Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/56—Acrylamide; Methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
  • C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
  • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• • 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
• • 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
  • H01M4/139—Processes of manufacture
• • 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
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/42—Acrylic resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/423—Polyamide resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
• • 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

• This disclosure relates to an electricity storage device binder aqueous solution, an electricity storage device slurry, an electricity storage device electrode, an electricity storage device separator, an electricity storage device separator/electrode laminate, and an electricity storage device.
• the applicant is considering a method of using water-soluble polymers as binders in electricity storage devices.
• the problem that the present invention aims to solve is to provide an aqueous binder solution for producing an electricity storage device that has excellent pencil hardness, breaking strength, initial coulombic efficiency, and discharge capacity retention rate.
• the present disclosure provides the following: (Item 1) An aqueous binder solution for an electricity storage device, the electricity storage device binder aqueous solution contains a water-soluble polymer, (meth)acrylamide, and (meth)acrylonitrile, the water-soluble polymer comprises 0.01% to 1% by weight of a polymerization initiator unit; The aqueous binder solution for an electricity storage device, wherein the content of the (meth)acrylamide relative to the water-soluble polymer is 0.01 ppm by mass or more and less than 1000 ppm by mass.
• the electricity storage device slurry contains a water-soluble polymer, (meth)acrylamide, (meth)acrylonitrile, and water, the water-soluble polymer comprises 0.01% to 1% by weight of a polymerization initiator unit; The content of the (meth)acrylamide relative to the water-soluble polymer is equal to or greater than 0.01 ppm by mass and less than 1000 ppm by mass.
• the electricity storage device slurry according to the above item containing an electrode active material.
• the electricity storage device slurry according to the preceding item comprising non-conductive particles.
• Item 5 Item 11.
• An electricity storage device electrode having a current collector formed thereon a dried product of the electricity storage device slurry according to any one of the preceding items.
• An electricity storage device separator having a substrate on which a dried product of the electricity storage device slurry according to any one of the preceding items is provided.
• An electricity storage device separator/electrode laminate having a dried product of the electricity storage device slurry according to any one of the preceding items on the active material side of an electrode.
• An electricity storage device comprising the electricity storage device electrode described in the above item.
• (Item 10) An electricity storage device comprising the electricity storage device separator/electrode laminate described in the above item.
• (Item A1) The aqueous binder solution for an electricity storage device according to the above items or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 1 mol % to 99.998 mol % of (meth)acrylamide units.
• (Item A2) The aqueous binder solution for an electricity storage device or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 10 mol % to 99.9 mol % of (meth)acrylamide units.
• (Item A3) The aqueous binder solution for an electricity storage device or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 20 mol % or more and less than 99.65 mol % of (meth)acrylamide units.
• (Item A4) The aqueous binder solution for an electricity storage device or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 55 mol % to 95 mol % of (meth)acrylamide units.
• (Item A7) The aqueous binder solution for an electricity storage device or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 20% by mass or more and less than 99.65% by mass of (meth)acrylamide units.
• (Item A8) The aqueous binder solution for an electricity storage device according to the above items or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 55% by mass to 95% by mass of (meth)acrylamide units.
• the water-soluble polymer contains an N-monosubstituted mono(meth)acrylamide unit, and the N-monosubstituted mono(meth)acrylamide is represented by the following structural formula: (R m1 represents a hydrogen atom or a methyl group. R m2 represents a substituted or unsubstituted alkyl group or an acetyl group. R m3 and R m4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a hydroxyl group, an amino group, or an acetyl group. The amino group is represented by -NR ma R mb .
• R ma and R mb each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
• substituent of the substituted alkyl group include a hydroxy group, an amino group, an acetyl group, and a sulfonic acid group.
• the N-monosubstituted mono(meth)acrylamide is one or more selected from the group consisting of monoalkyl(meth)acrylamide, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt, and dimethylaminoethyl(meth)acrylate benzyl chloride quaternary salt.
• the water-soluble polymer contains an N-disubstituted mono(meth)acrylamide unit, and the N-disubstituted mono(meth)acrylamide is represented by the following structural formula:
• R d1 represents a hydrogen atom or a methyl group.
• R d2 and R d3 each independently represent a substituted or unsubstituted alkyl group or an acetyl group, or R 2 and R 3 taken together represent a group which forms a ring structure.
• R d4 and R d5 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a hydroxyl group, an amino group, or an acetyl group.
• the amino group is represented by -NR da R db .
• R da and R db each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
• substituent of the substituted alkyl group include a hydroxy group, an amino group, an acetyl group, and a sulfonic acid group.
• the N-disubstituted mono(meth)acrylamide is one or more selected from the group consisting of N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, and (meth)acryloylmorpholine.
• the unsaturated hydrocarbon sulfonic acid or a salt thereof is one or more selected from the group consisting of (meth)allyl sulfonic acid and sodium (meth)allyl sulfonate.
• (Item A40) The aqueous binder solution for an electricity storage device or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 10% by mass to 70% by mass of a hydroxyl group-containing monomer unit.
• (Item A41) The aqueous binder solution for an electricity storage device or the slurry for an electricity storage device according to the above items, wherein the water-soluble polymer contains 25% by mass to 45% by mass of a hydroxyl group-containing monomer unit.
• the hydroxyl group-containing monomer is one or more selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxyethyl vinyl ether.
• aqueous binder solution for an electricity storage device disclosed herein, it is possible to manufacture an electricity storage device that has excellent pencil hardness, breaking strength, initial coulombic efficiency, and discharge capacity retention rate.
• the range of the values of each physical property, content, etc. may be set as appropriate (e.g., by selecting from the values described in each item below).
• the range of the value ⁇ may be, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 ... etc.
• ingredients, conditions, values, etc. are not limited to those described in the specification.
• ⁇ amount (A/B) means the ⁇ amount ( ⁇ ) of A relative to 100 ⁇ % of B.
• ⁇ can be expressed, for example, in mass%, mol%, or parts by mass.
• ⁇ amount can be expressed, for example, in content or amount used.
• ⁇ ratio (A/B) means the ⁇ ratio calculated by the formula "A ⁇ B". Examples of the ⁇ ratio include mass ratio and molar ratio.
• non-volatile content refers to the total mass of components other than organic solvents and water.
• the non-volatile content of object A is the total mass of components remaining when 1 g of object A is heated at 105°C and reaches a constant weight.
• (Meth)acrylic means “at least one selected from the group consisting of acrylic and methacrylic".
• (Meth)acrylate means “at least one selected from the group consisting of acrylate and methacrylate”.
• (Meth)acryloyl means “at least one selected from the group consisting of acryloyl and methacryloyl”.
• alkyl groups include straight-chain alkyl groups, branched alkyl groups, and cycloalkyl groups.
• straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decamethyl groups.
• Branched alkyl group means a group that does not have a cyclic structure, in which at least one hydrogen atom of a linear alkyl group is replaced by an alkyl group.
• branched alkyl groups include i-propyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl groups.
• cycloalkyl groups include monocyclic cycloalkyl groups, bridged-ring cycloalkyl groups, and condensed-ring cycloalkyl groups. Note that a cycloalkyl group in which at least one hydrogen atom is replaced by an alkyl group is also considered a cycloalkyl group.
• “Monocyclic ring” means a ring structure formed by covalent carbon bonds with no internal bridges. "Fused ring” means a ring structure in which two or more monocyclic rings share two atoms in common (i.e., each ring shares one edge with the other (fused)). "Bridged ring” means a ring structure in which two or more monocyclic rings share three or more atoms in common.
• Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl groups.
• bridged ring cycloalkyl groups include tricyclodecyl, adamantyl, and norbornyl groups.
• Alkyl groups also include groups that combine linear alkyl groups, branched alkyl groups, and cycloalkyl groups. Examples of such combined groups include cycloalkylalkyl groups.
• salts include inorganic salts and organic salts.
• Organic salt means a salt in which the cationic portion is a metal cation.
• inorganic salts examples include sodium salts, lithium salts, calcium salts, etc.
• organic salts examples include ammonium salts and amine salts.
• the present disclosure provides an aqueous binder solution for an electrical storage device, comprising: the electricity storage device binder aqueous solution contains a water-soluble polymer, (meth)acrylamide, and (meth)acrylonitrile, the water-soluble polymer comprises 0.01% to 1% by weight of a polymerization initiator unit;
• the present invention relates to an aqueous binder solution for an electricity storage device, wherein the content of the (meth)acrylamide relative to the water-soluble polymer is 0.01 ppm by mass or more and less than 1000 ppm by mass.
• Water-soluble polymer polymer>
• the water-soluble polymers may be used alone or in combination of two or more.
• Water-soluble means that when 0.5 g of the compound is dissolved in 100 g of water at 25°C, the water-insoluble content is less than 0.5 mass% (less than 2.5 mg).
• water-insoluble content examples include less than 0.5% by mass, less than 0.4% by mass, less than 0.3% by mass, less than 0.2% by mass, less than 0.1% by mass, and 0% by mass.
• the (meth)acrylamides may be used alone or in combination of two or more.
• the mol% content ((meth)acrylamide units/water-soluble polymer) can be, for example, 99.998 mol%, 99.99 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, etc.
• the content is preferably 1 mol% to 99.998 mol%, more preferably 10 mol% to 99.9 mol%, even more preferably 20 mol% or more and less than 99.65 mol%, and particularly preferably 55 mol% to 95 mol%.
• the reason for this preference can be, for example, improved dispersibility and improved storage stability.
• the mass% content ((meth)acrylamide units/water-soluble polymer) can be, for example, 99.998 mass%, 99.99 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, etc.
• the content is preferably 1 mass% to 99.998 mass%, more preferably 10 mass% to 99.9 mass%, even more preferably 20 mass% or more and less than 99 mass%, and particularly preferably 55 mass% to 95 mass%.
• the reason for this preference can be, for example, improved dispersibility and improved storage stability.
• the water-soluble polymer may optionally contain N-substituted mono(meth)acrylamide units.
• the N-substituted mono(meth)acrylamides may be used alone or in combination of two or more.
