Classifications

• • 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
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/38—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/24—Haloalkylation
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/28—Condensation with aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/002—Pigment pastes, e.g. for mixing in paints in organic medium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • 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
• • 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
  • 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
  • H01M4/623—Binders being polymers fluorinated polymers
• • 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
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2203—Oxides; Hydroxides of metals of lithium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2289—Oxides; Hydroxides of metals of cobalt
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention is a modified polyvinyl acetal resin that is excellent in dispersibility, adhesiveness, and stability over time, can prevent deterioration due to an electrolytic solution when used as an electrode of a storage battery, and can produce a high-output storage battery.
• the present invention relates to a composition for a storage battery electrode and a pigment composition using the modified polyvinyl acetal resin.
• the polyvinyl acetal resin is a resin synthesized from polyvinyl alcohol as a raw material, and has an acetyl group, a hydroxyl group, and an acetal group in the side chain. As a result, excellent toughness and adhesiveness can be exhibited. Further, it is possible to change the resin physical properties by changing the ratio of the side chain groups. Taking advantage of these characteristics, polyvinyl acetal resins are used in many applications such as electrodes for storage batteries, pigment compositions, and ceramic green sheets.
• the most widely used binder for electrodes of lithium secondary batteries is a fluororesin typified by polyvinylidene fluoride (PVDF).
• PVDF polyvinylidene fluoride
• a fluororesin is used as a binder, a flexible thin film can be produced, but the binding property between the current collector and the active material is poor. Therefore, a part or all of the active material is used in the battery manufacturing process. May peel off from the current collector and fall off. Further, when the battery is charged and discharged, lithium ions are repeatedly inserted and discharged in the active material, and there is a problem that the active material may be peeled off or dropped from the current collector.
• a binder other than PVDF In order to solve the above-mentioned problems, it has been attempted to use a binder other than PVDF.
• a non-aqueous secondary composed of a copolymer of an acidic functional group-containing monomer and an amide group-containing monomer is used.
• Binders for batteries are listed. By using such a binder, it is possible to have excellent resistance to the electrolytic solution, good adhesion to the electrode, and to realize safety during manufacturing.
• a binder resin in which pigments and other additives are mixed and dispersed in a solvent is used.
• the binder resin polyvinyl acetal resins such as polyvinyl butyral resin are widely used. It is used.
• Patent Document 2 describes that a polyvinyl acetal resin is used as a resin in an ink for an oil-based ballpoint pen using a resin having a solubility in ethanol at 25 ° C. of more than 7% by weight.
• the modified polyvinyl acetal resin according to the present invention is excellent in dispersibility, adhesiveness, and stability over time. Further, when used as an electrode of a storage battery, the electrode resistance can be lowered and deterioration due to the electrolytic solution can be prevented, and a high output storage battery can be manufactured. That is, an object of the present invention is to provide a modified polyvinyl acetal resin excellent in the above-mentioned characteristics, a composition for a storage battery electrode using the modified polyvinyl acetal resin, and a pigment composition.
• the present invention is a modified polyvinyl acetal resin containing a structural unit having a chlorine atom.
• the present invention will be described in detail below.
• total acetal group amount of Japanese Patent Application No. 2020-120668 and Japanese Patent Application No. 2021-047650 is described as “acetalization degree”
• acetalization degree is described as “non-chlorinated acetalization degree”. do.
• a modified polyvinyl acetal resin containing a structural unit having a chlorine atom is excellent in dispersibility, adhesiveness, and stability over time. Furthermore, they have found that when used as an electrode of a storage battery, the electrode resistance can be reduced, deterioration due to an electrolytic solution can be prevented, and a high-output storage battery can be manufactured, and the present invention has been completed. ..
• the modified polyvinyl acetal resin of the present invention contains a structural unit having a chlorine atom.
• the structural unit having a chlorine atom By including the structural unit having a chlorine atom, the adhesiveness and dispersibility are excellent, and the stability of the obtained composition with time is excellent. Further, when used as an electrode of a storage battery, the electrode resistance can be lowered and deterioration due to the electrolytic solution can be prevented, and a high output storage battery can be manufactured.
• the stability over time means that there is little change in physical properties such as viscosity (particularly thickening) over time.
• the structural unit having a chlorine atom is preferably one having 1 to 3 chlorine atoms.
• the structural unit having a chlorine atom is not particularly limited as long as it has a structure having a chlorine atom, but a structure in which a chlorine atom is bonded via an acetal bond, or a structure having a chlorine atom or a chlorine atom-containing group in a side chain. Etc. are preferable.
• the structure in which a chlorine atom is bonded via an acetal bond includes a case where a linking group other than the acetal bond is further bonded.
• the structural unit having a chlorine atom has a structure in which chlorine atoms are bonded via an acetal bond (hereinafter, such a structural unit is also referred to as a chlorinated modified acetal bond unit), it is represented by the following formula (3). It is preferable that it is a structural unit.
• R 6 represents a chlorine atom-containing hydrocarbon group.
• Chlorine atom-containing hydrocarbon group in the above R 6 may be a chlorine atom-containing aliphatic groups, may be a chlorine atom-containing aromatic group, but is preferably a chlorine atom-containing aliphatic group. Further, the number of carbon atoms in the R 6, the proportion of the number of chlorine atoms [carbon atoms / number of chlorine atoms] is preferably from 0.1 to 5.
• the chlorinated modified acetal bond unit is preferably a structural unit represented by the following formula (1).
• the structural unit represented by the following formula (1) it is possible to maintain an appropriate distance between the main chain of the modified polyvinyl acetal resin and the chlorine atom.
