WO2015008619A1 - リチウム二次電池の電極用結着剤 - Google Patents
リチウム二次電池の電極用結着剤 Download PDFInfo
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- WO2015008619A1 WO2015008619A1 PCT/JP2014/067562 JP2014067562W WO2015008619A1 WO 2015008619 A1 WO2015008619 A1 WO 2015008619A1 JP 2014067562 W JP2014067562 W JP 2014067562W WO 2015008619 A1 WO2015008619 A1 WO 2015008619A1
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- binder
- active hydrogen
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- polyurethane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/325—Polyamines containing secondary or tertiary amino groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
Definitions
- the present invention relates to a binder for an active material for a lithium secondary battery.
- Lithium batteries have high voltage and good energy density, and have improved safety compared to Ni—Cd batteries and the like, and have been widely used as power sources for portable electronic devices.
- the demand for smaller and lighter batteries has led to higher drive voltage, longer life and higher energy than conventional lithium batteries. Improved battery characteristics such as density are required.
- the characteristics of the battery are greatly influenced by the electrode, electrolyte and other battery materials used.
- the characteristics are determined by the electrode active material, the current collector, and the binder that provides an adhesive force between them. Is determined.
- the amount and type of active material used can determine the amount of lithium ions that can bind to the active material, the higher the amount of active material and the higher the specific capacity active material, the higher the capacity.
- a battery can be obtained.
- the binder has an excellent adhesive force between the active materials and between the active material and the current collector, electrons and lithium ions move smoothly in the electrode, and the internal resistance of the electrode is reduced. Therefore, highly efficient charging / discharging becomes possible.
- a composite electrode such as carbon and graphite, carbon and silicon is required as the negative electrode active material, so that the volume expansion and contraction of the active material greatly occurs during charging and discharging.
- the binder must have excellent elasticity in addition to excellent adhesive force, and must maintain its original adhesive force and restoring force despite repeated considerable expansion and contraction of the electrode volume.
- a binder for obtaining such an electrode a material obtained by dissolving a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride in an organic solvent is known.
- a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride
- the fluororesin is not sufficiently high in adhesion to the metal constituting the current collector and is not sufficiently high in flexibility, it can be obtained particularly when a wound battery is manufactured.
- a crack occurs in the obtained electrode layer, or peeling between the obtained electrode layer and the current collector occurs.
- the amount of input In order to maintain sufficient adhesive strength, the amount of input must be large, so there is a limit to downsizing, and there is a disadvantage that manufacturing is complicated because it is used in combination with an organic solvent. .
- a binder made of styrene-butadiene latex is known as a binder capable of forming a highly flexible electrode layer having high adhesion to the metal constituting the current collector.
- Patent Documents 1, 2, and 3 a binder made of styrene-butadiene latex (SBR) is known as a binder capable of forming a highly flexible electrode layer having high adhesion to the metal constituting the current collector.
- SBR styrene-butadiene latex
- the present invention has been made on the basis of the above circumstances, and its purpose is to form a volume expansion of the active material during charging and discharging in the formation of an electrode layer in which silicon is used alone or in combination with the negative electrode active material.
- An object of the present invention is to provide a binder capable of maintaining the binding property against shrinkage.
- a binder for an electrode of a lithium secondary battery containing a polyurethane water dispersion wherein the polyurethane water dispersion has at least (A) an organic polyisocyanate and (B) one or more active hydrogen groups.
- a compound having one or more active hydrogen groups is (B1) a compound having two or more active hydrogen groups and (B2) a compound having one or more active hydrogen groups and one or more ionic hydrophilic groups.
- the binder for electrodes of a lithium secondary battery characterized by containing. 2)
- the polyurethane resin aqueous dispersion described in 1) comprises (B) a compound having two or more active hydrogen groups, and (C) one or more active hydrogen groups and one or more hydrophilic groups.
- the polyurethane resin aqueous dispersion described in 1) includes an aromatic ring structure or an alicyclic structure, and the total content of the aromatic ring structure or the alicyclic structure is preferably 40% by mass or more.
- the index indicating the branch density per 1000 molecular weight of the polyurethane is in the range of 0.3 to 1.0.
- membrane formed from the polyurethane resin aqueous dispersion of said 1) to electrolyte solution for 3 days on 60 degreeC conditions is 50% or less.
- the elastic modulus at 60 ° C. of the swollen film after the film formed from the polyurethane resin aqueous dispersion described in 1) is immersed in an electrolytic solution for 3 days at 60 ° C. is 10 MPa or more.
- the film formed by immersing the film formed from the polyurethane resin aqueous dispersion described in 1) above in an electrolytic solution for 3 days under a condition of 60 ° C. and dried under reduced pressure at 80 ° C. for 24 hours has a weight reduction rate of 10 wt%. The following is preferable.
- the film formed from the aqueous polyurethane resin dispersion of the present invention has a low swelling ratio with respect to the electrolytic solution and has a high elastic modulus after being immersed in the electrolytic solution.
- the electrode used as the binder for the electrode of the secondary battery can maintain the binding property against the volume expansion and contraction of the active material even in the formation of an electrode layer in which silicon is used alone or in combination with the negative electrode active material. .
- the binder for electrodes of the lithium secondary battery of the present invention contains a polyurethane water dispersion. Further, the polyurethane water dispersion contains (A) an organic polyisocyanate and (B) a hydrophilic group-containing polyurethane obtained by using at least a compound having one or more active hydrogen groups.
- the (A) organic polyisocyanate used in the preparation of the polyurethane resin aqueous dispersion composition of the binder for an electrode of the lithium secondary battery of the present invention is not particularly limited and is generally used in the technical field.
- Isocyanates can be used. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
- aliphatic polyisocyanate examples include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Examples thereof include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
- alicyclic polyisocyanates examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, 2,2′-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 1 , 3-bis (isocyanatomethyl) cyclohexane and the like.
- aromatic polyisocyanate examples include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1, Examples include 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.
- araliphatic polyisocyanate examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate and the like.
- modified bodies such as dimers and trimers of these organic polyisocyanates and bullet-modified isocyanates can be exemplified. In addition, these can also be used individually or in combination of 2 or more types.