• N-substituted mono(meth)acrylamide means a compound having one (meth)acrylamide group in which one or more of the hydrogen atoms on the nitrogen has been replaced with a group other than hydrogen.
• R 1 is a hydrogen atom or a methyl group.
• N-substituted mono(meth)acrylamides examples include N-monosubstituted mono(meth)acrylamides and N,N-disubstituted mono(meth)acrylamides.
• the N-monosubstituted mono(meth)acrylamide is represented by the following structural formula: (R m1 represents a hydrogen atom or a methyl group.
• R m2 represents a substituted or unsubstituted alkyl group or an acetyl group.
• R m3 and R m4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a hydroxyl group, an amino group, or an acetyl group.
• the amino group is represented by -NR ma R mb .
• R ma and R mb each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the substituent of the substituted alkyl group include a hydroxy group, an amino group, an acetyl group, and a sulfonic acid group.
• N-monosubstituted mono(meth)acrylamides examples include monoalkyl(meth)acrylamides, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt, and dimethylaminoethyl(meth)acrylate benzyl chloride quaternary salt.
• “Monoalkyl (meth)acrylamide” refers to a compound in which one hydrogen atom directly bonded to the nitrogen atom of (meth)acrylamide is replaced with an unsubstituted alkyl group.
• Examples of monoalkyl(meth)acrylamides include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl(meth)acrylamide.
• the N,N-disubstituted mono(meth)acrylamide is represented by the following structural formula: (R d1 represents a hydrogen atom or a methyl group.
• R d2 and R d3 each independently represent a substituted or unsubstituted alkyl group or an acetyl group, or R 2 and R 3 taken together represent a group which forms a ring structure.
• R d4 and R d5 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a hydroxyl group, an amino group, or an acetyl group.
• the amino group is represented by -NR da R db .
• R da and R db each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
• substituent of the substituted alkyl group include a hydroxy group, an amino group, an acetyl group, and a sulfonic acid group.
• N-disubstituted mono(meth)acrylamides examples include dialkyl(meth)acrylamides and (meth)acryloylmorpholine.
• Dialkyl (meth)acrylamide refers to a compound in which the two hydrogen atoms directly bonded to the nitrogen atom of (meth)acrylamide are replaced with unsubstituted alkyl groups.
• dialkyl(meth)acrylamides examples include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N,N-dipropyl(meth)acrylamide.
• the mol% content is, for example, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 19 mol%, 17 mol%, 15 mol%, 13 mol%, 11 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.7 mol%, 0.5 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, 0.3 mol%, 0.25 mol%, 0.20 mol%, 0.15 mol%, 0.10 mol%, 0.08 mol%, 0.06 mol%, 0.05 mol%, 0.03 mol%, 0.01 mol%,
• the content is preferably 0 mol% to 80 mol%, more preferably 1 mol% to 60 mol%, even more preferably 0.001 mol% or more and less than 5 mol%, and particularly preferably 0.001 to 1 mol%.
• the mass % content is, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, %, 0.9 mass%, 0.7 mass%, 0.5 mass%, 0.45 mass%, 0.4 mass%, 0.35 mass%, 0.3 mass%, 0.25 mass%, 0.20 mass%, 0.15 mass%, 0.10 mass%, 0.08 mass%, 0.06 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, 0.009 mass%, 0.007 mass%, 0.005 mass%, 0.003 mass%, 0.001 mass%, 0 mass%, etc.
• the mol% content is, for example, 0 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 19 mol%, 17 mol%, 15 mol%, 13 mol%, 11 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.7 mol%, 0.5 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, 0.3 mol%, 0.25 mol%, 0.20 mol%, 0.15 mol%, 0.10 mol%, 0.08 mol%, 0.06 mol%, 0.05 mol%, 0.03 mol%, 0.01 mol
• the content is preferably 0 mol% to 80 mol%, more preferably 0 mol% to 20 mol%, even more preferably 0.001 mol% or more and less than 5 mol%, and particularly preferably 0.001 to 1 mol%.
• the mass% content is, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, %, 0.9 mass%, 0.7 mass%, 0.5 mass%, 0.45 mass%, 0.4 mass%, 0.35 mass%, 0.3 mass%, 0.25 mass%, 0.20 mass%, 0.15 mass%, 0.10 mass%, 0.08 mass%, 0.06 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, 0.009 mass%, 0.007 mass%, 0.005 mass%, 0.003 mass%, 0.001 mass%, 0 mass%, etc.
• the mol% content is, for example, 0 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 19 mol%, 17 mol%, 15 mol%, 13 mol%, 11 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.7 mol%, 0.5 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, 0.3 mol%, 0.25 mol%, 0.20 mol%, 0.15 mol%, 0.10 mol%, 0.08 mol%, 0.06 mol%, 0.05 mol%, 0.03 mol%, 0.01 mol
• the content is preferably 0 mol% to 80 mol%, more preferably 0 mol% to 20 mol%, even more preferably 0.001 mol% or more and less than 5 mol%, and particularly preferably 0.001 to 1 mol%.
• the mass% content is, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, %, 0.9 mass%, 0.7 mass%, 0.5 mass%, 0.45 mass%, 0.4 mass%, 0.35 mass%, 0.3 mass%, 0.25 mass%, 0.20 mass%, 0.15 mass%, 0.10 mass%, 0.08 mass%, 0.06 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, 0.009 mass%, 0.007 mass%, 0.005 mass%, 0.003 mass%, 0.001 mass%, 0 mass%, etc.
• the water-soluble polymer may optionally contain unsaturated hydrocarbyl sulfonic acid and/or salt units thereof.
• the unsaturated hydrocarbyl sulfonic acid and/or salt thereof may be used alone or in combination of two or more.
• Unsaturated hydrocarbon sulfonic acid means a sulfonic acid whose structure other than the sulfonic acid (salt) group consists only of carbon atoms and hydrogen atoms.
• unsaturated hydrocarbon sulfonic acids or salts thereof include vinyl sulfonic acid, styrene sulfonic acid, (meth)allyl sulfonic acid, sodium vinyl sulfonate, sodium styrene sulfonate, and sodium (meth)allyl sulfonate.
• mol% content examples include 1.0 mol%, 0.95 mol%, 0.9 mol%, 0.85 mol%, 0.8 mol%, 0.75 mol%, 0.7 mol%, 0.65 mol%, 0.6 mol%, 0.55 mol%, 0.5 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, 0.3 mol%, 0.25 mol%, 0.20 mol%, 0.15 mol%, 0.10 mol%, 0.08 mol%, 0.06 mol%, 0.05 mol%, 0.03 mol%, 0.01 mol%, 0.009 mol%, 0.007 mol%, 0.005 mol%, 0.003 mol%, 0.001 mol%, and 0 mol%, etc.
• the content is preferably 0 mol% to 1.0 mol%, more preferably 0.001 mol% to 0.5 mol%, even more preferably 0.001 mol% to 0.1 mol%, and particularly preferably less than 0.01 mol%.
• Reasons for this include, for example, improved pencil hardness and improved breaking strength.
• Examples of the mass% content include 1.0 mass%, 0.95 mass%, 0.9 mass%, 0.85 mass%, 0.8 mass%, 0.75 mass%, 0.7 mass%, 0.65 mass%, 0.6 mass%, 0.55 mass%, 0.5 mass%, 0.45 mass%, 0.4 mass%, 0.35 mass%, 0.3 mass%, 0.25 mass%, 0.20 mass%, 0.15 mass%, 0.10 mass%, 0.08 mass%, 0.06 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, 0.009 mass%, 0.007 mass%, 0.005 mass%, 0.003 mass%, 0.001 mass%, and 0 mass%, etc.
• the content is preferably 0% by mass to 1.0% by mass, more preferably 0.001% by mass to 0.5% by mass, and even more preferably 0.001% by mass to 0.1% by mass.
• Reasons for this being preferable include, for example, improved pencil hardness and improved breaking strength.
• the neutralization rate [unit substance amount of unsaturated hydrocarbon sulfonate/(unit substance amount of unsaturated hydrocarbon sulfonate+unit substance amount of unsaturated hydrocarbon sulfonic acid)] can be, for example, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, etc. In one embodiment, the neutralization rate is preferably 10% to 100%.
• the water-soluble polymer may optionally include multifunctional monomer units.
• the multifunctional monomers may be used alone or in combination of two or more.
• Polyfunctional monomer means a monomer having two or more ethylenically unsaturated double bonds.
• polyfunctional monomers examples include polyfunctional (meth)acrylamide compounds, tri(allyl group)-containing monomers, and tri((meth)acryloyl group)-containing triazines.
• polyfunctional (meth)acrylamide compound refers to a compound having two or more (meth)acrylamide groups.
• R 1 is a hydrogen atom or a methyl group.
• polyfunctional (meth)acrylamide compounds include N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N-[tris(3-(meth)acrylamidopropoxymethyl)methyl](meth)acrylamide, N,N-bis(2-(meth)acrylamidoethyl)(meth)acrylamide, N,N-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bis(meth)acrylamide, and N,N-1,2-ethanediylbis ⁇ N-[2-((meth)acryloylamino)ethyl](meth)acrylamide ⁇ .
• tri(allyl group)-containing monomers examples include triallyl isocyanurate, triallyl trimellitate, triallylamine, triallyl (meth)acrylamide, etc.
• tri((meth)acryloyl group)-containing triazines examples include 1,3,5-tri((meth)acryloyl)-1,3,5-triazine and 1,3,5-tri((meth)acryloyl)hexahydro-1,3,5-triazine.
• the mol% content (polyfunctional monomer unit/water-soluble polymer) can be, for example, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.7 mol%, 0.5 mol%, 0.3 mol%, 0.1 mol%, 0.05 mol%, 0 mol%, etc.
• the content is preferably 0 to 10 mol%, and more preferably 0.05 to 2 mol%.
• the mass% content can be, for example, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.7 mass%, 0.5 mass%, 0.3 mass%, 0.1 mass%, 0.05 mass%, 0 mass%, etc.
• the content is preferably 0 mass% to 10 mass%, and more preferably 0.05 mass% to 2 mass%.