• the modified polyvinyl acetal resin is excellent in adhesiveness and dispersibility, and is further excellent in stability over time of the obtained composition. Further, when used as an electrode of a storage battery, the electrode resistance can be reduced.
• R 1 represents a chlorine atom or a chloroalkyl group
• R 2 and R 3 independently represent a hydrogen atom or a chlorine atom, respectively.
• R 2 and R 3 may be a chloroalkyl group.
• chloroalkyl group examples include a chloromethyl group (-CH 2 Cl), a chloroethyl group (-CH 2 CH 2 Cl), a dichloroethyl group, a chloropropyl group, a trichloromethyl group and the like.
• R 1 is preferably a chlorine atom, —CH 2 Cl or —CH 2 CH 2 Cl. Further, in the present invention, it is preferable to use a combination of R 1 as a chlorine atom and R 2 and R 3 as a hydrogen atom.
• R 6 is a chlorine atom-containing aromatic group.
• the adhesiveness and dispersibility to the aromatic compound and the compound having the aromatic functional group can be further improved.
• the chlorine atom-containing aromatic group include a chlorophenyl group and a chloroalkylphenyl group.
• the chlorophenyl group include a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2,4-dichlorophenyl group, a 3,4-dichlorophenyl group and the like.
• chloroalkylphenyl group examples include a 2-chloromethylphenyl group, a 3-chloromethylphenyl group, a 4-chloromethylphenyl group and the like.
• the chlorophenyl group and the chloroalkylphenyl group may have other substituents in addition to the chloro group.
• the structural unit having a chlorine atom has a structure having a chlorine atom or a chlorine atom-containing group in the side chain (hereinafter, such a structural unit is also referred to as a chlorinated modified side chain bonding unit), the following formula (2) It is preferable that the structure (constituent unit) is represented by.
• the modified polyvinyl acetal resin is excellent in adhesiveness and dispersibility, and further excellent in stability over time of the obtained composition. Further, when used as an electrode of a storage battery, the electrode resistance can be reduced.
• R 4 represents a single bond or an alkylene group
• R 5 represents a hydrogen atom, a chlorine atom or a chloroalkyl group.
• R 4 may be chloro alkylene group.
• the alkylene group shown in R 4 preferably has 1 to 20 carbon atoms, and for example, a linear alkylene group, a branched alkylene group, and a cyclic alkylene group are preferable.
• the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group and the like.
• Examples of the branched alkylene group include a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group and the like.
• cyclic alkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclohexylene group and the like.
• a linear alkyl group such as a methylene group, an ethylene group, an n-propylene group and an n-butylene group is preferable, and a methylene group and an ethylene group are more preferable.
• the chloroalkyl groups shown above R 5, can be used the same as R 1. Further, in the present invention, it is preferable to use R 4 as a single bond and R 5 as a combination of hydrogen atoms.
• the content of the structural unit having a chlorine atom (chlorination modification unit amount) in the modified polyvinyl acetal resin of the present invention is preferably 0.1 mol% at the lower limit.
• the more preferable lower limit of the chlorination modification unit amount is 1.0 mol%, and the more preferable lower limit is 4.0 mol%.
• the upper limit of the chlorination modification unit amount is preferably 35 mol%, more preferably 30 mol%, from the viewpoint of handleability in manufacturing.
• the chlorinated modified unit amount means the total of both.
• the more preferable lower limit of the content of the chlorinated modified acetal bond unit is 0. It is 1 mol%.
• the more preferable lower limit of the content of the chlorinated modified acetal binding unit is 1.0 mol%, and the more preferable lower limit is 4.0 mol%.
• the upper limit of the content of the chlorinated modified acetal binding unit is preferably 30 mol%.
• the modified polyvinyl acetal resin of the present invention contains a structure having a chlorine atom or a chlorine atom-containing group in the side chain (chlorinated modified side chain bonding unit), the content of the chlorinated modified side chain bonding unit is more preferable.
• the lower limit is 0.1 mol% and the more preferred upper limit is 15 mol%. Further, a more preferable lower limit is 0.5 mol%, and a further preferable upper limit is 10 mol%. Within the above range, the adhesiveness, dispersibility, and stability of the obtained composition over time can be improved.
• the ratio of both (chlorinated modified acetal binding unit / chlorinated modified side chain binding unit). Is preferably 0.5 or more and 3 or less, and more preferably 1 or more and 2 or less.
• the modified polyvinyl acetal resin of the present invention has a structural unit having a hydroxyl group, a structural unit having an acetyl group, and a structural unit having an acetal group.
• the modified polyvinyl acetal resin of the present invention has the above-mentioned structural unit having a hydroxyl group.
• the preferable lower limit of the content (hydroxyl group amount) of the structural unit having a hydroxyl group is 20 mol%, and the preferable upper limit is 70 mol%.
• the amount of the hydroxyl group is 20 mol% or more, the solubility in an organic solvent is improved and it can be suitably used as a composition, and when it is 70 mol% or less, the flexibility of the resin is maintained. be able to.
• the more preferable lower limit of the amount of the hydroxyl group is 25 mol%, and the more preferable upper limit is 65 mol%.
• the modified polyvinyl acetal resin of the present invention has the above-mentioned structural unit having an acetyl group.
• the preferable lower limit of the content (acetyl group amount) of the structural unit having an acetyl group is 0.1 mol%
• the preferable upper limit is 20 mol%.
• the resistance to the liquid is improved, and it is possible to prevent the resin from being eluted into the electrolytic liquid and deteriorating the battery.
• the more preferable lower limit of the amount of the acetyl group is 0.3 mol%, and the more preferable upper limit is 10 mol%.
