WO2021215381A1 - Procédé de production d'un polymère réticulé, contenant un groupe carboxyle, ou d'un sel de celui-ci - Google Patents

Procédé de production d'un polymère réticulé, contenant un groupe carboxyle, ou d'un sel de celui-ci Download PDF

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WO2021215381A1
WO2021215381A1 PCT/JP2021/015808 JP2021015808W WO2021215381A1 WO 2021215381 A1 WO2021215381 A1 WO 2021215381A1 JP 2021015808 W JP2021015808 W JP 2021015808W WO 2021215381 A1 WO2021215381 A1 WO 2021215381A1
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mass
polymer
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monomer
crosslinked polymer
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朋子 仲野
篤史 西脇
直彦 斎藤
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東亞合成株式会社
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the present invention relates to a method for producing a carboxyl group-containing crosslinked polymer or a salt thereof.
  • Carboxyl group-containing polymers are used in various applications such as thickeners and viscosity modifiers for cosmetics, binders for non-aqueous electrolyte secondary battery electrodes, sedimentation inhibitors for pigments, and dispersion stabilizers for metal powders. ing.
  • thickener for cosmetics when the carboxyl group-containing polymer is linear, it has a spinnability and feels sticky, but as the degree of cross-linking is increased, the spinnability becomes higher. It has the characteristic that it decreases and you can feel the freshness.
  • a carboxyl group-containing crosslinked polymer is often used because of the advantage that high viscosity can be obtained with a small amount of use.
  • a carboxyl group-containing crosslinked polymer is often used because of the advantages of being able to impart good binding properties and cycle characteristics.
  • the precipitation polymerization method is a polymerization method in which a polymerizable monomer is dissolved in a solvent, but the obtained polymer is insoluble in a solvent and precipitates to obtain a crosslinked polymer, and particles having a size of several ⁇ m to several hundreds of ⁇ m are generally obtained. ..
  • a carboxyl group-containing crosslinked polymer a microcrosslinked acrylic acid-based polymer is produced by precipitation polymerization, and an attempt is made to use it as a binder for a lithium ion secondary battery electrode.
  • the dispersion polymerization method is a method of obtaining a crosslinked polymer as primary particles by using a dispersion stabilizer or the like for precipitation polymerization, depending on the type and amount of the polymerizable monomer, solvent, and dispersion stabilizer.
  • This is a polymerization method capable of controlling the particle size of the produced fine particles, and is suitable for obtaining particles having a size of submicron to several ⁇ m.
  • a carboxyl group-containing crosslinked polymer a microcrosslinked acrylic acid-based polymer is produced by dispersion polymerization, and an attempt is made to use it as a binder for a lithium ion secondary battery electrode.
  • the precipitation polymerization method and the dispersed weight described in Patent Documents 1 and 2 are used as a binder for particles in the slurry (for example, a binder for the active material in the lithium ion secondary battery electrode slurry).
  • a legally produced microcrosslinked acrylic acid-based polymer is used, the micro-crosslinking of the acrylic acid-based polymer can enhance the binding property between the particles in the slurry, while the polymer. Since the spread in water increases and the viscosity increases significantly even with a small amount of addition, there is a limit to the reduction of the slurry viscosity, and both coatability and coating performance (for example, cycle characteristics of a lithium ion secondary battery) can be achieved. There was a problem.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to achieve both coatability and coating performance of a composition containing a carboxyl group-containing crosslinked polymer or a salt thereof.
  • the present invention provides a method for producing a crosslinked polymer or a salt thereof.
  • the present inventors have conducted precipitation polymerization or dispersion polymerization in the presence of an exchange chain transfer mechanism type control agent to carry out a monomer containing an ethylenically unsaturated carboxylic acid monomer.
  • an exchange chain transfer mechanism type control agent to carry out a monomer containing an ethylenically unsaturated carboxylic acid monomer.
  • the present invention is as follows.
  • a polymer comprising a step of polymerizing a body component, wherein the exchange chain transfer mechanism type control agent has a polymer chain of one or more kinds of vinyl-based monomers and a living radical polymerization active unit by the exchange chain transfer mechanism.
  • the crosslinked polymer or a salt thereof is neutralized to a degree of neutralization of 80 to 100 mol%, and then the particle size measured in an aqueous medium is 0.1 ⁇ m or more and 5.0 ⁇ m or less in terms of volume-based median diameter.
  • the carboxyl group-containing crosslinked polymer or a salt thereof obtained by the production method of the present invention it is possible to achieve both the coatability and the coating film performance of the composition containing the crosslinked polymer or the salt thereof.
  • a carboxyl group-containing crosslinked polymer (hereinafter, "" This is a production method comprising a step of producing (also referred to as “the present crosslinked polymer") or a salt thereof.
  • (meth) acrylic means acrylic and / or methacrylic
  • (meth) acrylate means acrylate and / or methacrylate
  • (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • the crosslinked polymer has a structural unit derived from an ethylenically unsaturated carboxylic acid monomer (hereinafter, also referred to as “component (a)”), and is a single amount containing an ethylenically unsaturated carboxylic acid monomer.
  • component (a) ethylenically unsaturated carboxylic acid monomer
  • the body component can be introduced into the polymer by precipitation polymerization or dispersion polymerization. Since the crosslinked polymer has a carboxyl group by having such a structural unit, the adhesiveness to the substrate is improved and water swelling property is imparted.