• the water-soluble polymer may optionally contain unsaturated carboxylic acid and/or salt units thereof.
• the unsaturated carboxylic acid and/or salt thereof may be used alone or in combination of two or more.
• unsaturated carboxylic acids or salts thereof include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, sodium (meth)acrylate, sodium crotonate, sodium maleate, sodium fumarate, sodium itaconate, lithium (meth)acrylate, lithium crotonate, lithium maleate, lithium fumarate, lithium itaconate, calcium (meth)acrylate, calcium crotonate, calcium maleate, calcium fumarate, calcium itaconate, ammonium (meth)acrylate, ammonium crotonate, ammonium maleate, ammonium fumarate, and ammonium itaconate.
• the mol% content (unsaturated carboxylic acid and/or its salt unit/water-soluble polymer) can be, for example, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0 mol%, etc.
• the content is preferably 0 mol% to 70 mol%, and more preferably 2 mol% to 40 mol%.
• the mass% content (unsaturated carboxylic acid and/or its salt unit/water-soluble polymer) can be, for example, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 29 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0 mass%, etc.
• the content is preferably 0 mass% to 70 mass%, more preferably 0 mass% to 40 mass%, and even more preferably 2 mass% to 40 mass%.
• the neutralization rate [unsaturated carboxylate unit substance amount/(unsaturated carboxylate unit substance amount+unsaturated carboxylic acid unit substance amount)] can be, for example, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, etc. In one embodiment, the neutralization rate is preferably 10% to 100%.
• the water-soluble polymer may optionally contain ⁇ , ⁇ -unsaturated nitrile units.
• the ⁇ , ⁇ -unsaturated nitriles may be used alone or in combination of two or more.
• ⁇ , ⁇ -unsaturated nitriles examples include (meth)acrylonitrile, ⁇ -chloro(meth)acrylonitrile, ⁇ -ethyl(meth)acrylonitrile, vinylidene cyanide, etc.
• the mol% content ( ⁇ , ⁇ -unsaturated nitrile units/water-soluble polymer) can be, for example, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0 mol%, etc.
• the content is preferably 0 mol% to 50 mol%, more preferably 0 mol% to 40 mol%, and even more preferably 10 mol% to 40 mol%.
• the mass% content ( ⁇ , ⁇ -unsaturated nitrile units/water-soluble polymer) can be, for example, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0 mass%, etc.
• the content is preferably 0 mass% to 50 mass%, more preferably 0 mass% to 30 mass%, and even more preferably 5 mass% to 30 mass%.
• the water-soluble polymer may optionally include alkoxyalkyl (meth)acrylate units.
• the alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more.
• alkoxyalkyl (meth)acrylates include methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 1-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 1-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 1-methoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 1-ethoxypropyl (meth)acrylate, propoxymethyl (meth)acrylate, 2-propoxyethyl
• the mole percent content (alkoxyalkyl (meth)acrylate units/water-soluble polymer) can be, for example, 40 mole percent, 35 mole percent, 30 mole percent, 25 mole percent, 20 mole percent, 15 mole percent, 10 mole percent, 9 mole percent, 5 mole percent, 4 mole percent, 2 mole percent, 1 mole percent, 0 mole percent, etc.
• the content is preferably 0 mole percent to 40 mole percent.
• the mass% content (alkoxyalkyl (meth)acrylate units/water-soluble polymer) can be, for example, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0 mass%, etc.
• the content is preferably 0 mass% to 60 mass%.
• the water-soluble polymer may optionally include hydroxyl-containing monomer units.
• the hydroxyl-containing monomers may be used alone or in combination of two or more.
• hydroxyl group-containing monomers examples include hydroxyl group-containing (meth)acrylic esters and hydroxyl group-containing vinyl ethers.
• hydroxyl group-containing (meth)acrylic acid esters examples include hydroxyl group-containing linear (meth)acrylic acid esters and hydroxyl group-containing branched (meth)acrylic acid esters.
• hydroxyl group-containing linear (meth)acrylic acid esters examples include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
• hydroxyl group-containing branched (meth)acrylic acid esters examples include 1-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 1-hydroxy-2-methylethyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1-hydroxy-1-methylpropyl (meth)acrylate, 2-hydroxy-1-methylpropyl (meth)acrylate, 3-hydroxy-1-methylpropyl (meth)acrylate, 1-ethyl-2-hydroxyethyl (meth)acrylate, 1-hydroxy-2-methylpropyl (meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, 3-hydroxy-2-methylpropyl (meth)acrylate, and 1,1-dimethyl-2-hydroxyethyl (meth)acrylate
• hydroxyl group-containing vinyl ethers examples include hydroxyalkyl vinyl ethers and polyalkylene glycol monovinyl ethers.
• hydroxyalkyl vinyl ethers examples include hydroxy linear alkyl vinyl ethers, hydroxy branched alkyl vinyl ethers, and hydroxy cycloalkyl vinyl ethers.
• hydroxy linear alkyl vinyl ethers examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 5-hydroxypentyl vinyl ether.
• hydroxy branched alkyl vinyl ethers examples include 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, and 4-hydroxy-2-methylbutyl vinyl ether.
• hydroxycycloalkyl vinyl ethers examples include 4-hydroxycyclopentyl vinyl ether.
• polyalkylene glycol monovinyl ethers examples include polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and polypropylene glycol monovinyl ether.
• polymethylene glycol monovinyl ethers examples include dimethylene glycol monovinyl ether, trimethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, pentamethylene glycol monovinyl ether, hexamethylene glycol monovinyl ether, heptamethylene glycol monovinyl ether, octamethylene glycol monovinyl ether, nonamethylene glycol monovinyl ether, and decamethylene glycol monovinyl ether.
• polyethylene glycol monovinyl ethers examples include diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, hexaethylene glycol monovinyl ether, heptaethylene glycol monovinyl ether, octaethylene glycol monovinyl ether, nonaethylene glycol monovinyl ether, and decaethylene glycol monovinyl ether.
• polypropylene glycol monovinyl ethers examples include dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, hexapropylene glycol monovinyl ether, heptapropylene glycol monovinyl ether, octapropylene glycol monovinyl ether, nonapropylene glycol monovinyl ether, and decapropylene glycol monovinyl ether.
• the mol% content (hydroxyl group-containing monomer units/water-soluble polymer) can be, for example, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0 mol%, etc.
• the content is preferably 0 mol% to 80 mol%, more preferably 5 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%.
• the mass% content (hydroxyl group-containing monomer unit/water-soluble polymer) can be, for example, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0 mass%, etc.
• the content is preferably 0 mass% to 85 mass%, more preferably 10 mass% to 70 mass%, and even more preferably 25 mass% to 45 mass%.
• the polymerization initiators may be used alone or in combination of two or more.
• polymerization initiators examples include azo initiators.
• azo initiators examples include 2,2'-azobis-2-amidinopropane dihydrochloride.
• the mol% content (polymerization initiator units/water-soluble polymer) can be, for example, 1 mol%, 0.95 mol%, 0.9 mol%, 0.85 mol%, 0.8 mol%, 0.75 mol%, 0.7 mol%, 0.65 mol%, 0.6 mol%, 0.55 mol%, 0.5 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, 0.3 mol%, 0.25 mol%, 0.2 mol%, 0.15 mol%, 0.1 mol%, 0.07 mol%, 0.05 mol%, 0.03 mol%, 0.01 mol%, etc.
• the content is preferably 0.01 mol% to 1 mol%.
• the mass% content (polymerization initiator units/water-soluble polymer) can be, for example, 1 mass%, 0.95 mass%, 0.9 mass%, 0.85 mass%, 0.8 mass%, 0.75 mass%, 0.7 mass%, 0.65 mass%, 0.6 mass%, 0.55 mass%, 0.5 mass%, 0.45 mass%, 0.4 mass%, 0.35 mass%, 0.3 mass%, 0.25 mass%, 0.2 mass%, 0.15 mass%, 0.1 mass%, 0.07 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, etc.
• the content is preferably 0.01 mass% to 1 mass%.
• the water-soluble polymer may optionally contain a monomer (other component) unit that is not any of (meth)acrylamide, N-substituted mono(meth)acrylamide, unsaturated hydrocarbon sulfonic acid and/or a salt thereof, polyfunctional monomer, unsaturated carboxylic acid and/or a salt thereof, ⁇ , ⁇ -unsaturated nitrile, alkoxyalkyl (meth)acrylate, and hydroxyl group-containing monomer.
• the other components may be used alone or in combination of two or more.
• Other components include, for example, unsaturated phosphoric acid and/or its salt, alkyl (meth)acrylic acid ester, conjugated diene, aromatic vinyl compound, etc.
• unsaturated phosphoric acids include vinyl phosphonic acid, vinyl phosphate, bis((meth)acryloxyethyl)phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, monomethyl-2-(meth)acryloyloxyethyl phosphate, and 3-(meth)acryloxy-2-hydroxypropane phosphoric acid.
• alkyl (meth)acrylate esters examples include linear alkyl (meth)acrylate esters, branched alkyl (meth)acrylate esters, and alicyclic alkyl (meth)acrylate esters.
• linear alkyl (meth)acrylate esters examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.
• branched alkyl (meth)acrylate esters examples include i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
• alicyclic alkyl (meth)acrylate esters examples include cyclohexyl (meth)acrylate.
• conjugated dienes examples include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear conjugated pentadiene, and substituted and side-chain conjugated hexadienes.
• aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene.
• the mass% content can be, for example, less than 10 mass%, less than 9 mass%, less than 7 mass%, less than 5 mass%, less than 4 mass%, less than 2 mass%, less than 1 mass%, less than 0.9 mass%, less than 0.7 mass%, less than 0.5 mass%, less than 0.4 mass%, less than 0.2 mass%, less than 0.1 mass%, or 0 mass%.
• the content is preferably less than 10 mass%, more preferably less than 5 mass%, even more preferably less than 1 mass%, and particularly preferably 0 mass%.