• the polyvinyl acetal resin has a structural unit having the acetal group. Further, the polyvinyl acetal resin preferably has both a structural unit having a non-chlorinated acetal group and a structural unit having a chlorinated acetal group as the structural unit having the acetal group.
• the content (degree of non-chlorinated acetalization) of the structural unit having the non-chlorinated acetal group in the polyvinyl acetal resin is preferably 20 mol% or more and 75 mol% or less.
• the degree of non-chlorination acetalization By setting the degree of non-chlorination acetalization to 75 mol% or less, the adhesiveness and dispersibility can be maintained. More preferably, it is 25 mol% or more and 70 mol% or less.
• the degree of non-chlorinated acetalization is the hydroxyl group acetalized with an aldehyde (butyraldehyde, acetaldehyde, etc.) that does not contain a chlorine atom in the portion of the number of hydroxyl groups of polyvinyl alcohol excluding the aldehyde group. It is the ratio of numbers.
• the content of the above-mentioned "structure in which chlorine atoms are bonded via acetal bonds" is not included in the degree of non-chlorinated acetalization.
• a method for calculating the degree of non-chlorinated acetalization since the acetal group of the polyvinyl acetal resin is formed by acetalization from two hydroxyl groups, a method of counting the two acetalized hydroxyl groups is adopted. Then, the mol% of the degree of acetalization is calculated.
• the non-chlorinated acetal group is preferably an acetaldehyde group acetalized with acetaldehyde or a butyl acetal group acetalized with butyl aldehyde.
• the content of acetaldehyde-acetalized acetal acetal groups (acetal acetal group content) in the modified polyvinyl acetal resin of the present invention is preferably 10 mol% or more and 50 mol% or less. Further, the content (butyral group amount) of the butyraldehyde-acetalized butyl acetal group in the modified polyvinyl acetal resin of the present invention is preferably 3 mol% or more and 75 mol% or less. Within the above range, water resistance can be maintained and excellent viscosity characteristics can be obtained.
• the modified polyvinyl acetal resin of the present invention contains both a structural unit having a non-chlorinated acetal group and a chlorinated modified acetal bond unit, the degree of non-chlorinated acetalization and the amount of the chlorinated modified acetal bond unit amount.
• the total amount of acetalization is preferably 25 mol% or more. Further, the total amount is preferably 80 mol% or less. Within the above range, the composition having excellent adhesiveness and dispersibility while maintaining solubility in an organic solvent can realize high stability over time.
• the degree of acetalization is more preferably 30 mol% or more and 75 mol% or less.
• the ratio of the constituent units having the non-chlorinated acetal group to the content of the chlorinated modified acetal binding unit is preferably 15 or less. Further, the above ratio is more preferably 10 or less. The lower limit is not particularly limited, but is preferably 1 or more. Further, the ratio of the non-chlorinated acetalization degree to the acetalization degree [non-chlorinated acetalization degree / acetalization degree] is preferably 0.4 or more and 0.95 or less. Within the above range, the composition having excellent adhesiveness and dispersibility while maintaining solubility in an organic solvent can realize high stability over time.
• the ratio of the chlorinated modified acetal binding unit amount [chlorinated modified acetal binding unit amount / acetalization degree] to the acetalization degree is preferably 0.05 or more and 0.6 or less.
• the composition having excellent adhesiveness and dispersibility while maintaining solubility in an organic solvent can realize high stability over time.
• the ratio of the degree of non-chlorinated acetalization to the amount of hydroxyl groups [degree of non-chlorinated acetalization / amount of hydroxyl groups] is preferably 0.3 or more and 3.5 or less, and 0.5 or more and 3.0. The following is more preferable.
• the composition having excellent adhesiveness and dispersibility while maintaining solubility in an organic solvent can realize high stability over time.
• the total amount of the non-chlorinated acetalization degree and the chlorination modification unit amount in the modified polyvinyl acetal resin of the present invention is 25 mol% or more and 80 mol% or less. Is preferable. Within the above range, the adhesiveness, dispersibility, and the stability over time of the obtained composition are improved.
• the degree of dechlorination acetalization + chlorination modification unit amount is more preferably 30 mol% or more and 75 mol% or less.
• the ratio of the degree of non-chlorinated acetalization to the amount of the chlorinated modification unit in the modified polyvinyl acetal resin of the present invention is preferably 1 or more and 50 or less. It is more preferably 1.5 or more and 40 or less, further preferably 2 or more and 35 or less, and further preferably 5 or more and 30 or less. Within the above range, the adhesiveness, dispersibility, and the stability of the obtained composition over time are improved.
• the degree of non-chlorinated acetalization / chlorination modification unit amount is particularly preferably 8 or more and 20 or less.
• the preferred lower limit of the degree of polymerization of the modified polyvinyl acetal resin of the present invention is 200, and the preferred upper limit is 4000.
• the degree of polymerization is 200 or more, industrial production becomes easy.
• the degree of polymerization is 4000 or less, the viscosity of the solution becomes appropriate, and industrial production becomes possible.
• the more preferable lower limit of the degree of polymerization is 500, and the more preferable upper limit is 2500.
• the chlorine atom content A measured by combustion ion chromatography is preferably 0.1% by weight or more and 15% by weight or less, and more preferably 10% by weight or less. .. Within such a range, the effect of the present invention can be suitably obtained.
• the more preferable lower limit of the chlorine atom content A is 0.5% by weight, and the more preferable upper limit is 9% by weight.