- the organic polyisocyanate is preferably an alicyclic and / or aromatic isocyanate from the viewpoints of binding properties and electrolyte resistance, and 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-bisisocyanate. (Isocyanatomethyl) cyclohexane is particularly preferred.
- the content of the (A) organic polyisocyanate is 50 with respect to the polyurethane in the polyurethane aqueous dispersion. It is preferable that they are mass% or more and 80 mass% or less, and it is more preferable that they are 50 mass% or more and 75 mass% or less.
- the content of the organic polyisocyanate is 50% by mass or more, the electrolytic solution resistance is good, and when the content is 80% by mass or less, a polyurethane water dispersion having a good emulsification property of the polyurethane resin and a stable can be obtained.
- a compound having one or more active hydrogen groups is a compound having one or more hydroxyl groups, amino groups or mercapto groups.
- the active hydrogen group may be either at the molecular end, in the molecule, or both.
- the compound (B) having one or more active hydrogen groups has (B1) a compound having two or more active hydrogen groups and (B2) one or more active hydrogen groups and one or more ionic hydrophilic groups. A compound.
- Examples of the compound (B1) having two or more active hydrogen groups include generally known polyethers, polyesters, polyether esters, polycarbonates, polythioethers, polyacetals, polyolefins, polysiloxanes, fluorine-based and vegetable oil-based compounds. Preferable are compounds having two or more hydroxyl groups at the molecular terminals.
- the molecular weight of the compound having two or more active hydrogen groups is preferably in the range of 50 to 5000 from the viewpoint of workability.
- the ionicity in the compound having one or more active hydrogen groups and one or more ionic hydrophilic groups means an anion or a cation.
- the ionic hydrophilic group include a compound having a carboxyl group, a sulfonic acid group and a salt thereof, and a tertiary or quaternary ammonium salt. Among these, those containing a carboxyl group are preferable from the viewpoint of adhesion to the current collector.
- Examples of the compound containing a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3
- carboxylic acid-containing compounds such as 1,4-diaminobenzoic acid and derivatives thereof and salts thereof
- polyester polyols obtained by using these compounds can be mentioned.
- amino acids such as alanine, aminobutyric acid, aminocaproic acid, glycine, glutamic acid, aspartic acid, and histidine
- carboxylic acids such as succinic acid, adipic acid, maleic anhydride, phthalic acid, and trimellitic anhydride.
- sulfonic acid group-containing compound examples include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6-disulfone.
- acids, sulfonic acid-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid, and derivatives thereof, and polyester polyols, polyamide polyols, and polyamide polyester polyols obtained by copolymerizing these.
- the final polyurethane resin obtained can be made water-dispersible by neutralizing the carboxyl group or sulfonic acid group into a salt.
- the neutralizing agent in this case include non-volatile bases such as sodium hydroxide and potassium hydroxide, tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanolamine, and volatile properties such as ammonia. Examples include bases. Neutralization can be performed before, during or after the urethanization reaction.
- the quaternary ammonium salt it is introduced by quaternization by reaction with an alkyl halide or dialkyl sulfuric acid as described above.
- an alkanolamine such as dimethylaminoethanol or methyldiethanolamine is introduced.
- a neutralizing base is introduced, an organic carboxylic acid such as formic acid or acetic acid, an inorganic acid such as hydrochloric acid or sulfuric acid is added, and when a quaternary ammonium salt is introduced, methyl chloride is used as a quaternizing reagent.
- Alkyl halides such as methyl bromide and dialkyl sulfates such as dimethyl sulfate are used. From the viewpoint of ease of emulsification, a combination of methyldiethanolamine and an organic carboxylic acid or a combination of methyldiethanolamine and dimethylsulfate is preferable.
- the (B2) compound having one or more active hydrogen groups and one or more ionic hydrophilic groups may be used alone or in combination.
- the content of the compound (B2) having one or more active hydrogen groups and one or more ionic hydrophilic groups is at least 0.005 to 0.2 equivalents per 100 parts by weight of the finally obtained polyurethane resin solid content. Is preferable, and 0.01 to 0.1 equivalent is more preferable. If it is the said range, an emulsification characteristic will become favorable.
- a compound having one or more active hydrogen groups and one or more nonionic hydrophilic groups is used in combination. You can also.
- the nonionic group-containing compound is preferably a compound having a molecular weight of 300 to 20,000 containing at least 30% by weight of repeating units of ethylene oxide and containing at least one active hydrogen in the molecule.
- Nonionic group-containing compounds such as ethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or monoalkyl ethers thereof Or the polyester polyether polyol obtained by copolymerizing these is mentioned.
- a nonionic group-containing compound it is preferable to use at least 1 to 30 parts by weight, particularly 5 to 20 parts by weight of the compound per 100 parts by weight of the final polyurethane resin solid content.
- the average hydroxyl value of the compound (B) having one or more active hydrogen groups is 300 mgKOH / g to 2000 mgKOH / g, more preferably 350 mgKOH / g to 2000 mgKOH / g, and most preferably 400 mgKOH / g to 2000 mgKOH / g. If it is the said range, electrolyte solution resistance will become favorable.
- a chain extender is used in combination as the compound having one or more active hydrogen groups.
- a diamine or a polyamine that also functions to introduce an internal cross-linked structure is used.
- diamines include ethylenediamine, trimethylenediamine, piperazine, isophoronediamine, xylylenediamine, 4,4′-biphenyldiamine, 4,4′-methylenedianiline, 4,4′-oxydianiline, and the like.
- polyamines include diethylenetriamine, dipropylenetriamine, and triethylenetetramine.
- a surfactant may be used to disperse the hydrophilic group-containing polyurethane.
- a nonionic surfactant is preferably used.
- the use of a surfactant increases the weight reduction rate of the film when immersed in a carbonate-based solvent, so it is preferable not to use it as much as possible.
- the molecular weight of the hydrophilic group-containing polyurethane in the polyurethane water dispersion is preferably as large as possible by introducing a branched structure or an internal cross-linked structure, and preferably has a weight average molecular weight of 50,000 or more. This is because when the molecular weight is increased to make it insoluble in a solvent, a coating film excellent in electrolytic solution resistance can be obtained.
