反応時間は、所望の水素化率が達成されるのであれば特に限定されないが、通常0.1~10時間である。
水素添加反応後は、常法に従って、目的の重合体(α1)を回収すればよい。
本発明に用いる重合体(B)は、前記重合体(A)に対して非相溶性の重合体であって、熱変形温度が170℃未満のものである。
本発明において、非相溶性とは、ある重合体と混合して樹脂組成物や樹脂成形体にしたときに、海島構造を形成する性質をいう。重合体(B)が重合体(A)に対して非相溶性の重合体であることで、微多孔膜において、重合体(A)が有する優れた耐熱性(高い熱変形温度を有すること)と、重合体(B)が有する比較的低い温度で流動する特性がそれぞれ十分に生かされる。この結果、得られた微多孔膜からなるセパレータは、高いメルトダウン温度と低いシャットダウン温度を有する。
表面張力の差が2mN/m以上であることで、重合体の混合物がより海島構造をとりやすくなる。
重合体(B)の熱変形温度が170℃未満であることで、シャットダウン温度がより低い微多孔膜が得られ易くなる。
熱変形温度が低い重合体は、分子量を低くしたり、その立体規則性を低くしたりすることにより効率よく得ることができる。
重合体(B)の分子量分布(Mw/Mn)は、特に限定されないが、通常4.0以下であり、好ましくは3.5以下である。
重合体(B)としては、エチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキセン、及び1-オクテン等の単量体の単独重合体や共重合体等のポリオレフィン系重合体が挙げられる。
重合体(B)の具体例としては、低密度ポリエチレン、線状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、超高分子量ポリエチレン、ポリプロピレン、エチレン-プロピレンランダム共重合体、ポリブテン等が挙げられる。
これらの中でも、高密度ポリエチレン又はポリプロピレンが好ましい。
本発明において、重合体(B)は一種単独で、あるいは二種以上を組み合わせて用いることができる。
本発明の樹脂組成物は、重合体(A)の含有量が、重合体(A)と重合体(B)の合計に対して1~80重量%のものである。重合体(A)の含有量が少なすぎるときは、微多孔膜をセパレータとして使用したときに、メルトダウン温度が低くなり、重合体(A)の含有量が多すぎるときは、微多孔膜をセパレータとして使用したときに、シャットダウン温度が高くなる。
孔形成用溶剤は、微多孔を形成するために用いられる。孔形成用溶剤を含有する樹脂組成物を成形して樹脂シートを成形した後、その樹脂シート中の孔形成用溶剤を除去することにより、樹脂シート内に微多孔が形成される。
孔形成用溶剤の沸点は、通常、120~600℃、好ましくは150~500℃である。この範囲の沸点を有する孔形成用溶剤を用いることで、微多孔を効率よく形成することができる。
孔形成用溶剤としては、ノナン、デカン、ウンデカン、ドデカン、流動パラフィン等の炭化水素系溶媒が挙げられる。
孔形成用溶剤の含有量は、樹脂組成物全体に対して、通常、20~80重量%、好ましくは30~70重量%、より好ましくは40~60重量%である。
相溶化剤としては、スチレン・ブタジエンゴム、イソプレンゴム、クロロプレンゴム等のゴム系重合体やその水素添加物が挙げられる。
本発明の樹脂組成物が相溶化剤を含有するとき、その含有量は、重合体(A)と重合体(B)の合計に対して、通常、0.1~10重量%である。
無機充填剤としては、シリカ、アルミナ、ゼオライト、マグネシア、チタニア等が挙げられる。
本発明の樹脂組成物が無機充填剤を含有するとき、その含有量は、重合体(A)と重合体(B)の合計に対して、通常、1~50重量%である。
添加剤としては、酸化防止剤、結晶核剤、難燃剤、難燃助剤、着色剤、帯電防止剤、可塑剤、紫外線吸収剤、光安定剤、滑剤等が挙げられる。
これらの含有量は、目的に合わせて適宜決定することができるが、樹脂組成物全体に対して、通常、20重量%未満、好ましくは10重量%以下である。
溶融混練の方法は特に限定されない。例えば、単軸押出機、二軸押出機、バンバリーミキサー、ニーダー、ロール、フィーダールーダー等の溶融混練機を用いて、混錬を行うことができる。
混練温度は、好ましくは200~400℃、より好ましくは240~320℃である。また、混練するに際しては、各成分を一括に添加して混練してもよいし、数回に分けて添加しながら混練してもよい。
本発明の微多孔膜は、本発明の樹脂組成物を用いて形成されたものであって、重合体(B)中に、重合体(A)が分散してなる海島構造を有するものである。
島部分の平均径は、通常、0.05~100μm、好ましくは、0.1~50μmである。