• the chlorine atom content A can be measured by combustion ion chromatography based on JIS K 0127 (2013). In this measuring method, the chlorine atom content of the polyvinyl acetal resin powder can be obtained as a measurement result regardless of the presence or absence of the bond between the resin and the chlorine atom. Therefore, the chlorine atom content A is a value representing the total of the chlorine atom content bonded to the resin and the chlorine atom content not bonded to the resin.
• the modified polyvinyl acetal resin of the present invention preferably has a chlorine atom content B measured by NMR of 0.1% by weight or more and 10% by weight or less.
• the chlorine atom content B means the chlorine atom content calculated from the chlorination modification unit amount obtained by using NMR. Therefore, the chlorine atom content B is a value representing the chlorine atom content bonded to the resin. Further, the value (chlorine atom content difference C) obtained by the following formula (4) from the chlorine atom content A and the chlorine atom content B is preferably 0.5% by weight or less.
• Chlorine atom content difference C Chlorine atom content A-Chlorine atom content B (4)
• the chlorine atom content difference C obtained by the above formula (4) estimates the chlorine atom content not bonded to the resin, whereby the chloride ion content of, for example, NaCl can be estimated, and is equal to or less than the above upper limit. Therefore, for example, when used as an electrode of a storage battery, the durability of the battery can be improved.
• the value (chlorine atom content difference C) obtained by the above formula (4) is more preferably 0.1% by weight or less. Further, the preferable lower limit is not particularly limited, but it is preferably 0.001% by weight or more.
• a polyvinyl alcohol containing a structural unit having a chlorine atom is prepared and then acetalized, and a polyvinyl alcohol not containing a structural unit having a chlorine atom is acetalized.
• a method of adding a chlorine atom and the like is added.
• a method of preparing polyvinyl alcohol containing a structural unit having a chlorine atom and polyvinyl alcohol not containing a structural unit having a chlorine atom and then introducing the structural unit having a chlorine atom by acetalization can be mentioned.
• a method of preparing a polyvinyl alcohol having a structural unit represented by the above formula (2) in advance and then acetalizing the polyvinyl alcohol, or a polyvinyl alcohol having no structural unit represented by the above formula (2) is acetal.
• a method of adding a portion corresponding to R 4 and R 5 of the structural unit represented by the above formula (2) can be mentioned.
• polyvinyl alcohol having a structural unit represented by the above formula (2) in advance and polyvinyl alcohol having no structural unit represented by the above formula (2) are prepared, and then acetalized to be represented by the above formula (1).
• a method of introducing the structural unit to be used can be mentioned.
• polyvinyl alcohol containing a structural unit having a chlorine atom for example, after copolymerizing vinyl chloride and vinyl acetate, an acid or an alkali is added to an alcohol solution of the obtained copolymer to obtain saponification.
• the method of saponification can be mentioned.
• polyvinyl alcohol containing the above-mentioned structural unit having a chlorine atom may be prepared by a method of adding a chlorine atom.
• a method of adding the chlorine atom for example, a method of reacting polyvinyl alcohol with chlorine gas and the like can be mentioned.
• the polyvinyl alcohol containing no structural unit having a chlorine atom (hereinafter, also simply referred to as polyvinyl alcohol) can be obtained, for example, by saponifying a copolymer of vinyl ester and ethylene.
• the vinyl ester include vinyl formic acid, vinyl acetate, vinyl propionate, vinyl pivalate and the like. Of these, vinyl acetate is preferable from the viewpoint of economy.
• a method for introducing a structural unit having a chlorine atom by the acetalization a method of reacting polyvinyl alcohol with an aldehyde or an aldehyde equivalent having a chlorine atom can be used.
• Aldehydes having a chlorine atom such as chloroacetaldehyde are highly reactive, difficult to react uniformly with polyvinyl alcohol, and tend to have a high risk. Therefore, it is more preferable to use an aldehyde equivalent in the actual manufacturing process.
• aldehyde having a chlorine atom examples include chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, 3-chloropropionaldehyde, 4-chlorobutylaldehyde and the like.
• the aldehyde equivalent is a compound obtained by adding a protecting group to an aldehyde or a compound that can be converted into an aldehyde by a commonly used method, and examples thereof include acetal, hemiacetal, and aldehyde hydrate. Of these, an aldehyde equivalent having a chlorine atom is preferable.
• aldehyde equivalent having a chlorine atom examples include chloroacetaldehyde dimethyl acetal, chloroacetaldehyde diethyl acetal, 2-chloromethyl-1,3-dioxolane, dichloroacetaldehyde dimethyl acetal, dichloroacetaldehyde diethyl acetal, and 2,2-dichloromethyl-1.
• the modified polyvinyl acetal resin of the present invention may be a copolymer of an ethylenically unsaturated monomer as long as the effects of the present invention are not impaired.
• the ethylenically unsaturated monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, (phthalic anhydride) phthalic acid, (maleic anhydride) maleic acid, and (anhydrous) itaconic acid. Further, examples thereof include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamide-3-dimethylpropyl) -ammonium chloride, acrylamide-2-methylpropanesulfonic acid and sodium salts thereof.
• ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinylsulfonate, sodium allylsulfonate and the like can be mentioned.
• a terminal-modified polyvinyl alcohol obtained by copolymerizing ethylene with a vinyl ester-based monomer such as vinyl acetate and saponifying it in the presence of a thiol compound such as thiol acetic acid or mercaptopropionic acid should also be used. Can be done.