- the method for producing the polyurethane water dispersion is not particularly limited, but generally has reactivity with isocyanate groups contained in polyols, hydrophilic functional group-introducing materials, single-chain polyols and chain extenders. Stoichiometric excess of polyisocyanate (equivalent ratio of isocyanate group to reactive functional group 1: 0.5 to 0.98) from the sum of functional groups without solvent or organic solvent having no active hydrogen After reacting in the reaction to synthesize an isocyanate-terminated urethane prepolymer, the hydrophilic functional group is neutralized and dispersed and emulsified in water.
- an equivalent chain extender (equivalent ratio of isocyanate group to chain extender 1: 0.5 to 0.95) less than the remaining isocyanate group is added to remove the isocyanate group and chain extender in the emulsion micelle.
- a polyamine is subjected to an interfacial polymerization reaction to form a urea bond.
- the crosslinking density in the emulsified micelle is improved, and a three-dimensional crosslinked structure is formed.
- a coating film having excellent electrolytic solution resistance can be obtained.
- the polyurethane water dispersion can be obtained by removing the solvent used as needed.
- the polyurethane water dispersion of the present invention has a total content of aromatic ring structure or alicyclic structure in the hydrophilic group-containing polyurethane of 40% by mass in the polyurethane. % Or more is preferable, and 43 mass% or more is more preferable.
- the aqueous polyurethane resin dispersion of the present invention preferably has an acid value representing the carboxyl group content of 3 mgKOH / g or more.
- the acid value is 3 mgKOH / g or more, the dispersibility in water is good.
- the acid value was measured according to JIS K 1557.
- a solvent that is inert with the isocyanate group and can dissolve the urethane prepolymer to be generated may be used.
- these solvents include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, propylene glycol monomethyl ether acetate and the like. These hydrophilic organic solvents used in the reaction are preferably finally removed.
- the crosslinking density of the hydrophilic group-containing polyurethane of the present invention is preferably 0.3 or more and 1.0 or less per 1000 molecular weight of the polyurethane resin aqueous dispersion.
- the crosslinking density can be determined by calculation according to the equation shown in Equation 1.
- an organic polyisocyanate (A) having a molecular weight MW A1 and a functional group number F A1 is WA A1 g
- an organic polyisocyanate (A) having a molecular weight MW A2 and a functional group number F A2 is WA 2 g
- a molecular weight MW Aj and a functional group number F Aj organic polyisocyanate (A) is W Aj g (j is an integer of 1 or more)
- the compound (B) having a molecular weight MW B1 and one or more active hydrogen groups having the functional group number F B1 is W B1 g
- a compound (B) having one or more active hydrogen groups having a molecular weight MW B2 and a functional group number F B2 is represented by W B2 g
- a compound (B) having one or more active hydrogen groups having a molecular weight MW Bk and a functional group number F Bk is represented by W.
- Equation 1 Equation 1 below It can be determined.
- the crosslink density is 0.3 or higher, the crosslink density is high, so that the electrolytic solution resistance and the elastic modulus at 60 ° C. are good. It becomes easy to obtain a layer.
- the film formed from the polyurethane water dispersion is immersed in the electrolyte under a specific temperature condition for a specific time, and the weight after immersion Evaluation can be made by measuring the rate of increase or the weight reduction rate after drying the film after immersion under reduced pressure.
- the electrolyte solution is not particularly limited as long as it is an organic solvent used in a non-aqueous electrolyte solution of a normal lithium secondary battery.
- a carbonate compound, a lactone compound, an ether compound, a sulfolane compound, a dioxolane compound, a ketone compound, A nitrile compound, a halogenated hydrocarbon compound, etc. can be mentioned.
- carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylene glycol dimethyl carbonate, propylene glycol dimethyl carbonate, ethylene glycol diethyl carbonate, vinylene carbonate, lactones such as ⁇ -butyl lactone, Ethers such as dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, sulfolanes such as sulfolane and 3-methylsulfolane, dioxolanes such as 1,3-dioxolane, 4-methyl-2- Ketones such as pentanone, nitriles such as acetonitrile, pyropionitrile, valeronitrile, benzonitrile, 1,2-di Halogenated hydrocarbons such as Roroetan, other methyl formate,
- organic solvents it is particularly preferable to contain at least one non-aqueous solvent selected from the group consisting of carbonates because of excellent solubility, dielectric constant and viscosity of the electrolyte.
- the polyurethane water dispersion of the present invention has five types of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, with a coating film formed from the hydrophilic group-containing polyurethane having an electrolytic solution resistance as a carbonate-based mixed solvent. It is preferable that the weight increase rate of the film after immersion for 3 days at 60 ° C. in a mixed solvent (composition of 1: 1: 1: 1: 1 by weight) is 50 wt% or less, and 40 wt% or less. More preferably it is.
- a carbonate-based mixed solvent a mixed solvent composed of five types of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate (composition having a weight ratio of 1: 1: 1: 1: 1) is used. It is preferable that the elastic modulus at 60 ° C. of the swollen film after immersion for 3 days under the condition of ° C. is 10 MPa or more, and more preferably 100 MPa or more. The elastic modulus at 60 ° C. of the swollen film was the value of the dynamic viscoelasticity measurement result in the temperature range of ⁇ 20 ° C. to 150 ° C. using Rheogel-E4000 manufactured by UBM.
- a carbonate-based mixed solvent a mixed solvent consisting of five types of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate (composition with a weight ratio of 1: 1: 1: 1: 1). It is preferable that the weight reduction rate of the film after drying under reduced pressure at 80 ° C. for 24 hours is preferably 10% or less, and more preferably 5% or less.
- the weight reduction rate of the film after drying under reduced pressure at 80 ° C. for 24 hours under a condition of 60 ° C. for 3 days exceeds 10%, the component of the film is eluted in the electrolytic solution. This is not preferable because there is a concern that the component transferred to the positive electrode side through the liquid deteriorates in acid value, thereby degrading battery performance.