• the mol% content (other component units/water-soluble polymer) can be, for example, less than 10 mol%, less than 9 mol%, less than 7 mol%, less than 5 mol%, less than 4 mol%, less than 3 mol%, less than 2 mol%, less than 1 mol%, or 0 mol%.
• the content is preferably less than 10 mol%, more preferably less than 5 mol%, even more preferably less than 1 mol%, and particularly preferably 0 mol%.
• the method of preparation includes a pre-polymerization step and a post-polymerization step.
• Prepolymerization step refers to a step of producing (polymerizing) a water-soluble polymer.
• the amount by mass (radical polymerization initiator/monomer group) used in the prepolymerization step can be, for example, 1.0 mass%, 0.9 mass%, 0.8 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.4 mass%, 0.3 mass%, 0.2 mass%, 0.1 mass%, 0.05 mass%, etc.
• the amount used in the prepolymerization step is preferably 0.05 mass% to 1.0 mass%.
• the prepolymerization temperature can be, for example, 100°C, 95°C, 90°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, 50°C, etc. In one embodiment, the prepolymerization temperature is preferably 50°C to 100°C.
• the prepolymerization time can be, for example, 10 hours, 9 hours, 8 hours, 7 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1.5 hours, 1 hour, etc.
• the prepolymerization time is preferably 1 hour to 10 hours, and more preferably 2 hours to 10 hours.
• post-polymerization step refers to a step of adding a polymerization initiator and carrying out a reaction after the pre-polymerization step.
• the post-polymerization step can be carried out once or twice or more.
• the amount by mass (radical polymerization initiator/monomer group) used in the post-polymerization step can be, for example, 1.0 mass%, 0.9 mass%, 0.8 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.4 mass%, 0.3 mass%, 0.2 mass%, 0.1 mass%, 0.05 mass%, etc. In one embodiment, the amount is preferably 0.05 mass% to 1.0 mass%.
• the post-polymerization temperature can be, for example, 100°C, 95°C, 90°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, or 50°C. In one embodiment, the post-polymerization temperature is preferably 50°C to 100°C.
• the post-polymerization time can be, for example, 10 hours, 9 hours, 8 hours, 7 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1.5 hours, 1 hour, etc.
• the post-polymerization time can be preferably 1 hour to 10 hours, and more preferably 2 hours to 10 hours.
• persulfate or a redox-based polymerization initiator may be used as a radical polymerization initiator in either the post-polymerization step or the pre-polymerization step.
• persulfates examples include potassium persulfate and ammonium persulfate.
• redox polymerization initiators examples include combination systems (persulfate and reducing agent).
• reducing agents examples include sodium hydrogen sulfite.
• weight average molecular weight examples include 6 million, 5.5 million, 5 million, 4.5 million, 4 million, 3.5 million, 3 million, 2.5 million, 2 million, 1.5 million, 1 million, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, and 100,000.
• the weight average molecular weight (Mw) is preferably 100,000 to 6 million, and more preferably 350,000 to 6 million.
• Number average molecular weights include, for example, 6 million, 5.5 million, 5 million, 4.5 million, 4 million, 3.5 million, 3 million, 2.5 million, 2 million, 1.5 million, 1 million, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 300,000, 200,000, 100,000, 50,000, and 10,000.
• the number average molecular weight (Mn) is preferably 10,000 or more.
• the molecular weight distribution (water-soluble polymer: Mw/Mn) can be, for example, 15, 14, 13, 11, 10, 9, 7.5, 5, 4, 3, 2.9, 2.5, 2, 1.5, 1.1, etc. In one embodiment, the molecular weight distribution (Mw/Mn) is preferably 1.1 to 15.
• the mass part content ((meth)acrylamide/water-soluble polymer) is, for example, less than 1000 mass ppm, 999 mass ppm, 950 mass ppm, 900 mass ppm, 850 mass ppm, 800 mass ppm, 750 mass ppm, 700 mass ppm, 650 mass ppm, 600 mass ppm, 550 mass ppm, 500 mass ppm, 450 mass ppm, 400 mass ppm, 350 mass ppm, 300 mass ppm, ppm, 250 ppm by mass, 200 ppm by mass, 150 ppm by mass, 100 ppm by mass, 50 ppm by mass, 25 ppm by mass, 10 ppm by mass, 5 ppm by mass, 1 ppm by mass, 0.9 ppm by mass, 0.7 ppm by mass, 0.5 ppm by mass, 0.3 ppm by mass, 0.1 ppm by mass, 0.09 ppm by mass, 0.07 ppm by mass, 0.05
• the mass part content ((meth)acrylonitrile/water-soluble polymer) is, for example, less than 1000 mass ppm, 999 mass ppm, 950 mass ppm, 900 mass ppm, 850 mass ppm, 800 mass ppm, 750 mass ppm, 700 mass ppm, 650 mass ppm, 600 mass ppm, 550 mass ppm, 500 mass ppm, 450 mass ppm, 400 mass ppm, 350 mass ppm, 300 mass ppm
• Examples of the content include 250 ppm by mass, 200 ppm by mass, 150 ppm by mass, 100 ppm by mass, 50 ppm by mass, 25 ppm by mass, 10 ppm by mass, 5 ppm by mass, 1 ppm by mass, 0.9 ppm by mass, 0.7 ppm by mass, 0.5 ppm by mass, 0.3 ppm by mass, 0.1 ppm by mass, 0.09 ppm by mass, 0.07 ppm by
• the mass part content is, for example, less than 2000 mass ppm, 1999 mass ppm, 1950 mass ppm, 1900 mass ppm, 1850 mass ppm, 1800 mass ppm, 1750 mass ppm, 1700 mass ppm, 1650 mass ppm, 1600 mass ppm, 1550 mass ppm, 1500 mass ppm, 1450 mass ppm, 1400 mass ppm, 1350 mass ppm, 1300 mass ppm, 1250 mass ppm, 1200 mass ppm, 1150 mass ppm, 1100 mass ppm, 1050 mass ppm, 1000 mass ppm, 999 mass ppm, 950 mass ppm, 900 mass ppm, 850 mass ppm, ppm by mass, 800 ppm by mass, 750 ppm by mass, 700 ppm by mass, 650 ppm by mass, 600 ppm by mass, 550 ppm by mass, 500 ppm by mass,
• the monomer content can be measured under the following conditions.
• Preparation (standard solution) Monomers ((meth)acrylamide, (meth)acrylonitrile) are collected in a 20 mL screw tube and diluted with ultrapure water to prepare standard aqueous solutions of 2000 ppm, 1000 ppm, 500 ppm, 100 ppm, 10 ppm, 1 ppm, and 0.5 ppm.
• (Meth)acrylamide calibration curve Using a standard solution, measure under the following conditions to create a calibration curve.
• Measurement equipment GC (Agilent 7890B)-MS (Agilent 5977A) Column: InertCap AQUATIC-2 Carrier gas: helium Measurement concentration: 1% by mass (water-soluble polymer concentration) Measurement conditions: 50°C (2 min.) ⁇ 230°C (5 min./min.) Injection volume: 1000 ⁇ L (4) Preparation (sample) Each sample is diluted 50-fold in a screw tube. Measurement is performed under the above conditions, and the monomer content in the sample is calculated from the calibration curve.
• (Meth)acrylamide can be produced by hydrolyzing (meth)acrylonitrile. Therefore, even if (meth)acrylonitrile is not used as a monomer, (meth)acrylonitrile can be present in the reaction system.
• the mass ppm content (sulfur/electricity storage device binder aqueous solution) can be, for example, 1000 ppm, 950 ppm, 900 ppm, 850 ppm, 800 ppm, 750 ppm, 700 ppm, 650 ppm, 600 ppm, 550 ppm, 500 ppm, 450 ppm, 400 ppm, 350 ppm, 300 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 90 ppm, 75 ppm, 50 ppm, 25 ppm, 15 ppm, 14 ppm, 13 ppm, 11 ppm, 10 ppm, 9 ppm, 7 ppm, 5 ppm, 3 ppm, 1 ppm, 0 ppm, etc.
• the content is preferably 1000 ppm or less.
• Reasons for this being preferable include, for example, improved pencil hardness and improved breaking strength.
• the sulfur content can be measured under the following conditions.
• the measurement is performed using an X-ray fluorescence analyzer (ZSX Primus IV, manufactured by Rigaku Corp.)
• the content is expressed as an oxide equivalent value.
• Measurement time Standard Measurement pretreatment: Place in a liquid sample container and cover with polypropylene (PP) film
• Quantitative method Semi-quantitative using the fundamental parameter method When the result is undetectable (0 ppm) using an X-ray fluorescence analyzer, measurement is performed using combustion ion chromatography (AQF-2100H, manufactured by Nitto Seiko Analytical Co., Ltd.).
• the B-type viscosity (electricity storage device binder aqueous solution) can be, for example, 100,000 mPa ⁇ s, 90,000 mPa ⁇ s, 80,000 mPa ⁇ s, 70,000 mPa ⁇ s, 60,000 mPa ⁇ s, 50,000 mPa ⁇ s, 40,000 mPa ⁇ s, 30,000 mPa ⁇ s, 20,000 mPa ⁇ s, 10,000 mPa ⁇ s, 9,000 mPa ⁇ s, 8,000 mPa ⁇ s, 7,000 mPa ⁇ s, 6,000 mPa ⁇ s, 5,000 mPa ⁇ s, 4,000 mPa ⁇ s, 3,000 mPa ⁇ s, 2,000 mPa ⁇ s, 1,000 mPa ⁇ s, etc.
• the B-type viscosity is preferably 1,000 mPa ⁇ s to 100,000 mPa ⁇ s.
• B-type viscosity The measurement conditions (B-type viscosity) are as follows. Non-volatile content: 15% by mass Measurement temperature: 25°C B-type viscometer: Toki Sangyo Co., Ltd. Product name: "B-type viscometer model TVB-10" Viscosity 100 to 10,000 mPa ⁇ s: No. 3 rotor, rotation speed 12 rpm Viscosity over 10,000 to 20,000 mPa ⁇ s: No. 3 rotor, rotation speed 6 rpm Viscosity over 20,000 to 100,000 mPa ⁇ s: No. 4 rotor, rotation speed 6 rpm
• the glass transition temperature (water-soluble polymer) can be, for example, 160°C, 155°C, 150°C, 145°C, 140°C, 135°C, 130°C, 125°C, 120°C, 115°C, 110°C, 105°C, 100°C, 95°C, 90°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, 15°C, 10°C, 5°C, 0°C, etc.