• modified polyvinyl acetal resin of the present invention include, for example, storage battery electrodes, binders and dispersants such as pigments, adhesive modifiers based on epoxy resins and phenolic resins, ceramic green sheets, conductive pastes and the like. Can be mentioned. It can also be used as a binder for ink products such as gel ink, as a raw material for 3D printer resins, actuators, gas separation membranes, adhesives, paints, films and the like. In particular, when the modified polyvinyl acetal resin of the present invention is used as a binder used for the storage battery electrode, the electrode resistance can be lowered, deterioration due to the electrolytic solution can be prevented, and a high output storage battery can be manufactured.
• the modified polyvinyl acetal resin of the present invention is used as a dispersant for pigments, for example, dispersibility and dispersion with halogen-substituted pigments such as halogenated copper phthalocyanine green (Pigment Green 7, Pigment Green 36, etc.) and dispersion. It can be made excellent in stability over time later.
• halogen-substituted pigments such as halogenated copper phthalocyanine green (Pigment Green 7, Pigment Green 36, etc.) and dispersion. It can be made excellent in stability over time later.
• a composition for a storage battery electrode containing the modified polyvinyl acetal resin of the present invention, an organic solvent, and an active material is also one of the present inventions.
• Such a composition for a storage battery electrode is excellent in dispersibility and adhesiveness of the active material, can reduce the electric resistance, and can prevent deterioration due to the electrolytic solution, so that a high output storage battery can be produced.
• a composition for a storage battery electrode containing the modified polyvinyl acetal resin, polyvinylidene fluoride resin, organic solvent, and active material of the present invention is also one of the present inventions.
• the modified polyvinyl acetal resin of the present invention and the polyvinylidene fluoride resin by containing both the modified polyvinyl acetal resin of the present invention and the polyvinylidene fluoride resin, the modified polyvinyl acetal resin of the present invention or the polyvinylidene fluoride resin alone was used.
• the adhesiveness is further excellent and the electrical resistance can be reduced.
• the content of the structural unit having a chlorine atom of the modified polyvinyl acetal resin of the present invention is preferably 0.5 mol% or more, preferably 1 mol% or more, from the viewpoint of compatibility. It is more preferable to have.
• the weight average molecular weight of the polyvinylidene fluoride resin is preferably 400,000 or more and 12,000,000 or less, and more preferably 600,000 or more and 1,000,000 or less. The weight average molecular weight can be measured by an absolute molecular weight measurement method using gel permeation chromatography (GPC).
• the weight ratio of the modified polyvinyl acetal resin of the present invention to the polyvinylidene fluoride resin is preferably 0.5: 9.5 to 8: 2, and more preferably 1: 9 to 7: 3. Within the above range, the adhesiveness can be improved and the electric resistance can be further reduced.
• the amount of resin (total amount of the weight of the modified polyvinyl acetal resin of the present invention and the polyvinylidene fluoride resin) in the composition for the storage battery electrode of the present invention is preferably 0.5 to 4 parts by weight, preferably 0.6 to 3 parts. By weight is more preferred, and 0.7 to 2 parts by weight is even more preferred. When the amount of the resin is 0.5 parts by weight or more, high adhesiveness can be exhibited, and when it is 4 parts by weight or less, an electrode having low electric resistance can be manufactured.
• a pigment composition containing the modified polyvinyl acetal resin of the present invention, an organic solvent, and a pigment is also one of the present inventions.
• the dispersibility of the pigment is excellent and high stability over time can be realized.
• the active material examples include a positive electrode active material and a negative electrode active material.
• the positive electrode active material examples include lithium-containing composite metal oxides such as lithium nickel oxide, lithium cobalt oxide, and lithium manganese oxide. Specifically, for example, LiNiO 2 , LiCoO 2 , LiMn 2 O 4, and the like can be mentioned.
• the negative electrode active material for example, a material conventionally used as a negative electrode active material of a storage battery can be used, for example, spherical natural graphite, natural graphite, artificial graphite, amorphous carbon, carbon black, or. Examples thereof include those obtained by adding a different element to these components. These may be used alone or in combination of two or more.
• the composition for a storage battery electrode according to the present invention preferably further contains a conductive auxiliary agent (conducting agent).
• a conductive auxiliary agent conducting agent
• the electric resistance of the obtained composition for a storage battery electrode can be further reduced.
• the conductive auxiliary agent include carbon materials such as graphite, acetylene black, carbon black, Ketjen black, and vapor-grown carbon fiber.
• the pigment examples include phthalocyanine-based, isoindolinone-based, quinophthalone-based, isoindoline-based, anthraquinone-based, diketopyrrolopyrrole-based, perylene-based, perinone-based, quinacridone-based, and dioxazine-based pigments.
• the phthalocyanine pigment examples include metal phthalocyanine pigments and non-metal phthalocyanine pigments.
• the metal phthalocyanine pigment include a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and an aluminum phthalocyanine pigment.
• Pigment Greens 7 and 36 are preferable as the halogenated copper phthalocyanine pigment.
• Examples of the organic solvent include alcohols, polyhydric alcohols, glycol ethers, esters, amide solvents, amine solvents and the like.
• Examples of the alcohols include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butyl alcohol, pentanol, hexanol, n-heptanol, 2-heptanol, octanol, 2-ethylhexanol, 3,5.
• Examples thereof include other higher alcohols such as 5-trimethylhexanol, nonanol, decanol, cyclohexanol, benzyl alcohol, terpineol, dihydroterpineol and the like.
• Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, phenyl glycol and the like.
• Examples of the glycol ethers include propylene glycol monomethyl ether, propylene glycol monobutyl ether, methyl cell solve, ethyl cell solve, butyl cell solve, butyl carbitol, butyl triglycol, and methyl diglycol.
• esters examples include methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanate, ethyl pentanate, butyl pentanate, methyl hexanoate, ethyl hexanoate, and the like.