- the lithium secondary battery using the polyurethane water dispersion of the present invention comprises a positive electrode and a negative electrode, a separator provided between the positive electrode and the negative electrode and isolating both, lithium as a supporting electrolyte in a solvent for conducting lithium ions It is comprised with the electrolyte layer containing the nonaqueous electrolyte solution which melt
- the positive electrode and the negative electrode used in the lithium secondary battery using the polyurethane water dispersion of the present invention include an electrode active material, a conductive agent, a current collector of the electrode active material, and an electrode active material and a conductive agent bound to the current collector. It is composed of a binder to be worn.
- a lithium secondary battery using the polyurethane water dispersion of the present invention is composed of an electrode manufactured using the polyurethane water dispersion as the binder.
- the polyurethane water dispersion of the present invention can be used for either the positive electrode or the negative electrode, but is particularly preferably used as a binder for the negative electrode.
- PVDF polyvinylidene fluoride
- PVDF polyvinylidene fluoride
- PVDF copolymer resins such as copolymers with HFP
- PFMV perfluoromethyl vinyl ether
- TFE tetrafluoroethylene
- fluororesins such as polytetrafluoroethylene (PTFE) and fluororubber
- SBR rubber
- EPDM ethylene-propylene rubber
- the positive electrode active material used for the positive electrode of the lithium secondary battery using the polyurethane water dispersion of the present invention is not particularly limited as long as it can insert and desorb lithium ions.
- Examples include metal oxides such as CuO, Cu 2 O, MnO 2 , MoO 3 , V 2 O 5 , CrO 3 , MoO 3 , Fe 2 O 3 , Ni 2 O 3 , CoO 3 , LixCoO 2 , LixNiO 2.
- LixMn 2 O 4 , LiFePO 4 and other complex oxides of lithium and transition metals TiS 2 , MoS 2 , NbSe 3 and other metal chalcogenides, polyacene, polyparaphenylene, polypyrrole, polyaniline and other conductive polymers Compounds and the like.
- the negative electrode active material used for the negative electrode of the lithium secondary battery using the polyurethane water dispersion of the present invention is not particularly limited as long as it is capable of inserting / extracting metallic lithium or lithium ions.
- carbon materials such as natural graphite, artificial graphite, non-graphitizable carbon, and graphitizable carbon can be used.
- metallic materials such as metallic lithium, alloys, tin compounds, lithium transition metal nitrides, crystalline metal oxides, amorphous metal oxides, silicon compounds, conductive polymers, etc. can be used.
- a conductive agent is used for a positive electrode and a negative electrode of a lithium secondary battery using the polyurethane water dispersion of the present invention.
- the conductive agent any electronic conductive material that does not adversely affect the battery performance can be used.
- carbon black such as acetylene black and ketchin black is used, but natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon whisker, carbon fiber and metal (copper, nickel, aluminum,
- a conductive material such as silver, gold, etc.) powder, metal fiber, or conductive ceramic material may be used. These can be included as a mixture of two or more.
- the amount added is preferably 0.1 to 30% by weight, particularly preferably 0.2 to 20% by weight, based on the amount of active material.
- any electronic conductor can be used as long as it does not adversely affect the constructed battery.
- a positive electrode current collector aluminum, titanium, stainless steel, nickel, calcined carbon, conductive polymer, conductive glass, etc., in addition to aluminum for the purpose of improving adhesiveness, conductivity, and oxidation resistance.
- a material obtained by treating the surface of copper or copper with carbon, nickel, titanium, silver or the like can be used.
- molded bodies such as a film form, a sheet form, a net form, the punched or expanded thing, a lath body, a porous body, and a foam other than foil shape, are also used.
- the thickness is not particularly limited, but a thickness of 1 to 100 ⁇ m is usually used.
- separators used for ordinary lithium secondary batteries can be used without particular limitation, and examples thereof include porous resins made of polyethylene, polypropylene, polyolefin, polytetrafluoroethylene, ceramics, nonwoven fabrics, and the like. It is done.
- the electrolytic solution may be an electrolytic solution used for a normal lithium secondary battery, and includes general ones such as an organic electrolytic solution and an ionic liquid.
- electrolyte salt examples include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCl, LiBr, LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiI, LiAlCl 4. , NaClO 4, NaBF 4, and the like can be mentioned NaI, in particular, LiPF 6, LiBF 4, LiClO 4, inorganic lithium salts such as LiAsF 6, organic represented by LiN (SO 2 CxF2x + 1) (SO 2 CyF2y + 1) A lithium salt can be mentioned.
- x and y represent 0 or an integer of 1 to 4, and x + y is 2 to 8.
- LiN (SO 2 F) 2 LiN (SO 2 CF 3 ) (SO 2 C 2 F 5 ), LiN (SO 2 CF 3 ) (SO 2 C 3 F 7 ) LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 C 2 F 5 ) (SO 2 C 3 F 7 ), LiN (SO 2 C 2 F 5 ) (SO 2 C 4 F 9 ) and the like.
- LiPF 6 LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiN (SO 2 F) 2 , LiN (SO 2 C 2 F 5 ) 2 or the like as the electrolyte because it has excellent electrical characteristics.
- the above electrolyte salt may be used alone or in combination of two or more.
- Such a lithium salt is desirably contained in the electrolytic solution at a concentration of usually 0.1 to 2.0 mol / liter, preferably 0.3 to 1.5 mol / liter.
- the organic solvent for dissolving the electrolyte salt is not particularly limited as long as it is an organic solvent used for a non-aqueous electrolyte of a normal lithium secondary battery.
- carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylene glycol dimethyl carbonate, propylene glycol dimethyl carbonate, ethylene glycol diethyl carbonate, vinylene carbonate, lactones such as ⁇ -butyl lactone, Ethers such as dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, sulfolanes such as sulfolane and 3-methylsulfolane, dioxolanes such as 1,3-dioxolane, 4-methyl-2- Ketones such as pentanone, nitriles such as acetonitrile, pyropionitrile, valeronitrile, benzonitrile, 1,2-di Halogenated hydrocarbons such as Roroetan, other methyl formate,
- organic solvents it is particularly preferable to contain one or more types of non-aqueous solvents selected from the group consisting of carbonates because they are excellent in electrolyte solubility, dielectric constant and viscosity.