島部分の平均径は、微多孔膜を電子顕微鏡で観察して任意に選択した複数の島をそれぞれ同面積の円に置き換え、その円の直径を測定し、それらの平均値をとることにより算出することができる。
微多孔の平均径は、通常、0.01~1μm、好ましくは、0.05~0.3μmである。
微多孔の平均径は、微多孔膜を電子顕微鏡で観察して任意に選択した孔をそれぞれ同面積の円に置き換え、その円の直径を測定し、それらの平均値をとることにより算出することができる。
揮発性溶剤の沸点は、100℃以下が好ましく、80℃以下がより好ましい。
孔形成用溶剤として流動パラフィン等の炭化水素系溶媒を使用する場合、揮発性溶剤としては、n-ペンタン、n-ヘキサン、n-ヘプタン、2-メチルペンタン等の脂肪族炭化水素系溶剤が挙げられる。
この浸漬処理を行うときの揮発性溶剤の温度は特に限定されないが、通常、10~80℃、好ましくは20~60℃である。
浸漬処理の時間は、特に限定されないが、通常、30秒から1時間、好ましくは1~30分である。
樹脂シートの加熱条件は特に限定されないが、例えば、20~150℃で、30秒から24時間である。
延伸倍率は、面倍率で好ましくは10倍以上、より好ましくは15~400倍である。
熱固定処理における樹脂シート等の温度は、通常、100~140℃、好ましくは110~120℃である。
熱固定処理の時間は、通常、1~60秒である。
本発明のセパレータは、本発明の微多孔膜からなる。したがって、本発明のセパレータは、高いメルトダウン温度と、所望のシャットダウン温度を有する。
本発明のセパレータのメルトダウン温度は、通常、260℃超であり、シャットダウン温度は、通常、170℃以下である。
メルトダウン温度とシャットダウン温度は、実施例に記載の方法により測定することができる。
さらに、本発明のセパレータは、上記のように、高いメルトダウン温度と、所望のシャットダウン温度を有する。
上記特性を有することから、本発明のセパレータは極めて安全性に優れ、かつ、実用性にも優れるものである。
本発明の二次電池は、例えば、正極と、負極とを、セパレータを介して重ね合わせ、これを必要に応じて電池形状に応じて巻く、折る等して電池容器に入れ、電池容器に電解液を注入して封口することにより製造することができる。二次電池の内部の圧力上昇、過充放電等の発生を防止するために、必要に応じて、ヒューズ、PTC素子等の過電流防止素子、エキスパンドメタル、リード板等を設けてもよい。二次電池の形状は、例えば、コイン型、ボタン型、シート型、円筒型、角形、扁平型等、何れであってもよい。
(1)脂環構造含有重合体の分子量(重量平均分子量及び数平均分子量)
テトラヒドロフランを溶媒として、40℃でゲル・パーミエーション・クロマトグラフィー(GPC)を行い、脂環構造含有重合体の分子量を標準ポリスチレン換算値として求めた。
システム:東ソー社製、HLC-8220
カラム:東ソー社製、Hタイプカラム
(2)脂環構造含有重合体の水素添加反応における水素化率
1H-NMR測定により、脂環構造含有重合体の水素添加反応における水素化率を求めた。
示差走査熱量計を用いて10℃/分で昇温して熱重量分析を行い、脂環構造含有重合体水素添加物の融点を測定した。
(4)脂環構造含有重合体水素添加物のラセモ・ダイアッドの割合
1,3,5-トリクロロベンゼン-d3/オルトジクロロベンゼン-d4の混合溶媒(体積比:2/1)を溶媒として、200℃で13C-NMR測定を行い、メソ・ダイアッド由来の43.35ppmのシグナルと、ラセモ・ダイアッド由来の43.43ppmのシグナルの強度比に基づいて、脂環構造含有重合体水素添加物のラセモ・ダイアッドの割合を決定した。
HDT試験機(東洋精機社製、6M-2)を用いて、JIS K 7206に従い、荷重50N、昇温速度50℃/時間の条件でビカット軟化点を測定し、これを熱変形温度とした。
(6)表面張力
自動接触角計(協和界面科学社製、DropMaster DM500型)を用いて、溶媒として水(イオン交換水)を用いたときの接触角を測定し、表面張力を求めた。
熱機械的分析装置(セイコー電子工業社製、TMA/SS6100)を用いて、10mm(TD)×3mm(MD)の試験片を、荷重2gで試験片の長手方向に引っ張りながら、5℃/分の速度で室温(20℃、以下にて同じ)から昇温し、融点付近で観測された変曲点の温度をシャットダウン温度とした。このシャットダウン温度が170℃以下のものを「○(good)」、170℃を超えるものを「×(bad)」と評価した。
(8)メルトダウン温度