• the glass transition temperature is preferably 0°C or higher, and more preferably 30°C or higher.
• the glass transition temperature (water-soluble polymer) can be calculated by the Fox equation.
• 1/Tg ( W1 / Tg1 )+( W2 / Tg2 )+( W3 / Tg3 )+...+( Wn / Tgn )
• Tg is the glass transition temperature (K) of the polymer to be determined
• W 1 to W n are the mass fractions of the respective monomers
• Tg 1 to Tg n are the glass transition temperatures (homopolymers) (K) of the respective monomers
• the glass transition temperature can be measured by a DSC (differential scanning calorimeter), a DTA (differential thermal analyzer), a TMA (thermomechanical analyzer), or the like.
• the measurement conditions are as follows. Temperature range: -100°C to 300°C Heating rate: 10° C./min
• the glass transition temperature (homopolymer) may be a value described in a literature.
• the literature may be "Chemical Handbook, Basics II, edited by the Chemical Society of Japan (revised 5th edition)", p. 325.
• the glass transition temperature (homopolymer) may be the following temperature.
• Acrylonitrile 105°C
• the mass% content (water-soluble polymer/electricity storage device binder aqueous solution) can be, for example, 25 mass%, 20 mass%, 19 mass%, 15 mass%, 14 mass%, 12 mass%, 10 mass%, 9 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, etc.
• the content is preferably 1 mass% to 25 mass%.
• Water> Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.
• the mass % content (water/electric storage device binder aqueous solution) can be, for example, 99.9 mass %, 99 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, etc. In one embodiment, the content is preferably 75 mass % to 99.9 mass %.
• the mass ratio (water-soluble polymer/water) can be, for example, 0.33, 0.30, 0.25, 0.24, 0.22, 0.20, 0.18, 0.15, 0.12, 0.10, 0.09, 0.07, 0.05, etc. In one embodiment, the mass ratio is preferably 0.05 to 0.33.
• the electrical storage device binder aqueous solution may optionally contain a hydrolysis partial condensate of a polyalkoxysilane.
• the hydrolysis partial condensate may be used alone or in combination of two or more kinds.
• polyalkoxysilanes examples include trialkoxysilanes and tetraalkoxysilanes.
• the trialkoxysilane is represented by the formula: (In the formula, R s1 represents a substituted or unsubstituted alkyl group or alkenyl group. R s2 to R s4 each independently represent an alkyl group.)
• Substituted alkyl group refers to a group in which the hydrogen atoms constituting the alkyl group have been replaced with groups other than hydrogen atoms or alkyl groups.
• substituents examples include an amino group, a mercapto group, an isocyanate group, and a (meth)acryloyloxy group.
• the amino group (amino group-containing group) is represented by the following formula: -NR am1 R am2 (R am1 to R am2 each independently represent a hydrogen atom, an alkyl group, or an aryl group.)
• amino group-containing trialkoxysilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.
• Examples of mercapto group-containing trialkoxysilanes include 3-mercaptopropyltrimethoxysilane.
• trialkoxysilanes containing isocyanate groups include 3-isocyanatepropyltriethoxysilane.
• Examples of (meth)acryloyloxy group-containing trialkoxysilanes include 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane.
• alkenyl groups examples include vinyl groups and allyl groups.
• alkenyl group-containing trialkoxysilanes examples include vinyltrimethoxysilane and vinyltriethoxysilane.
• tetraalkoxysilanes examples include tetramethoxysilane, tetramethoxysilane oligomer, tetraethoxysilane, and tetraethoxysilane oligomer.
• Partial hydrolysis condensate of polyalkoxysilane means a hydrolysis condensate in which an alkoxy group is present. From the viewpoint of not gelling, a partial hydrolysis condensate of polyalkoxysilane is used instead of a complete hydrolysis condensate of polyalkoxysilane.
• the degree of condensation can be, for example, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 19, 17, 15, 14, 13, 12, 11, 10, 9, 5, 3, 2, 1.7, 1.5, 1.4, 1.2, 1.1, 1.01, etc.
• the degree of condensation is preferably 1.01 to 1000, and more preferably 1.01 to 100.
• the weight average molecular weight (hydrolysis partial condensate) can be, for example, 190,000, 170,000, 150,000, 130,000, 100,000, 90,000, 70,000, 50,000, 30,000, 20,000, 10,000, 9,000, 7,500, 5,000, 2,500, 1,000, 900, 750, 500, 250, 200, 175, 160, 150, 125, 110, 100, etc.
• the weight average molecular weight is preferably 100 to 190,000.
• a hydrolyzed partial condensate of polyalkoxysilane can be produced by hydrolyzing and partially condensing 100 parts by mass of polyalkoxysilane in the presence of 0 to 5 parts by mass of an acid catalyst or base catalyst (preferably an acid catalyst) at a reaction temperature of 30 to 60°C for 0.5 to 5.0 hours.
• acid catalysts examples include nitric acid, hydrochloric acid, sulfurous acid, phosphoric acid, formic acid, and acetic acid.
• base catalysts include sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, and amine compounds.
• the mass% content (hydrolyzed partial condensate/electric storage device binder aqueous solution) can be, for example, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4.5 mass%, 4 mass%, 3.5 mass%, 3 mass%, 2.5 mass%, 2 mass%, 1.5 mass%, 1 mass%, 0.9 mass%, 0.5 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, etc. In one embodiment, the content is preferably 0.01 mass% to 10 mass%.
• the electrical storage device binder aqueous solution may optionally contain a binder other than the water-soluble polymer (other binder).
• the other binders may be used alone or in combination of two or more kinds.
• binders include, for example, diene copolymers, fluorine-based copolymers, amide-imide copolymers, and copolymers other than those mentioned above.
• diene copolymers examples include styrene-butadiene copolymers, polybutadiene polymers, acrylonitrile-butadiene copolymers, methyl methacrylate-butadiene copolymers, and carboxy-modified styrene-butadiene copolymers.
• fluorine-based copolymers examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and ethylene-tetrafluoroethylene copolymer (ETFE).
• PVDF polyvinylidene fluoride
• PTFE polytetrafluoroethylene
• FEP tetrafluoroethylene-hexafluoropropylene copolymer
• PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
• ETFE ethylene-tetrafluoroethylene copolymer
• amide-imide copolymers examples include polyamide (PA), polyimide (PI), polyamideimide (PAI), and aromatic polyamide.
• copolymers other than those mentioned above include polyurethane polymers, poly(meth)acrylate polymers, vinyl chloride polymers, vinyl acetate polymers, vinyl acetate-ethylene copolymers, polyethylene, polypropylene, polyethylene terephthalate, polystyrene polymers, alginic acid and/or its salts, etc.
• the part by mass content can be, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, etc.
• the content is preferably 0 parts by mass to 100 parts by mass.
• the electrical storage device binder aqueous solution may optionally contain a dispersion (emulsion).
• the dispersion (emulsion) may be used alone or in combination of two or more kinds.
• Dispersions include, for example, styrene-butadiene copolymer latex, polystyrene polymer latex, polybutadiene polymer latex, acrylonitrile-butadiene copolymer latex, polyurethane polymer latex, polymethyl methacrylate polymer latex, methyl methacrylate-butadiene copolymer latex, polyacrylate polymer latex, vinyl chloride polymer latex, vinyl acetate polymer emulsion, vinyl acetate-ethylene copolymer emulsion, polyethylene emulsion, carboxy-modified styrene
• examples of such materials include polybutadiene copolymer resin emulsion, acrylic resin emulsion, polyethylene, polypropylene, polyethylene terephthalate, polyamide (PA), polyimide (PI), polyamideimide (PAI), aromatic polyamide, alginic acid and its salts, polyvinylidene fluoride (P
• the part by mass content can be, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, etc.
• the content is preferably 0 parts by mass to 100 parts by mass.
• the electrical storage device binder aqueous solution may optionally contain a thickener.
• the thickener may be used alone or in combination of two or more kinds.
• Thickeners include, for example, cellulose-based polymers and/or their salts, polyvinyl alcohols, (modified) poly(meth)acrylic acid and/or its salts, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, oxidized starch, starch phosphate, casein, modified starch, hydrogenated acrylonitrile-butadiene copolymer, etc.
• cellulose-based polymers and/or their salts examples include carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose.
• polyvinyl alcohols examples include copolymers of maleic acid (anhydride) and/or fumaric acid with vinyl alcohol.
• the part by mass content can be, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, etc.
• the content is preferably 0 parts by mass to 100 parts by mass.
• the aqueous binder solution for the electric storage device may optionally contain, as additives, a water-soluble polymer, water, a partial hydrolysis condensate of a polyalkoxysilane, and other agents that do not fall under any of the categories of a binder, a dispersion (emulsion), and a thickener.
• the additives may be used alone or in combination of two or more kinds.
• Additives include, for example, dispersants, leveling agents, antioxidants, etc.
• dispersants examples include anionic dispersants, cationic dispersants, nonionic dispersants, and polymeric dispersants.
• leveling agents examples include surfactants.
• Surfactants include, for example, alkyl surfactants, silicone surfactants, fluorine surfactants, metal surfactants, etc.
• antioxidants include phenol compounds, hydroquinone compounds, organic phosphorus compounds, sulfur compounds, phenylenediamine compounds, and polymeric phenol compounds.
• Polymer-type phenol compound refers to a polymer having a phenol structure.
• the weight average molecular weight is preferably 200 to 1000, and more preferably 600 to 700.