- the polymer compound used in the polymer electrolyte or polymer gel electrolyte is a polymer such as ether, ester, siloxane, acrylonitrile, vinylidene fluoride, hexafluoropropylene, acrylate, methacrylate, styrene, vinyl acetate, vinyl chloride, oxetane, or a co-polymer thereof.
- examples thereof include a polymer having a polymer structure or a crosslinked product thereof, and the polymer may be one type or two or more types.
- the polymer structure is not particularly limited, but a polymer having an ether structure such as polyethylene oxide is particularly preferable.
- the liquid type battery contains an electrolytic solution
- the gel type battery contains a precursor solution in which a polymer is dissolved in the electrolytic solution
- the solid electrolyte battery contains an uncrosslinked polymer in which an electrolyte salt is dissolved in a battery container.
- the above-mentioned components are mixed to prepare a paste-like electrode material, and an aluminum foil or a copper foil that serves as a current collector
- the dispersion medium may be volatilized by applying to the substrate.
- ⁇ Thickeners such as water-soluble polymers can be used as a viscosity modifier for pasting electrode materials.
- celluloses such as carboxymethylcellulose (CMC), methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose;
- ⁇ ⁇ polycarboxylic acid compounds such as polyacrylic acid and sodium polyacrylate; polyvinylpyrrolidone, etc.
- Compounds having a vinylpyrrolidone structure Polyacrylamide, polyethylene oxide, polyvinyl alcohol, sodium alginate, xanthan gum, carrageenan, guar gum, agar, starch and the like can be used, among which carboxymethyl cellulose salt Is preferred.
- the mixing method and order of the above components are not particularly limited.
- the active material and the conductive agent can be mixed and used in advance.
- mortar, mill mixer, planetary ball mill can be used.
- a ball mill such as a shaker type ball mill, a mechano-fusion, or the like can be used.
- the lithium secondary battery using the polyurethane water dispersion of the present invention can be formed into a cylindrical shape, a coin shape, a square shape, or any other shape, and the basic configuration of the battery is the same regardless of the shape.
- the design can be changed according to the situation.
- a wound body in which a negative electrode obtained by applying a negative electrode active material to a negative electrode current collector and a positive electrode obtained by applying a positive electrode active material to a positive electrode current collector are wound via a separator. It is housed in a battery can, sealed with a non-aqueous electrolyte injected, and insulating plates placed on top and bottom.
- a disc-shaped negative electrode, a separator, a disc-shaped positive electrode, and a stainless steel plate are stacked and stored in a coin-type battery can, and a non-aqueous electrolyte is injected. Sealed.
- the present invention will be described in more detail by way of examples of polyurethane resin aqueous dispersions, but the present invention is not limited to the following examples.
- Example 1 Kuraray polyol P-520 (trade name, manufactured by Kuraray Co., Ltd., average hydroxyl value 224 mgKOH / g, number of active hydrogen atoms 2) 34.0 weight in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Parts, trimethylolpropane (3 active hydrogen atoms) 3.0 parts by weight, dimethylolpropionic acid (2 active hydrogen atoms 2) 4.8 parts by weight, dicyclohexylmethane diisocyanate 54.2 parts by weight, methyl ethyl ketone 60 parts by weight And a reaction at 75 ° C.
- Kuraray polyol P-520 (trade name, manufactured by Kuraray Co., Ltd., average hydroxyl value 224 mgKOH / g, number of active hydrogen atoms 2) 34.0 weight in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 6.0% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution prepared by diluting 4.0 parts by weight of diethylenetriamine (3 active hydrogen atoms) with 30 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C.
- 20 parts by weight of ethyl cellosolve is added to 20 parts by weight of the obtained polyurethane water dispersion, and the resultant is poured on a Teflon (registered trademark) processed plate so that the dry film thickness is about 200 ⁇ m, and further at 60 ° C. for 4 hours.
- Test pieces were prepared by drying at 80 ° C. for 2 hours and further at 130 ° C. for 2 hours.
- a carbonate-based mixed solvent a mixed solvent composed of five kinds of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate (weight ratio: 1) : 1: 1: 1: 1 composition).
- the polyurethane aqueous dispersion of the present invention was measured for the rate of increase in weight of the film after immersion of the film formed from the polyurethane water dispersion in the mixed solvent in the mixed solvent at 60 ° C. for 3 days. Moreover, the elastic modulus at 60 degreeC of the swelling film
- Example 2 Kuraray polyol P-520 (trade name, manufactured by Kuraray Co., Ltd., average hydroxyl value 224 mgKOH / g, number of active hydrogen atoms 2) 27.0 weight in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Parts, 5.2 parts by weight of trimethylolpropane (3 active hydrogen atoms), 4.8 parts by weight of dimethylolpropionic acid (2 active hydrogen atoms), 28.0 parts by weight of dicyclohexylmethane diisocyanate, 28.0 parts by weight of isophorone diisocyanate And 60 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C.
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 7.6% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution prepared by diluting 15.8 parts by weight of piperazine hexahydrate (2 active hydrogen atoms) with 70 parts by weight of warm water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C.
- Example 3 ETERNACOLL UH-50 (trade name, manufactured by Ube Industries, average hydroxyl value 224 mgKOH / g, number of active hydrogen atoms 2) 22.4 weight in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Part, trimethylolpropane (active hydrogen atom number 3) 5.2 parts by weight, dimethylolpropionic acid (active hydrogen atom number 2) 4.8 parts by weight, dicyclohexylmethane diisocyanate 60.6 parts by weight, methyl ethyl ketone 60 parts by weight And a reaction at 75 ° C.
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 8.3% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution prepared by diluting 15.8 parts by weight of piperazine hexahydrate (2 active hydrogen atoms) with 70 parts by weight of warm water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C.
- Example 4 A four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube was charged with Newpol BPE-20NK (trade name, manufactured by Sanyo Chemical Industries, bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, activity 2) 22.3 parts by weight of hydrogen atoms, 5.0 parts by weight of trimethylolpropane (3 active hydrogen atoms), 4.8 parts by weight of dimethylolpropionic acid (2 active hydrogen atoms), 56.9 parts of dicyclohexylmethane diisocyanate Part by weight and 60 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C.