• examples thereof include butyl hexaneate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate and the like.
• butyl cellsolve acetate, butyl carbitol acetate, terpineol acetate, dihydroterpineol acetate and the like can also be used.
• the amide-based solvent include N, N-dimethylformamide, N, N-dimethyltesetoamide, N-methylpyrrolidone, acetanilide and the like.
• the amine-based solvent include ammonia, trimethylamine, triethylamine, n-butylamine, din-butylamine, trin-butylamine, aniline, N-methylaniline, N, N-dimethylaniline, and pyridine. Further, two or more kinds of the above organic solvents may be mixed and used.
• composition for the storage battery electrode and the pigment composition of the present invention may include, if necessary, a flame retardant aid, a thickener, an antifoaming agent, a leveling agent, and an adhesion-imparting agent. Additives may be added.
• a modified polyvinyl alcohol resin containing a structural unit having a chlorine atom can be used.
• the structural unit having a chlorine atom is the same as that of the modified polyvinyl acetal resin of the present invention, and preferably has a structure having a chlorine atom or a chlorine atom-containing group in the side chain, and is represented by the above formula (2). It is preferably a unit.
• the modified polyvinyl alcohol resin has a ratio of the amount of hydroxyl group to the content of the structural unit having a chlorine atom (the amount of hydroxyl group: the content of the structural unit having a chlorine atom) of 70:35 to 99.9. : It is preferably 0.1.
• the amount of hydroxyl groups is preferably 70 mol% or more and 99.9 mol% or less, and the content of the structural unit having a chlorine atom is 0.1 mol% or more and 35 mol% or less. It is preferably 30 mol% or less, and more preferably 30 mol% or less.
• a modified polyvinyl acetal resin capable of producing a high output storage battery can be provided. Further, it is possible to provide a composition for a storage battery electrode and a pigment composition using the modified polyvinyl acetal resin.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination. The amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) is used to increase the amount of hydroxyl groups, the amount of acetyl groups, the amount of butyral groups, and the amount of acet acetal groups. , And the amount of chlorinated modified acetal binding unit was measured.
• the results are shown in Table 1.
• the solid content concentration in the system at the time of stopping the polymerization was 53% by weight, and the polymerization yield with respect to all the monomers was 65% by weight. After removing the unreacted monomer under reduced pressure, a 45% by weight methanol solution of the copolymer was obtained. It was confirmed from the quantification of unreacted monomers that the obtained copolymer contained 92.4 mol% of vinyl acetate unit and 7.6 mol% of vinyl chloride unit.
• modified polyvinyl alcohol (d) The degree of saponification of the modified polyvinyl alcohol (d) was 98.5 mol%, the amount of the chlorinated modified side chain bond unit amount was 7.6 mol%, and the degree of polymerization was 800.
• modified polyvinyl alcohol (e) having a structural unit having a degree of saponification of 98.5 mol%, a chlorinated modified side chain bond unit amount of 3.9 mol%, and a degree of polymerization of 800 chlorine atoms. ) was used. Further, a chlorinated modified polyvinyl acetal resin solution (resin content: 5% by weight) containing a structural unit having a chlorine atom was obtained by the same method as in Production Example 1 except that 64 g of n-butyraldehyde was added.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) is used to increase the amount of hydroxyl groups, the amount of acetyl groups, the amount of butyral groups, and the amount of acet acetal groups. , And the amount of chlorinated modified acetal binding unit was measured.
• the results are shown in Table 1.
• polyvinyl alcohol (f) having a saponification degree of 98.6 mol% and a degree of polymerization of 1800 was used. Further, a structural unit having a chlorine atom was prepared by the same method as in Production Example 1 except that 48 g of n-butyraldehyde and 26 g of chloroacetaldehyde dimethyl acetal were added instead of 50 g of n-butyraldehyde and 28 g of chloroacetaldehyde dimethyl acetal. A chlorinated modified polyvinyl acetal resin powder containing the mixture was obtained.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• polyvinyl alcohol (g) having a saponification degree of 99.5 mol% and a degree of polymerization of 1800 was used. Further, a structural unit having a chlorine atom was prepared by the same method as in Production Example 1 except that 24 g of n-butyraldehyde and 20 g of chloroacetaldehyde dimethyl acetal were added instead of 50 g of n-butyraldehyde and 28 g of chloroacetaldehyde dimethyl acetal. A chlorinated modified polyvinyl acetal resin powder containing the mixture was obtained.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• modified polyvinyl alcohol (h) having a structural unit having a chlorine atom having a degree of saponification of 98.6 mol%, a chlorinated modified side chain bond unit amount of 5.4 mol%, and a degree of polymerization of 1800. ) was used. Further, a structural unit having a chlorine atom was prepared by the same method as in Production Example 1 except that 45 g of n-butyraldehyde and 14 g of chloroacetaldehyde dimethyl acetal were added instead of 50 g of n-butyraldehyde and 28 g of chloroacetaldehyde dimethyl acetal.
• a chlorinated modified polyvinyl acetal resin powder containing the mixture was obtained.
• the obtained polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) is used to increase the amount of hydroxyl groups, the amount of acetyl groups, the amount of butyral groups, and the chlorinated modified acetal bond.
• the unit amount was measured.
• the results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• polyvinyl alcohol (i) having a saponification degree of 98.2 mol% and a degree of polymerization of 2700 was used.
• a structural unit having a chlorine atom was prepared by the same method as in Production Example 1 except that 47 g of n-butyraldehyde and 1 g of chloroacetaldehyde dimethyl acetal were added instead of 50 g of n-butyraldehyde and 28 g of chloroacetaldehyde dimethyl acetal.