• the content in parts by mass can be, for example, less than 5 parts by mass, less than 4 parts by mass, less than 2 parts by mass, less than 1 part by mass, less than 0.9 parts by mass, less than 0.5 parts by mass, less than 0.4 parts by mass, less than 0.2 parts by mass, less than 0.1 parts by mass, less than 0.09 parts by mass, less than 0.05 parts by mass, less than 0.04 parts by mass, less than 0.02 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.
• the mass% content can be, for example, less than 5 mass%, less than 4 mass%, less than 2 mass%, less than 1 mass%, less than 0.9 mass%, less than 0.5 mass%, less than 0.4 mass%, less than 0.2 mass%, less than 0.1 mass%, less than 0.09 mass%, less than 0.05 mass%, less than 0.04 mass%, less than 0.02 mass%, less than 0.01 mass%, 0 mass%, etc.
• the pH (electric storage device binder aqueous solution) can be, for example, 9, 8.9, 8.5, 8, 7.9, 7.5, 7, 6.9, 6.5, 6, 5.9, 5.6, 5.5, 5.4, 5.2, 5.1, or 5.
• the pH is preferably 5 to 9, and more preferably 5 to 7.
• Electrode storage device binder aqueous solution include, for example, electricity storage device electrode binder aqueous solution, battery electrode binder aqueous solution, non-aqueous secondary battery electrode binder aqueous solution, lithium ion battery electrode binder aqueous solution, sodium ion battery electrode binder aqueous solution, electricity storage device negative electrode binder aqueous solution, battery negative electrode binder aqueous solution, non-aqueous secondary battery negative electrode binder aqueous solution, lithium ion battery negative electrode binder aqueous solution, sodium ion battery negative electrode binder aqueous solution, electricity storage device positive electrode binder aqueous solution, battery positive electrode binder aqueous solution, non-aqueous secondary battery positive electrode binder aqueous solution, lithium ion battery positive electrode binder aqueous solution, sodium ion battery positive electrode binder aqueous solution, electricity storage device separator binder aqueous solution, battery separator binder aqueous solution, non-aqueous solution
• the present disclosure provides an electricity storage device slurry,
• the electricity storage device slurry contains a water-soluble polymer, (meth)acrylamide, (meth)acrylonitrile, and water, the water-soluble polymer comprises 0.01% to 1% by weight of a polymerization initiator unit;
• the present invention relates to an electricity storage device slurry, wherein the content of the (meth)acrylamide relative to the water-soluble polymer is equal to or greater than 0.01 ppm by mass and less than 1000 ppm by mass.
• slurry means a suspension of liquid and solid particles.
• water-soluble polymers examples include, for example, the substances listed above.
• the mass% content (water-soluble polymer/slurry) can be, for example, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.7 mass%, 0.5 mass%, 0.3 mass%, 0.1 mass%, etc. In one embodiment, the content is preferably 0.1 mass% to 10 mass%.
• the mass% content (water/slurry) can be, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, etc. In one embodiment, the content is preferably 30 mass% to 80 mass%.
• the mass% content (hydrolyzed partial condensate/slurry) can be, for example, 5 mass%, 4.5 mass%, 4 mass%, 3.5 mass%, 3 mass%, 2.5 mass%, 2 mass%, 1.5 mass%, 1 mass%, 0.9 mass%, 0.5 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.03 mass%, 0.01 mass%, etc. In one embodiment, the content is preferably 0.01 mass% to 5 mass%.
• the mass ppm content can be, for example, 1000 ppm, 950 ppm, 900 ppm, 850 ppm, 800 ppm, 750 ppm, 700 ppm, 650 ppm, 600 ppm, 550 ppm, 500 ppm, 450 ppm, 400 ppm, 350 ppm, 300 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 90 ppm, 75 ppm, 50 ppm, 25 ppm, 15 ppm, 14 ppm, 13 ppm, 11 ppm, 10 ppm, 9 ppm, 7 ppm, 5 ppm, 3 ppm, 1 ppm, 0 ppm, etc.
• the content is preferably 1000 ppm or less.
• Reasons for this being preferable include, for example, improved pencil hardness and improved breaking strength.
• the content (polymerization initiator unit), content ((meth)acrylamide), content ((meth)acrylonitrile), content (monomer), content (other binder), content (dispersion (emulsion)), and content (thickener) are, for example, the contents described above.
• the electricity storage device slurry contains an electrode active material.
• the electrode active material include a negative electrode active material and a positive electrode active material.
• the electrode active materials may be used alone or in combination of two or more kinds.
• Negative Electrode Active Material examples include carbon materials, materials that are alloyed with lithium, silicon materials, and oxides containing lithium atoms.
• Examples of carbon materials include graphite, low crystalline carbon, carbon black, fullerene, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon fibrils, mesocarbon microbeads (MCMB), pitch-based carbon fibers, and activated carbon.
• MCMB mesocarbon microbeads
• Examples of graphite include natural graphite and artificial graphite.
• Examples of low crystalline carbon include soft carbon and hard carbon.
• Examples of carbon black include ketjen black, acetylene black, channel black, lamp black, oil furnace black, and thermal black.
• Examples of materials that can be alloyed with lithium include lead compounds, tin compounds, arsenic compounds, antimony compounds, and aluminum compounds.
• the silicon oxide is preferably a silicon oxide represented by the composition formula SiO z (0 ⁇ z ⁇ 2, preferably 0.1 ⁇ z ⁇ 1).
• Silicon alloys include silicon-titanium alloys, silicon-zirconium alloys, silicon-nickel alloys, silicon-copper alloys, silicon-iron alloys, silicon-molybdenum alloys, etc.
• the silicon alloy is preferably a silicon-nickel alloy or a silicon-titanium alloy, and more preferably a silicon-titanium alloy.
• the mole percent content (silicon atoms/total metal elements) is preferably 10 mole percent or more, and more preferably 20 mole percent to 70 mole percent.
• the shape of the silicon material can be, for example, single crystal, polycrystalline, amorphous, etc.
• an electrode active material When a silicon material is used as an electrode active material, an electrode active material other than a silicon material may be used in combination.
• Examples of electrode active materials other than silicon materials include carbon materials, conductive polymers, and composite metal oxides.
• An example of a conductive polymer is polyacene.
• the composite metal oxide is represented, for example, by the following general formula.
• a ⁇ B ⁇ O ⁇ (A represents an alkali metal or a transition metal.
• B represents at least one selected from transition metals such as cobalt, nickel, aluminum, tin, and manganese.
• O represents an oxygen atom.
• ⁇ , ⁇ , and ⁇ each independently satisfy the conditions: 0.05 ⁇ 1.10, 0.85 ⁇ 4.00, and 1.5 ⁇ 5.00.)
• the silicon material is preferably silicon covered with a carbon layer, or silicon oxide covered with a carbon layer.
• oxides containing lithium atoms include lithium-transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.
• lithium-transition metal composite oxides include lithium-manganese composite oxide, lithium-nickel composite oxide, lithium-cobalt composite oxide, lithium-iron composite oxide, lithium-titanium composite oxide, lithium-nickel-manganese composite oxide, and lithium-nickel-cobalt composite oxide.
• the mass% content (carbon material and/or material alloyed with lithium/negative electrode active material) can be, for example, 100 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, etc.
• the content is preferably 50 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass%.
• the mass % content (silicon covered with a carbon layer and/or silicon oxide covered with a carbon layer/negative electrode active material) can be, for example, 100 mass %, 90 mass % or more, 75 mass % or more, 50 mass % or more, 25 mass % or more, 10 mass % or more, 5 mass % or more, 2 mass % or more, 1 mass % or more, 0 mass %, etc.
• the mass % content (silicon material/negative electrode active material) can be, for example, 100 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, etc.
• Examples of the positive electrode active material include a positive electrode inorganic active material and a positive electrode organic active material.
• Examples of the positive electrode inorganic active material include transition metal oxides, lithium-transition metal composite oxides, transition metal sulfides, activated carbon, etc.
• the inorganic active material may be partially elementally substituted. By making a carbon source material present during reduction firing, the inorganic active material may be used as an electrode active material covered with a carbon material.
• Examples of the positive electrode organic active material include conductive polymers.
• Examples of conductive polymers include polyacetylene and poly-p-phenylene.
• the shape may be, for example, fine particles, thin film, or the like.
• the average particle size is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 45 ⁇ m, even more preferably 1 to 10 ⁇ m, and particularly preferably 5 ⁇ m.
• particle diameter refers to the maximum distance between any two points on the contour line of a particle.
• Average particle diameter refers to the value calculated as the average particle diameter of particles observed in several to several tens of fields of view using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
• the part by mass content (water-soluble polymer/electrode active material) can be 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1.5 parts by mass, 1 part by mass, 0.5 parts by mass, etc.
• the content is preferably 0.5 parts by mass to 15 parts by mass.
• the slurry may optionally contain a conductive assistant.
• the conductive assistant may be used alone or in combination of two or more kinds.
• Examples of conductive additives include fibrous carbon, carbon black, and metal powder.
• fibrous carbon examples include vapor grown carbon fiber (VGCF), carbon nanotubes (CNT), and carbon nanofibers (CNF).
• VGCF vapor grown carbon fiber
• CNT carbon nanotubes
• CNF carbon nanofibers
• carbon black examples include graphite particles, acetylene black, ketjen black, furnace black, etc.
• metal micropowder examples include copper micropowder, nickel micropowder, aluminum micropowder, silicon micropowder, alloy micropowder, etc.
• the average particle size (metal micropowder) is preferably 10 ⁇ m.
• the content by weight is preferably 0 to 10 parts by weight, and more preferably 0 to 6 parts by weight.
• the electrical storage device slurry contains non-conductive particles.
• the non-conductive particles may be used alone or in combination of two or more kinds.
• non-conductive particles examples include oxide particles, hydroxide particles, nitride particles, covalent crystal particles, sparingly soluble ion crystal particles, clay particles, aluminum particles, barium particles, calcium particles, etc.
• oxide particles include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH), gibbsite (Al(OH) 3 ), bakelite, iron oxide, silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO 3 , ZrO, and alumina-silica composite oxide.
• AlOOH aluminum oxide hydrate
• Al(OH) 3 gibbsite
• bakelite iron oxide, silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO 3 , ZrO, and alumina-silica composite oxide.