- Newpol BPE-20NK trade name, manufactured by Sanyo Chemical Industries, bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, activity 22.3 parts by weight of hydrogen atoms, 5.0 parts by weight of trimethylolpropane (3 active
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 5.8% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an amine aqueous solution obtained by diluting 11.0 parts by weight of methylenedianiline (2 active hydrogen atoms) with 70 parts by weight of methyl ethyl ketone was added, and chain extension reaction was performed for 1 hour. The solvent was removed under reduced pressure at 50 ° C.
- Example 5 A four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube was charged with Newpol BPE-20NK (trade name, manufactured by Sanyo Chemical Industries, bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, activity Number of hydrogen atoms 2) 9.0 parts by weight, trimethylolpropane (active hydrogen atoms 3) 7.1 parts by weight, dimethylolpropionic acid (active hydrogen atoms 2) 4.8 parts by weight, dicyclohexylmethane diisocyanate 62.7 Part by weight and 60 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C.
- Newpol BPE-20NK trade name, manufactured by Sanyo Chemical Industries, bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, activity Number of hydrogen atoms 2 9.0 parts by weight, trimethylolpropane (active hydrogen atoms
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 9.9% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution prepared by diluting 16.4 parts by weight of methylenedianiline (2 active hydrogen atoms) with 90 parts by weight of methyl ethyl ketone was added to carry out a chain extension reaction for 1 hour.
- Example 6 Adeca polyether BPX-11 (trade name, manufactured by ADEKA, propylene oxide adduct of bisphenol A, average hydroxyl value of 312 mgKOH / g, activity, in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube 2) 25.0 parts by weight of hydrogen, 5.0 parts by weight of trimethylolpropane (3 active hydrogen atoms), 4.8 parts by weight of dimethylolpropionic acid (2 active hydrogen atoms), 58.0 dicyclohexylmethane diisocyanate Part by weight and 60 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C.
- Adeca polyether BPX-11 (trade name, manufactured by ADEKA, propylene oxide adduct of bisphenol A, average hydroxyl value of 312 mgKOH / g, activity, in a four-necked flask equipped with a stirrer, reflux
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 5.4% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution prepared by diluting 7.2 parts by weight of xylylenediamine (2 active hydrogen atoms) with 80 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C.
- Example 7 6.4 parts by weight of 1,4-cyclohexanedimethanol (2 active hydrogen atoms), trimethylolpropane (3 active hydrogen atoms) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube 7.1 parts by weight, dimethylolpropionic acid (number of active hydrogen atoms 2) 7.8 parts by weight, dicyclohexylmethane diisocyanate 72.0 parts by weight, methyl ethyl ketone 60 parts by weight are reacted at 75 ° C. for 4 hours.
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 8.4% was obtained.
- the solution was cooled to 45 ° C., neutralized by adding 5.9 parts by weight of triethylamine, and then 300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer.
- an amine aqueous solution obtained by diluting 6.7 parts by weight of ethylenediamine (number of active hydrogen atoms 2) with 70 parts by weight of water was added, and a chain extension reaction was performed for 1 hour.
- the solvent was removed under reduced pressure at 50 ° C.
- Example 8 6.4 parts by weight of 1,4-cyclohexanedimethanol (2 active hydrogen atoms), trimethylolpropane (3 active hydrogen atoms) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube 7.1 parts by weight, dimethylolpropionic acid (number of active hydrogen atoms 2) 7.8 parts by weight, dicyclohexylmethane diisocyanate 72.0 parts by weight, methyl ethyl ketone 60 parts by weight are reacted at 75 ° C. for 4 hours.
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 8.4% was obtained.
- This solution was cooled to 45 ° C., an aqueous solution in which 2.3 parts by weight of sodium hydroxide was dissolved in 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer.
- an amine aqueous solution obtained by diluting 6.7 parts by weight of ethylenediamine (number of active hydrogen atoms 2) with 70 parts by weight of water was added, and a chain extension reaction was performed for 1 hour.
- the solvent was removed under reduced pressure at 50 ° C.
- Comparative Example 1 ETERNACOLL UH-100 (trade name, manufactured by Ube Industries, average hydroxyl value 112 mgKOH / g, number of active hydrogen atoms 2) 41.0 weight in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Parts, 4.5 parts by weight of trimethylolpropane (3 active hydrogen atoms), 4.8 parts by weight of dimethylolpropionic acid (2 active hydrogen atoms), 46.0 parts by weight of dicyclohexylmethane diisocyanate, and 60 parts by weight of methyl ethyl ketone were added.
- ETERNACOLL UH-100 (trade name, manufactured by Ube Industries, average hydroxyl value 112 mgKOH / g, number of active hydrogen atoms 2) 41.0 weight in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Parts, 4.5 parts by weight of
- Comparative Example 2 41.0 weight of Kuraray polyol P-1020 (trade name, manufactured by Kuraray Co., Ltd., average hydroxyl value 112 mgKOH / g, number of active hydrogen atoms 2) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Parts, 4.5 parts by weight of trimethylolpropane (3 active hydrogen atoms), 4.8 parts by weight of dimethylolpropionic acid (2 active hydrogen atoms), 46.0 parts by weight of dicyclohexylmethane diisocyanate, and 60 parts by weight of methyl ethyl ketone were added.
- Kuraray polyol P-1020 trade name, manufactured by Kuraray Co., Ltd., average hydroxyl value 112 mgKOH / g, number of active hydrogen atoms 2
- a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 9.1% based on the nonvolatile content This solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added to neutralize, 300 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution prepared by diluting 17.6 parts by weight of piperazine hexahydrate (2 active hydrogen atoms) with 80 parts by weight of warm water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C.
- Example 3 In Comparative Example 3 in which ETERNCOLLU UH-50 in Example 3 was replaced with ETERNCOLLU UH-100, the content of the structure having an aromatic or alicyclic group was lower than that of polyurethane. Under the conditions, the weight increase rate of the film after being immersed for 3 days is increased and the resistance to electrolyte solution is poor. Moreover, the elasticity modulus at 60 degreeC of the swelling film
- Example 4 In Comparative Example 4 in which diethylenetriamine in Example 1 was replaced with ethylenediamine, the index indicating the branch density per 1000 resin molecular weight of polyurethane was low, and a film immersed in a carbonate solvent for 3 days at 60 ° C. for 24 days at 80 ° C. The weight reduction rate of the film after drying under reduced pressure for a long time increases.