• a chlorinated modified polyvinyl acetal resin powder containing the mixture was obtained.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• modified polyvinyl alcohol (j) having a structural unit having a degree of saponification of 98.3 mol%, a chlorinated modified side chain bond unit amount of 0.8 mol%, and a degree of polymerization of 2700 chlorine atoms. ) was used. Further, a chlorinated modified polyvinyl acetal resin powder containing a structural unit having a chlorine atom was obtained by the same method as in Production Example 1 except that 62 g of n-butyraldehyde was added.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• Polyvinyl alcohol (k) having a saponification degree of 98.7 mol% and a degree of polymerization of 4000 was used. Further, a structural unit having a chlorine atom was prepared by the same method as in Production Example 1 except that 60 g of n-butyraldehyde and 6 g of chloroacetaldehyde dimethyl acetal were added instead of 50 g of n-butyraldehyde and 28 g of chloroacetaldehyde dimethyl acetal. A chlorinated modified polyvinyl acetal resin powder containing the mixture was obtained.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• a structural unit having a chlorine atom is contained by the same method as in Production Example 6 except that 61 g of n-butyraldehyde and 0.1 g of chloroacetaldehyde dimethyl acetal are added instead of 51 g of n-butyraldehyde and 33 g of chloroacetaldehyde dimethyl acetal.
• a chlorinated modified polyvinyl acetal resin powder was obtained.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• modified polyvinyl alcohol (l) having a structural unit having a degree of saponification of 98.5 mol%, a chlorinated modified side chain bond unit amount of 0.06 mol%, and a degree of polymerization of 800 chlorine atoms. ) was used. Further, a chlorinated modified polyvinyl acetal resin powder containing a structural unit having a chlorine atom was obtained by the same method as in Production Example 1 except that 63 g of n-butyraldehyde was added.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the obtained chlorinated modified polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to chlorinate the amount of hydroxyl groups, acetyl groups, butyral groups, and chlorination.
• the amount of modified acetal binding unit was measured. The results are shown in Table 1.
• a polyvinyl acetal resin powder was obtained by the same method as in Production Example 6 except that 66 g of n-butyraldehyde was added instead of 51 g of n-butyraldehyde and 33 g of chloroacetaldehyde dimethyl acetal.
• the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and the amount of hydroxyl groups, the amount of acetyl groups, and the amount of butyral groups were measured using 1 H-NMR (nuclear magnetic resonance spectrum). The results are shown in Table 1.
• a polyvinyl acetal resin powder was obtained by the same method as in Production Example 12 except that 66 g of n-butyraldehyde was added instead of 48 g of n-butyraldehyde and 26 g of chloroacetaldehyde dimethyl acetal.
• the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and the amount of hydroxyl groups, the amount of acetyl groups, and the amount of butyral groups were measured using 1 H-NMR (nuclear magnetic resonance spectrum). The results are shown in Table 1.
• Example 1 Preparation of composition for storage battery electrode 20 parts by weight of a resin solution containing a chlorinated modified polyvinyl acetal resin (polyvinyl acetal resin: 3 parts by weight) of Production Example 1 and 55 parts by weight of lithium cobaltate (Celseed C-5H, manufactured by Nippon Kagaku Kogyo Co., Ltd.) as an active material. , 5 parts by weight of acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 25 parts by weight of N-methylpyrrolidone were added as a conductivity-imparting agent. Then, it was mixed with Awatori Rentaro manufactured by Shinky Co., Ltd. to obtain a composition for a storage battery electrode.
• Examples 2 to 24, Comparative Examples 1 to 3 Preparation of composition for storage battery electrode
• a composition for a storage battery electrode was obtained in the same manner as in Example 1 except that the chlorinated modified polyvinyl acetal resin of the type and addition amount shown in Table 2 was used.
• Example 25 (Preparation of composition for storage battery electrode) 15 g of the chlorinated modified polyvinyl acetal resin obtained in Production Example 2 was dissolved in 85 g of N-methylpyrrolidone to obtain a polyvinyl acetal resin solution. Further, 5 g of a polyvinylidene fluoride resin (weight average molecular weight 600,000) was dissolved in 95 g of N-methylpyrrolidone to obtain a polyvinylidene fluoride resin solution.
• a polyvinylidene fluoride resin weight average molecular weight 600,000
• Example 26 The polyvinyl acetal resin solution and polyfluoride are the same as in Example 25, except that the chlorinated modified polyvinyl acetal resin obtained in Production Example 13 is used instead of the chlorinated modified polyvinyl acetal resin obtained in Production Example 2.
• a vinylidene resin solution was prepared to obtain a composition for a storage battery electrode.
• Example 27 The polyvinyl acetal resin solution and polyfluoride are the same as in Example 25, except that the chlorinated modified polyvinyl acetal resin obtained in Production Example 18 is used instead of the chlorinated modified polyvinyl acetal resin obtained in Production Example 2.
• a vinylidene resin solution was prepared to obtain a composition for a storage battery electrode.
• Example 28 A polyvinylidene fluoride resin solution and a polyvinylidene fluoride resin solution were prepared in the same manner as in Example 26, except that the polyvinylidene fluoride resin (weight average molecular weight 100000) was used instead of the polyvinylidene fluoride resin (weight average molecular weight 600,000). , A composition for a storage battery electrode was obtained.
• Example 29 When producing a composition for a storage battery electrode using the chlorinated modified polyvinyl acetal obtained in Production Example 12, a polyvinyl acetal resin solution is used instead of 20 parts by weight of the polyvinyl acetal resin solution (polyvinyl acetal resin: 3 parts by weight).