上記熱機械的分析装置を用い、10mm(TD:Transverse Direction)×3mm(MD:Machine Direction)の試験片を、荷重2gで試験片の長手方向に引っ張りながら、5℃/分の速度で室温から昇温し、溶融により破膜した温度をメルトダウン温度とした。このメルトダウン温度が260℃を超えるものを「○(good)」、260℃以下のものを「×(bad)」と評価した
内部を十分に乾燥した後、窒素置換したガラス製耐圧反応容器に、ジシクロペンタジエン(エンド体含有率99%以上)のシクロヘキサン溶液(濃度75%)40部(ジシクロペンタジエンの量として30部)を仕込み、さらに、シクロヘキサン738部及び1-ヘキセン2.0部を加え、全容を攪拌しながら、50℃に加熱した。
一方、テトラクロロタングステンフェニルイミド(テトラヒドロフラン)錯体1.1部を56部のトルエンに溶解した溶液に、ジエチルアルミニウムエトキシド/n-ヘキサン溶液(濃度19%)4.6部を加えて10分間攪拌し、触媒溶液を調製した。
反応器の内容物を攪拌しながら、この触媒溶液を反応器内に加えて開環重合反応を開始させた。その後、全容を50℃に保ちながら、5分毎にジシクロペンタジエンのシクロヘキサン溶液(濃度75重量%)40部を9回添加した(ジシクロペンタジエンの合計添加量270部)後、さらに50℃で2時間反応を継続した。
次いで、反応液に少量のイソプロパノールを加えて、重合反応を停止させた後、重合反応溶液を多量のイソプロパノール中に注ぎ、開環重合体を析出させた。析出した重合体を濾過により回収した。得られた開環重合体を減圧下40℃で20時間乾燥した。
重合体の収量は296部(収率99%)であった。また、この重合体の数平均分子量(Mn)及び重量平均分子量(Mw)は、それぞれ14,200及び27,000であり、これらから求められる分子量分布(Mw/Mn)は1.90であった。
得られたジシクロペンタジエン開環重合体水素添加物の水素化率は99%以上、ラセモ・ダイアッドの割合は85%であり、融点は265℃であった。
・ジシクロペンタジエン開環重合体水素添加物(製造例1)(以下、「COP」と省略することがある。)
熱変形温度:263℃、表面張力:34mN/m
・高密度ポリエチレン(日本ポリエチレン社製、HF560)(以下、「HDPE」と省略することがある。)
熱変形温度:122℃、表面張力:31mN/m
・ポリプロピレン(プライムポリマー社製、F-300SP)(以下、「PP」と省略することがある。)
熱変形温度:162℃、表面張力:29mN/m
二軸押出機(東芝機械社製、TEM-37BS)を用いて、COP60部及びHDPE40部を、樹脂温度270℃で混練した。その際、流動パラフィンを、その量が樹脂組成物全体の50%となるようにサイドフィーダーから供給した。
得られた樹脂組成物をフィルム押出機(GSIクレオス社製)に投入し、これをギヤポンプ及びTダイを通過させ、厚さ50μmの樹脂シートに成形した。
得られたシートをn-ヘキサン溶液に3分間浸漬させ、流動パラフィンを除去した。その後シートの四辺を固定したまま120℃で30秒加熱して熱固定し、微多孔膜を得た。これを試験片として使用して、シャットダウン温度及びメルトダウン温度を測定した。
実施例1において、樹脂成分を第1表に記載のものに変更したことを除き、実施例1と同様にして、樹脂組成物、及び微多孔膜を得、シャットダウン温度及びメルトダウン温度を測定した。
実施例1~5で得られた微多孔膜は、シャットダウン温度が低く、メルトダウン温度が高いものである。したがって、この微多孔膜からなるセパレータは安全性に優れる。
一方、比較例1、3で得られた微多孔膜は、メルトダウン温度が低く、比較例2、4で得られた微多孔膜はシャットダウン温度が高いものであった。したがって、これらの微多孔膜からなるセパレータは安全性に劣る。
Claims (5)
- 下記重合体(A)及び重合体(B)を含有する樹脂組成物であって、重合体(A)の含有量が、重合体(A)と重合体(B)の合計に対して1~80重量%である樹脂組成物。
重合体(A):熱変形温度が170℃以上の脂環構造含有重合体水素添加物
重合体(B):重合体(A)に対して非相溶性の重合体であって、熱変形温度が170℃未満の重合体 - 重合体(A)の水に対する表面張力と、重合体(B)の水に対する表面張力の差が2mN/m以上である、請求項1に記載の樹脂組成物。
- 請求項1又は2に記載の樹脂組成物を用いて形成された微多孔膜であって、重合体(B)中に、重合体(A)が分散してなる海島構造を有する微多孔膜。
- 請求項3に記載の微多孔膜からなるセパレータ。
- 請求項4に記載のセパレータを備える二次電池。
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