- the binder of the present invention can be used as a binder for an electrode for a lithium secondary battery, and an electrode manufactured using the binder can improve charge / discharge characteristics. Used in the manufacture of secondary batteries.
- the obtained lithium secondary battery can be used in various portable devices such as mobile phones, notebook computers, personal digital assistants (PDAs), video cameras, and digital cameras, as well as medium-sized devices for industrial, electric bicycles, and electric vehicles. Or it can use for a large sized lithium secondary battery.
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Abstract
Description
1)ポリウレタン水分散体を含有するリチウム二次電池の電極用結着剤であって、前記ポリウレタン水分散体が、少なくとも(A)有機ポリイソシアネート及び(B)1個以上の活性水素基を有する化合物を用いて得られる親水基含有ポリウレタンを含有し、前記(A)有機ポリイソシアネートの含有量が、前記親水基含有ポリウレタンに対して50質量%以上80質量%以下であり、且つ、前記(B)1個以上の活性水素基を有する化合物が、(B1)2個以上の活性水素基を有する化合物及び(B2)1個以上の活性水素基と1個以上のイオン性親水基を有する化合物を含有することを特徴とするリチウム二次電池の電極用結着剤を提供する。
2)前記1)記載のポリウレタン樹脂水分散体は、前記(B)2個以上の活性水素基を有する化合物と、前記(C)1個以上の活性水素基と1個以上の親水基とを有する化合物の平均水酸基価が300mgKOH/g以上であることが好ましい。
3)前記1)記載のポリウレタン樹脂水分散体は、芳香環構造または脂環構造を含み、かつ芳香環構造または脂環構造の含有割合の合計が40質量%以上であることが好ましい。
4)前記1)記載のポリウレタン樹脂水分散体は、該ポリウレタンの分子量1000あたりの分岐密度を示す指標が0.3~1.0の範囲であることが好ましい。
5)前記1)記載のポリウレタン樹脂水分散体から形成された皮膜を電解液に60℃条件下3日間浸漬後の皮膜の重量増加率が50%以下であることが好ましい。
6)前記1)記載のポリウレタン樹脂水分散体から形成された皮膜を電解液に60℃条件下3日間浸漬後の膨潤皮膜の60℃における弾性率が10MPa以上であることが好ましい。
7)前記1)記載のポリウレタン樹脂水分散体から形成された皮膜を電解液に60℃条件下3日間浸漬した皮膜を、80℃で24時間減圧乾燥した後の皮膜の重量減少率が10wt%以下であることが好ましい。
1に示す式によって計算することにより求めることができる。すなわち、分子量MWA1、官能基数FA1の有機ポリイソシアネート(A)をWA1 gと、分子量MWA2及び官能基数FA2の有機ポリイソシアネート(A)をWA2 gと、分子量MWAj及び官能基数FAjの有機ポリイソシアネート(A)をWAj g(jは1以上の整数)と、分子量MWB1及び官能基数FB1の1以上の活性水素基を有する化合物(B)をWB1 gと、分子量MWB2及び官能基数FB2の1以上の活性水素基を有する化合物(B)をWB2 gと、分子量MWBk及び官能基数FBkの1以上の活性水素基を有する化合物(B)をWBk g(kは1以上の整数)とを反応せしめて得られたポリウレタン水分散体に含まれる樹脂固形分の1000分子量あたりの架橋密度は、下記の数1により計算で求めることができる。架橋密度が、0.3以上では架橋密度が高いため耐電解液性や60℃における弾性率が良好であり、1.0以下であれば電極層作成時にひび割れを生じ難くなるため、最適な電極層を得ることが容易となる。
以下、ポリウレタン樹脂水分散体の実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
実施例1
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP-520(商品名、クラレ社製、平均水酸基価224mgKOH/g、活性水素原子数2)34.0重量部、トリメチロールプロパン(活性水素原子数3)3.0重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート54.2重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量6.0%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素原子数3) 4.0重量部を水30重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.64)。
得られたポリウレタン水分散体20重量部に対してエチルセロソルブ20重量部を加え、乾燥膜厚が約200μmになるようにテフロン(登録商標)加工板上に流して、60℃で4時間、さらに80℃で2時間、さらに130℃で2時間乾燥して試験片を作成した。耐電解液性を判断するための具体的な方法としては、カーボネート系の混合溶媒として、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート、エチレンカーボネート、プロピレンカーボネートの5種類からなる混合溶媒(重量比で1:1:1:1:1となる組成)を用いて試験を実施した。本発明のポリウレタン水分散体は、耐電解液性が前記ポリウレタン水分散体から形成された皮膜を前記混合溶媒に60℃条件下で3日間浸漬後の皮膜の重量増加率を測定した。また、60℃条件下で3日間浸漬後の膨潤皮膜の60℃における弾性率を測定した。さらには、60℃条件下3日間浸漬した皮膜を、80℃で24時間減圧乾燥した後の皮膜の重量減少率を測定した。
以下の実施例2~比較例4についても同様に評価した。
実施例2
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP-520(商品名、クラレ社製、平均水酸基価224mgKOH/g、活性水素原子数2)27.0重量部、トリメチロールプロパン(活性水素原子数3)5.2重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート28.0重量部、イソホロンジイソシアネート28.0重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量7.6%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ピペラジン・6水和物(活性水素原子数2) 15.8重量部を温水70重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.42)。
実施例3
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにETERNACOLL UH-50(商品名、宇部興産社製、平均水酸基価224mgKOH/g、活性水素原子数2)22.4重量部、トリメチロールプロパン(活性水素原子数3)5.2重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート60.6重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量8.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ピペラジン・6水和物(活性水素原子数2) 15.8重量部を温水70重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.42)。
実施例4
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにニューポールBPE-20NK(商品名、三洋化成社製、ビスフェノールAのエチレンオキサイド付加物、平均水酸基価360mgKOH/g、活性水素原子数2)22.3重量部、トリメチロールプロパン(活性水素原子数3)5.0重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート56.9重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量5.8%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、メチレンジアニリン(活性水素原子数2) 11.0重量部をメチルエチルケトン70重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.41)。
実施例5
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにニューポールBPE-20NK(商品名、三洋化成社製、ビスフェノールAのエチレンオキサイド付加物、平均水酸基価360mgKOH/g、活性水素原子数2)9.0重量部、トリメチロールプロパン(活性水素原子数3)7.1重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート62.7重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量9.9%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、メチレンジアニリン(活性水素原子数2) 16.4重量部をメチルエチルケトン90重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.56)。