• hydroxide particles examples include calcium hydroxide and magnesium hydroxide.
• nitride particles examples include aluminum nitride, silicon nitride, and boron nitride.
• covalently bonded crystal particles examples include silicon and diamond.
• poorly soluble ionic crystal particles examples include barium sulfate, calcium fluoride, barium fluoride, etc.
• clay particles examples include silica, talc, montmorillonite, and other clay particles.
• aluminum particles examples include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH), gibbsite (Al(OH) 3 ), and aluminum nitride.
• barium particles examples include barium sulfate and barium fluoride.
• Examples of calcium particles include calcium hydroxide, magnesium hydroxide, calcium fluoride, etc.
• the non-conductive particles are preferably boehmite, alumina, magnesium oxide, and barium sulfate.
• the average particle size (non-conductive particles) can be, for example, 30 ⁇ m, 25 ⁇ m, 20 ⁇ m, 15 ⁇ m, 10 ⁇ m, 5 ⁇ m, 1 ⁇ m, 0.5 ⁇ m, 0.1 ⁇ m, 0.05 ⁇ m, 0.01 ⁇ m, etc. In one embodiment, the average particle size is preferably 0.01 ⁇ m to 30 ⁇ m.
• the mass% content can be, for example, 99.9 mass%, 95 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, 1 mass%, 0.5 mass%, 0.2 mass%, 0.1 mass%, etc.
• the content is preferably 0.1 mass% to 99.9 mass%.
• the part by mass content can be, for example, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1.5 parts by mass, 1 part by mass, etc.
• the content is preferably 1 part by mass to 15 parts by mass, more preferably 1.5 parts by mass to 14 parts by mass, and even more preferably 2 parts by mass to 12 parts by mass.
• the slurry viscosity adjusting solvent may be used alone or in combination of two or more.
• slurry viscosity adjusting solvents examples include amide solvents, hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, amine solvents, lactone solvents, sulfoxide/sulfone solvents, water, etc.
• amide solvents examples include N-methylpyrrolidone, dimethylformamide, and N,N-dimethylacetamide.
• hydrocarbon solvents examples include toluene, xylene, n-dodecane, and tetralin.
• alcohol solvents examples include methanol, ethanol, 2-propanol, isopropyl alcohol, 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol, etc.
• Ketone solvents include, for example, acetone, methyl ethyl ketone, cyclohexanone, phorone, acetophenone, isophorone, etc.
• Ether solvents include, for example, dioxane and tetrahydrofuran (THF).
• ester solvents examples include benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, and butyl lactate.
• amine solvents examples include o-toluidine, m-toluidine, and p-toluidine.
• lactone solvents examples include gamma-butyrolactone and delta-butyrolactone.
• sulfoxide and sulfone solvents examples include dimethyl sulfoxide and sulfolane.
• the slurry viscosity adjusting solvent is preferably N-methylpyrrolidone.
• the mass% content (slurry viscosity adjusting solvent/slurry) can be, for example, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 to 10 mass%.
• the above-mentioned slurry may optionally contain, as an additive, a water-soluble polymer, water, or other agent that does not fall under any of the following: a binder, a dispersion (emulsion), a thickener, an electrode active material, a non-conductive particle, and a slurry viscosity adjusting solvent.
• a binder a dispersion (emulsion), a thickener, an electrode active material, a non-conductive particle, and a slurry viscosity adjusting solvent.
• the mass% content can be, for example, 0 mass% to 5 mass%, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, etc.
• the parts by weight content can be, for example, 0 parts by weight to 5 parts by weight, less than 1 part by weight, less than 0.1 parts by weight, less than 0.01 parts by weight, 0 parts by weight, etc.
• the above slurry can be produced by mixing a water-soluble polymer, water, and an electrode active material or non-conductive particles, as well as a hydrolyzed partial condensate of polyalkoxysilane, as required, and other binders, dispersions (emulsions), thickeners, slurry viscosity adjusting solvents, and additives.
• mixing means examples include ball mills, sand mills, pigment dispersers, crushers, ultrasonic dispersers, homogenizers, planetary mixers, and Hobart mixers.
• Applications include, for example, electricity storage device electrode slurry, battery electrode slurry, non-aqueous secondary battery electrode slurry, lithium ion battery electrode slurry, sodium ion battery electrode slurry, electricity storage device negative electrode slurry, battery negative electrode slurry, non-aqueous secondary battery negative electrode slurry, lithium ion battery negative electrode slurry, sodium ion battery negative electrode slurry, electricity storage device positive electrode slurry, battery positive electrode slurry, non-aqueous secondary battery positive electrode slurry, lithium ion battery positive electrode slurry, sodium ion battery positive electrode slurry, electricity storage device separator slurry, battery separator slurry, non-aqueous secondary battery separator slurry, lithium ion battery separator slurry, sodium ion battery separator slurry, etc.
• Electrode electrode
• the present disclosure relates to an electricity storage device electrode having a current collector formed from the dried electricity storage device slurry.
• the electricity storage device electrode is obtained by applying the electricity storage device slurry to a current collector and drying it.
• Examples of the current collector include metal materials and carbon materials.
• metal materials include copper, iron, aluminum, nickel, stainless steel, and nickel-plated steel.
• Examples of the form of the metal material include metal foil, metal cylinder, metal coil, metal plate, etc.
• Examples of carbon materials include carbon cloth and carbon paper.
• Examples of the form (carbon material) include carbon plates, thin carbon films, and carbon cylinders.
• Examples of application means include a comma coater, gravure coater, microgravure coater, die coater, bar coater, etc.
• the drying temperature is preferably 60°C to 200°C, and more preferably 70°C to 195°C.
• dry atmospheres include dry air and inert atmospheres.
• the thickness is preferably 5 ⁇ m to 300 ⁇ m, and more preferably 10 ⁇ m to 250 ⁇ m.
• Electrode storage device electrodes include, for example, electricity storage device positive electrodes, electricity storage device negative electrodes, battery electrodes, battery positive electrodes, battery negative electrodes, non-aqueous secondary battery electrodes, non-aqueous secondary battery positive electrodes, non-aqueous secondary battery negative electrodes, lithium ion battery electrodes, lithium ion battery positive electrodes, lithium ion battery negative electrodes, sodium ion battery electrodes, sodium ion battery negative electrodes, etc.
• the present disclosure relates to an electricity storage device separator having a substrate on which a dried product of the electricity storage device slurry is formed.
• the above-mentioned electricity storage device separator can be manufactured by applying the above-mentioned electricity storage device separator slurry to one or both sides of a substrate and drying it.
• Examples of the substrate include porous polyolefin resin substrates and plastic nonwoven fabrics.
• porous polyolefin resin substrate refers to a microporous film containing 30% by mass or more of a resin such as polyolefin or a mixture or copolymer thereof.
• Polyolefin resins can be used alone or in combination of two or more types.
• Examples of polyolefin resins include homopolymers and copolymers of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.
• polyolefins examples include isotactic, syndiotactic, and atactic.
• the polyolefin resin is preferably high density polyethylene, and more preferably high density polyethylene and polypropylene.
• the mass % content (polyolefin resin/substrate) is preferably 30 mass % to 100 mass %, more preferably 40 mass % to 100 mass %, and even more preferably 50 mass % to 100 mass %.
• the porous polyolefin resin substrate may optionally contain a filler or a fiber compound.
• the strength, hardness, and heat shrinkage rate of the porous polyolefin resin substrate can be controlled by the filler and the fiber compound.
• the porous polyolefin resin substrate may be surface-treated as necessary.
• Examples of surface treatments include coating treatment, electromagnetic radiation treatment, and plasma treatment.
• the surface treatment is preferably a coating treatment using a polar group-containing polymer.
• the coating treatment can improve the electrolyte impregnation and adhesion to the dried slurry.
• polar groups include carboxylic acid groups, hydroxyl groups, and sulfonic acid groups.
• the thickness (of the porous polyolefin resin substrate) is preferably 2 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m to 50 ⁇ m.
• Plastic nonwoven fabric An example of the plastic nonwoven fabric is a nonwoven fabric made only of synthetic fibers.
• Synthetic fibers include, for example, polyolefin resins, polyester resins, acrylonitrile resins, polyamide resins, polyvinyl acetate resins, ethylene-vinyl acetate copolymer resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl ether resins, polyvinyl ketone resins, polyether resins, polyvinyl alcohol resins, diene resins, polyurethane resins, phenol resins, melamine resins, furan resins, urea resins, aniline resins, unsaturated polyester resins, alkyd resins, fluorine resins, silicone resins, polyamideimide resins, polyphenylene sulfide resins, polyimide resins, polycarbonate resins, polyazomethine resins, polyesteramide resins, polyetheretherketone resins, poly-p-phenylenebenzobisoxazole resins, polybenzimidazole
• polyolefin resins examples include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl alcohol copolymers, and olefin copolymers.
• polyester resins examples include polyethylene terephthalate (PET) resins, polybutylene terephthalate (PBT) resins, polytrimethylene terephthalate (PPT) resins, polyethylene naphthalate (PEN) resins, polybutylene naphthalate resins, polyethylene isonaphthalate resins, and wholly aromatic polyester resins.
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PPT polytrimethylene terephthalate
• PEN polyethylene naphthalate
• polybutylene naphthalate resins polyethylene isonaphthalate resins
• wholly aromatic polyester resins examples include polyethylene isonaphthalate resins.
• acrylonitrile-based resins examples include polyacrylonitrile, copolymers of acrylonitrile with (meth)acrylic acid derivatives, vinyl acetate, etc.
• polyamide-based resins examples include aliphatic polyamides, fully aromatic polyamides, and semi-aromatic polyamides.
• An example of an aliphatic polyamide is nylon.
• Poly-aromatic polyamide means a polyimide in which part of the aromatic polyamide main chain is an aliphatic chain.
• Fibers other than synthetic resin fibers include, for example, solvent-spun cellulose, fibrillated solvent-spun cellulose, regenerated cellulose, fibrillated regenerated cellulose, natural cellulose fibers, pulped natural cellulose fibers, fibrillated natural cellulose fibers, inorganic fibers, etc.