• a composition for a storage battery electrode was obtained in the same manner as in Example 1 except that 13.3 parts by weight (polyvinyl acetal resin: 2 parts by weight) was added.
• Example 30 When producing a composition for a storage battery electrode using the chlorinated modified polyvinyl acetal obtained in Production Example 12, a polyvinyl acetal resin solution is used instead of 20 parts by weight of the polyvinyl acetal resin solution (polyvinyl acetal resin: 3 parts by weight). 26.7 parts by weight (polyvinyl acetal resin: 4 parts by weight) was added. Further, a composition for a storage battery electrode was obtained in the same manner as in Example 1 except that 10 parts by weight of N-methylpyrrolidone was added instead of 25 parts by weight of N-methylpyrrolidone.
• polyvinylidene fluoride resin solution polyvinylidene fluoride resin: 3 parts by weight
• 55 parts by weight of lithium cobaltate (Celseed C-5H manufactured by Nippon Kagaku Kogyo Co., Ltd.) as an active material
• a conductivity-imparting agent As a result, 5 parts by weight of acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) and 5 parts by weight of N-methylpyrrolidone were added. Then, it was mixed with Awatori Rentaro manufactured by Shinky Co., Ltd. to obtain a composition for a storage battery electrode.
• Examples 31 to 46, Comparative Examples 5 to 7 (Preparation of pigment composition) 2.25 g of the (modified) polyvinyl acetal resin, 22.5 g of the pigment and 147.75 g of the organic solvent obtained in Production Examples 1 to 11, 19 to 23 and 25 to 27 shown in Table 3 were mixed and stirred with a stirrer for 1 hour. The pigment dispersion was prepared by stirring. Pigment Green 7 (manufactured by Regino Color Industry Co., Ltd., phthalocyanine green, average particle diameter 80 ⁇ m) was used as the pigment, and benzyl alcohol was used as the organic solvent.
• Pigment Green 7 manufactured by Regino Color Industry Co., Ltd., phthalocyanine green, average particle diameter 80 ⁇ m
• composition for storage battery electrode Adhesiveness (peeling force)
• peeling force The obtained composition for a storage battery electrode was evaluated for its adhesiveness to aluminum foil.
• An electrode composition was applied onto an aluminum foil (thickness 20 ⁇ m) so that the film thickness after drying was 20 ⁇ m, and dried to obtain a test piece having electrodes formed in a sheet shape on the aluminum foil.
• This sample is cut into 1 cm in length and 2 cm in width, and the electrode sheet is pulled up while fixing the test piece using AUTOGRAPH (manufactured by Shimadzu Corporation, "AGS-J") until the electrode sheet is completely peeled off from the aluminum foil.
• AUTOGRAPH manufactured by Shimadzu Corporation, "AGS-J”
• Electrolyte resistance (solvent solubility) (Preparation of electrode sheet)
• the composition for a storage battery electrode obtained in Examples and Comparative Examples is applied onto a release-treated polyalkylene terephthalate (PET) film so that the film thickness after drying is 20 ⁇ m, and the electrode sheet is dried. Made. The electrode sheet was cut into 2 cm squares to prepare an electrode sheet test piece.
• PET polyalkylene terephthalate
• the elution amount of the resin was calculated from the weight change before and after the test, and the elution rate of the resin was calculated from the ratio of the elution amount to the weight of the resin calculated in advance, and evaluated according to the following criteria.
• Elution rate is 2.0% or more
• Electrode resistance value measurement For the test piece obtained in the above "(2-1) Adhesiveness", the electrode resistance value was measured using an electrode resistance measuring instrument (manufactured by Hioki Electric Co., Ltd.), and the following Evaluated by criteria.
• ⁇ Electrode resistance value is less than 400 ⁇ / sq ⁇ : Electrode resistance value is 400 ⁇ / sq or more and less than 700 ⁇ / sq ⁇ : Electrode resistance value is 700 ⁇ / sq or more and less than 1000 ⁇ / sq ⁇ : Electrode resistance value is 1000 ⁇ / sq or more
• Viscosity change rate is less than 10%
• Viscosity change rate is 10% or more
• ⁇ Viscosity change rate is 15% or more
• modified polyvinyl which is excellent in dispersibility, adhesiveness, and stability over time, can prevent deterioration due to an electrolytic solution when used as an electrode of a storage battery, and can produce a high-output storage battery. It is possible to provide a composition for a storage battery electrode and a pigment composition using an acetal resin and the modified polyvinyl acetal resin.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Electrochemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Manufacturing & Machinery (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Battery Electrode And Active Subsutance (AREA)

Priority Applications (5)

Applications Claiming Priority (4)

Publications (1)

Family

ID=79555504

Family Applications (1)

Country Status (7)

Citations (8)

Family Cites Families (12)

• 2021
  • 2021-07-13 CN CN202180020605.5A patent/CN115279801B/zh active Active
  • 2021-07-13 KR KR1020227025316A patent/KR20230037482A/ko active Pending
  • 2021-07-13 WO PCT/JP2021/026318 patent/WO2022014596A1/ja not_active Ceased
  • 2021-07-13 EP EP21842935.5A patent/EP4163307A4/en active Pending
  • 2021-07-13 JP JP2021542535A patent/JPWO2022014596A1/ja active Pending
  • 2021-07-13 US US18/014,535 patent/US20230250203A1/en active Pending
  • 2021-07-14 TW TW110125826A patent/TWI886307B/zh active

Patent Citations (8)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events