実施例6
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにアデカポリエーテルBPX-11(商品名、ADEKA社製、ビスフェノールAのプロピレンオキサイド付加物、平均水酸基価312mgKOH/g、活性水素原子数2)25.0重量部、トリメチロールプロパン(活性水素原子数3)5.0重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート58.0重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量5.4%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、キシリレンジアミン(活性水素原子数2) 7.2重量部を水80重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.41)。
実施例7
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコに1,4-シクロヘキサンジメタノール(活性水素原子数2)6.4重量部、トリメチロールプロパン(活性水素原子数3)7.1重量部、ジメチロールプロピオン酸(活性水素原子数2)7.8重量部、ジシクロヘキシルメタンジイソシアネート72.0重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量8.4%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを5.9重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素原子数2) 6.7重量部を水70重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.56)。
実施例8
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコに1,4-シクロヘキサンジメタノール(活性水素原子数2)6.4重量部、トリメチロールプロパン(活性水素原子数3)7.1重量部、ジメチロールプロピオン酸(活性水素原子数2)7.8重量部、ジシクロヘキシルメタンジイソシアネート72.0重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量8.4%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、水300重量部に水酸化ナトリウム2.3重量部を溶解させた水溶液を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素原子数2) 6.7重量部を水70重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.56)。
比較例1
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにETERNACOLL UH-100(商品名、宇部興産社製、平均水酸基価112mgKOH/g、活性水素原子数2)41.0重量部、トリメチロールプロパン(活性水素原子数3)4.5重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート46.0重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量6.0%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ピペラジン・6水和物(活性水素原子数2) 8.3重量部を温水40重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.34)。
比較例2
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP-1020(商品名、クラレ社製、平均水酸基価112mgKOH/g、活性水素原子数2)41.0重量部、トリメチロールプロパン(活性水素原子数3)4.5重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート46.0重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量6.0%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ピペラジン・6水和物(活性水素原子数2) 8.3重量部を温水40重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.34)。
比較例3
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにETERNACOLL UH-50(商品名、宇部興産社製、平均水酸基価224mgKOH/g、活性水素原子数2)27.0重量部、トリメチロールプロパン(活性水素原子数3)5.2重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、イソホロンジイソシアネート55.2重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量9.1%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ピペラジン・6水和物(活性水素原子数2) 17.6重量部を温水80重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.42)。
比較例4
攪 拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP-520(商品名、クラレ社製、平均水酸基価224mgKOH/g、活性水素原子数2)34.0重量部、トリメチロールプロパン(活性水素原子数3)3.0重量部、ジメチロールプロピオン酸(活性水素原子数2)4.8重量部、ジシクロヘキシルメタンジイソシアネート54.5重量部、メチルエチルケトン60重量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量6.0%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを3.6重量部加え中和後、水300重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素原子数2) 3.7重量部を水40重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体を得た(架橋密度:0.23)。
[遊離のイソシアネート基含有量]JIS K 7301に準じて測定した。
[水性ポリウレタン樹脂分散体中の不揮発分の重量]JIS K 6828に準じて測定した。
[水性ポリウレタン樹脂組成物の樹脂固形分中の架橋密度]数1の式より算出した。
[芳香環構造の含有割合、脂環構造の含有割合、芳香環構造または脂環構造の含有割合の合計]親水基含有ポリウレタンを構成する分子構造における芳香環構造、脂環構造の質量%から算出した。
[酸価]JIS K 1557に準じて測定した。
Claims (7)
- ポリウレタン水分散体を含有するリチウム二次電池の電極用結着剤であって、
前記ポリウレタン水分散体が、少なくとも(A)有機ポリイソシアネート及び(B)1個以上の活性水素基を有する化合物を用いて得られる親水基含有ポリウレタンを含有し、
前記(A)有機ポリイソシアネートの含有量が、前記親水基含有ポリウレタンに対して50質量%以上80質量%以下であり、且つ、
前記(B)1個以上の活性水素基を有する化合物が、(B1)2個以上の活性水素基を有する化合物及び(B2)1個以上の活性水素基と1個以上のイオン性親水基を有する化合物を含有する
ことを特徴とするリチウム二次電池の電極用結着剤。 - 前記(B)1個以上の活性水素基を有する化合物の平均水酸基価が300mgKOH/g以上であることを特徴とする、請求項1に記載のリチウム二次電池の電極用結着剤。
- 前記親水基含有ポリウレタンが、芳香環構造または脂環構造を含み、かつ芳香環構造または脂環構造の含有割合の合計が40質量%以上であることを特徴とする、請求項1または2に記載のリチウム二次電池の電極用結着剤。
- 前記親水基含有ポリウレタンが、該ポリウレタンの分子量1000あたり0.3以上1.0以下の架橋密度であることを特徴とする、請求項1~3のいずれか1項に記載のリチウム二次電池の電極用結着剤。
- 前記親水基含有ポリウレタンから形成された皮膜を電解液に60℃条件下3日間浸漬後の皮膜の重量増加率が50%以下であることを特徴とする、請求項1~4のいずれか1項に記載のリチウム二次電池の電極用結着剤。
- 前記親水基含有ポリウレタンから形成された皮膜を電解液に60℃条件下3日間浸漬後の膨潤皮膜の60℃における弾性率が10MPa以上であることを特徴とする、請求項1~5のいずれか1項に記載のリチウム二次電池の電極用結着剤。
- 前記親水基含有ポリウレタンから形成された皮膜を電解液に60℃条件下3日間浸漬した皮膜を、80℃で24時間減圧乾燥した後の皮膜の重量減少率が10%以下であることを特徴とする、請求項1~6のいずれか1項に記載のリチウム二次電池の電極用結着剤。
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