• the mass% content is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 10 mass% or less.
• Examples of the form (morphology) include single fiber, composite fiber, etc.
• Single fiber means a fiber made of a single resin.
• Composite fiber means a fiber made of two or more types of resin.
• configuration examples include core-sheath type, eccentric type, side-by-side type, sea-island type, orange type, and multi-bimetal type.
• the average fiber diameter (plastic nonwoven fabric) is preferably 1 ⁇ m to 15 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m.
• Average fiber diameter refers to the average fiber diameter of 20 fibers randomly selected from a scanning electron microscope photograph.
• the average pore diameter (plastic nonwoven fabric) is preferably 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m, and even more preferably 5 ⁇ m to 20 ⁇ m.
• Pore diameter refers to the width of the gap between fibers.
• Average pore diameter refers to the average pore diameter of 20 fibers randomly selected from a scanning electron microscope photograph.
• the thickness is preferably 5 ⁇ m to 25 ⁇ m, and more preferably 5 ⁇ m to 15 ⁇ m.
• the production method may, for example, be a method including a coating step of coating a base material with an electricity storage device separator slurry, and a drying step of drying the coated electricity storage device separator slurry.
• Examples of the coating method include a coating method, a printing method, a transfer method, and a dipping method.
• coating methods include blade, rod, reverse roll, lip, die, curtain, and air knife.
• Printing methods include, for example, flexography, screen printing, offset printing, gravure printing, and inkjet printing.
• Transfer methods include, for example, roll transfer and film transfer.
• Examples of the immersion method include dipping.
• drying process examples include air drying, irradiation drying, and vacuum drying.
• air drying examples include warm air drying, hot air drying, and low-humidity air drying.
• radiation drying examples include infrared radiation drying, far-infrared radiation drying, and electron beam radiation drying.
• the drying temperature is preferably 40°C to 90°C, and more preferably 50°C to 80°C.
• the drying time is preferably 5 seconds to 3 minutes, and more preferably 15 seconds to 2 minutes.
• the manufacturing method may optionally include a pressing step.
• Examples of pressing means include die pressing and roll pressing.
• the above-mentioned power storage device separator can be used, for example, as a battery separator, a non-aqueous secondary battery separator, a lithium ion battery separator, a sodium ion battery separator, etc.
• the present disclosure relates to an electricity storage device separator/electrode laminate having a dried product of the electricity storage device slurry on the active material side of an electrode.
• the power storage device separator/electrode laminate is obtained by applying the above power storage device slurry to an electrode and drying it.
• the production method may be, for example, a method including the following steps. (1) A step of applying an electrode material-containing slurry to a current collector; (2) A step of drying the electrode material-containing slurry; (3) A step of pressing the dried electrode material-containing slurry; (4) A step of applying an electricity storage device separator slurry to the dried electrode material-containing slurry; and (5) A step of drying the electricity storage device separator slurry.
• Examples of the coating method, drying method, and pressing method include the methods described above.
• Electrode separator/electrode laminate include, for example, battery separator/electrode laminate, battery separator/negative electrode laminate, battery separator/positive electrode laminate, non-aqueous secondary battery separator/electrode laminate, non-aqueous secondary battery separator/negative electrode laminate, non-aqueous secondary battery separator/positive electrode laminate, lithium ion battery separator/electrode laminate, lithium ion battery separator/negative electrode laminate, lithium ion battery separator/positive electrode laminate, sodium ion battery separator/electrode laminate, sodium ion battery separator/negative electrode laminate, sodium ion battery separator/positive electrode laminate, etc.
• the present disclosure relates to an electricity storage device.
• the power storage device includes the power storage device electrode.
• the power storage device includes the power storage device separator.
• the energy storage device includes the energy storage device separator/electrode laminate.
• the power storage device may optionally contain an electrolyte solution, such as a solution in which a supporting electrolyte is dissolved in a non-aqueous solvent.
• Non-aqueous solvents may be used alone or in combination of two or more.
• non-aqueous solvents examples include chain carbonate solvents, cyclic carbonate solvents, chain ether solvents, cyclic ether solvents, chain ester solvents, cyclic ester solvents, acetonitrile, etc.
• chain carbonate solvents examples include diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.
• Cyclic carbonate solvents include, for example, ethylene carbonate, propylene carbonate, butylene carbonate, etc.
• An example of a chain ether solvent is 1,2-dimethoxyethane.
• Cyclic ether solvents include, for example, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, 1,3-dioxolane, etc.
• chain ester solvents examples include methyl formate, methyl acetate, and methyl propionate.
• cyclic ester solvents examples include gamma-butyrolactone and gamma-valerolactone.
• the non-aqueous solvent is preferably a combination of a cyclic carbonate and a chain carbonate.
• the supporting electrolytes may be used alone or in combination of two or more.
• Examples of the supporting electrolyte include lithium salts.
• Examples of the lithium salt include LiPF6 , LiAsF6 , LiBF4 , LiSbF6 , LiAlCl4, LiClO4 , CF3SO3Li, C4F9SO3Li , CF3COOLi , ( CF3CO ) 2NLi , (CF3SO2 ) 2NLi , ( C2F5SO2 ) NLi , etc.
• the supporting electrolyte is preferably LiPF6 , LiClO4 , or CF3SO3Li .
• the non-aqueous electrolyte may optionally contain a film-forming agent.
• the film-forming agents may be used alone or in combination of two or more.
• film-forming agents include carbonates, alkene sulfides, sultones, and acid anhydrides.
• carbonates examples include vinylene carbonate, vinyl ethylene carbonate, vinyl ethyl carbonate, methyl phenyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate.
• alkene sulfides examples include ethylene sulfide and propylene sulfide.
• sultones examples include 1,3-propane sultone and 1,4-butane sultone.
• acid anhydrides examples include maleic anhydride and succinic anhydride.
• the mass % content (film-forming agent/electrolyte) is preferably 10 mass % or less, more preferably 8 mass % or less, even more preferably 5 mass % or less, and particularly preferably 2 mass % or less.
• Examples of the form (electricity storage device) include a cylinder type in which the sheet electrode and separator are spirally wound, a cylinder type with an inside-out structure that combines a pellet electrode and separator, and a coin type in which pellet electrodes and separators are stacked.
• the manufacturing method (electricity storage device) can be, for example, the method described in JP 2013-089437 A.
• Applications include, for example, batteries, non-aqueous secondary batteries, lithium ion batteries, sodium ion batteries, etc.
• Example 1 In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube, and three dropping funnels, 733.6 g of ion-exchanged water, 100 g (40 mol%) of 50% acrylamide, 47.5 g (30 mol%) of 80% acrylic acid, and 28.0 g (30 mol%) of acrylonitrile were placed. After removing oxygen from the reaction system by passing nitrogen gas through it, the temperature was raised to 55°C.
• the hydrolyzed partial condensate of the polyalkoxysilane was added to the aqueous solution in the amount shown in the table below.
• the aqueous solution was then obtained by stirring for 30 minutes.
• AM Acrylamide
• AA Acrylic acid
• AN Acrylonitrile
• SMAS Sodium methallylsulfonate
• Na Sodium hydroxide
• Ca Calcium hydroxide
• Si-HC Partial condensate of hydrolyzed polyalkoxysilane
• APS Ammonium persulfate
• SPS Sodium persulfate
• KPS Potassium persulfate.
• Neutralization rate refers to the rate relative to 100 mol % of carboxyl groups in the acrylic acid units.
• the monomer content was determined as follows.
• (2) (Meth)acrylamide Calibration Curve Using a standard solution, measurements were performed under the following conditions to prepare a calibration curve.
• ⁇ Breaking strength> The aqueous solution of the binder for the electric storage device was applied onto the surface of a flat polypropylene plate and heated in an oven at 120° C. until the weight reached a constant value, thereby obtaining a non-volatile portion of the aqueous solution of the binder for the electric storage device as a residue.
• the obtained non-volatile portion was molded into a size of 50 mm in length, 20 mm in width, and 50 ⁇ m in thickness, to produce a molded film made of the non-volatile portion of the aqueous solution of the binder for the electric storage device.
• the breaking strength of the produced molded film was measured at a tensile speed of 50 mm/min using a universal testing machine (AGX-V, manufactured by Shimadzu Corporation). A: 30 MPa or more B: less than 30 MPa
• ⁇ Pencil hardness> A film was produced by coating the aqueous binder solution under the following conditions and drying. The pencil hardness (film) was measured by the following test method. Substrate: Glass plate Coating method: Applicator (thickness 200 ⁇ m) Drying conditions: 100°C, 30 minutes Test method: General test method of JIS K-5401 A: 3H or more B: 2H or less
• (1-4) Charge/Discharge Measurement The lithium half-cell was placed in a thermostatic chamber at 25° C., and charging was started at a constant current (0.1 C), and charging was completed (cut off) when the voltage reached 0.01 V. Next, discharging was started at a constant current (0.1 C), and charging/discharging was repeated 30 times, with discharging completed (cut off) when the voltage reached 1.0 V.
• “1C” means a current value at which a cell having a certain capacitance is discharged at a constant current and the discharge is completed in 1 hour.
• 0.1C means a current value at which the discharge is completed in 10 hours
• “10C” means a current value at which the discharge is completed in 0.1 hour.
• Initial coulombic efficiency was calculated from the initial charge capacity (mAh) and initial discharge capacity (mAh) when a charge/discharge cycle test was performed at room temperature (25° C.) using the following formula.
• Initial coulombic efficiency (initial discharge capacity)/(initial charge capacity) ⁇ 100 (%)
• Discharge capacity retention rate ⁇ (discharge capacity at 30th cycle)/(discharge capacity at 1st cycle) ⁇ 100(%)
• the electricity storage device having the electricity storage device separator produced using the electricity storage device binder aqueous solution of the example functioned without any problems.

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• 2023
  • 2023-09-07 EP EP23871792.0A patent/EP4597636A1/en active Pending
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