  • the composition containing the crosslinked polymer or a salt thereof can be enhanced.
  • the adhesiveness to the current collector, which is the base material is improved, and the lithium ion desolvation effect and ionic conductivity are excellent, so the resistance is small and the high rate characteristics are excellent. An electrode is obtained.
  • Examples of the ethylenically unsaturated carboxylic acid monomer include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid; and (meth) acrylamide alkyl such as (meth) acrylamide hexane acid and (meth) acrylamide dodecanoic acid.
  • Carboxylic acid; ethylenically unsaturated monomers having carboxyl groups such as monohydroxyethyl succinate (meth) acrylate, ⁇ -carboxy-caprolactone mono (meth) acrylate, ⁇ -carboxyethyl (meth) acrylate, or (partial) thereof.
  • Alkali neutralized products may be mentioned, and one of these may be used alone, or two or more thereof may be used in combination.
  • a compound having an acryloyl group as a polymerizable functional group is preferable, and particularly preferably Acrylic acid.
  • Acrylic acid is used as the ethylenically unsaturated carboxylic acid monomer, a polymer having a high carboxyl group content can be obtained.
  • the content of the component (a) in the present crosslinked polymer is not particularly limited, but may be, for example, 10% by mass or more and 100% by mass or less with respect to all the structural units of the present crosslinked polymer.
  • the lower limit is, for example, 20% by mass or more, for example, 30% by mass or more, and for example, 40% by mass or more.
  • the lower limit is 50% by mass or more, the dispersion stability of the present composition becomes good and a higher binding force can be obtained, which is preferable, and it may be 60% by mass or more, or 70% by mass or more. It may be 80% by mass or more.
  • the upper limit is, for example, 99.9% by mass or less, for example, 99.5% by mass or less, for example, 99% by mass or less, for example, 98% by mass or less, and for example, 95% by mass. It is less than or equal to, for example, 90% by mass or less, and for example, 80% by mass or less.
  • the range may be a range in which such a lower limit and an upper limit are appropriately combined, and is, for example, 10% by mass or more and 100% by mass or less, and for example, 50% by mass or more and 100% by mass or less, and for example. It can be 50% by mass or more and 99.9% by mass or less, and can be, for example, 50% by mass or more and 99% by mass or less, and can be, for example, 50% by mass or more and 98% by mass or less.
  • the crosslinked polymer may contain a structural unit derived from another ethylenically unsaturated monomer copolymerizable with the component (hereinafter, also referred to as “component (b)”).
  • component (b) includes, for example, an ethylenically unsaturated monomer compound having an anionic group other than a carboxyl group such as a sulfonic acid group and a phosphoric acid group, or a nonionic ethylenically unsaturated monomer.
  • the structural unit from which it is derived can be mentioned.
  • These structural units are ethylenically unsaturated monomer compounds having anionic groups other than carboxyl groups such as sulfonic acid groups and phosphoric acid groups, or monomers containing nonionic ethylenically unsaturated monomers. Can be introduced by copolymerizing.
  • the ratio of the component (b) can be 0% by mass or more and 90% by mass or less with respect to all the structural units of the present crosslinked polymer.
  • the ratio of the component (b) may be 1% by mass or more and 60% by mass or less, 2% by mass or more and 50% by mass or less, and 5% by mass or more and 40% by mass or less. It may be 10% by mass or more and 30% by mass or less.
  • the affinity for the electrolytic solution is improved, so that the lithium ion conductivity is improved. Can also be expected to improve.
  • the component (b) among the above, structural units derived from nonionic ethylenically unsaturated monomers are preferable from the viewpoint of obtaining a coating film having good bending resistance, and nonionic ethylenically unsaturated.
  • the saturated monomer include (meth) acrylamide and its derivatives, a nitrile group-containing ethylenically unsaturated monomer, an alicyclic structure-containing ethylenically unsaturated monomer, a hydroxyl group-containing ethylenically unsaturated monomer, and the like. Be done.
  • Examples of the (meth) acrylamide derivative include N-alkyl (meth) acrylamide compounds such as isopropyl (meth) acrylamide and t-butyl (meth) acrylamide; Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl.
  • N-alkoxyalkyl (meth) acrylamide compounds such as (meth) acrylamide; N, N-dialkyl (meth) acrylamide compounds such as dimethyl (meth) acrylamide and diethyl (meth) acrylamide include one of them. It may be used alone or in combination of two or more.
  • nitrile group-containing ethylenically unsaturated monomer examples include (meth) achlorinitrile; (meth) cyanomethyl acrylate, (meth) cyanoethyl acrylate and other (meth) acrylate cyanoalkyl ester compounds; 4-cyanostyrene. , 4-Cyano- ⁇ -methylstyrene and other unsaturated aromatic compounds containing cyano groups; examples thereof include vinylidene cyanide, and one of these may be used alone or in combination of two or more. You may use it.
  • acrylonitrile is preferable because it has a high nitrile group content.
  • Examples of the alicyclic structure-containing ethylenically unsaturated monomer include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and (meth).
  • Cyclodecyl acrylate and cyclododecyl (meth) acrylate and other aliphatic substituents may have (meth) cycloalkyl acrylate; isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meth).
  • Cycloalkyl polyalcohol mono (meth) acrylate and the like can be mentioned, and one of these may be used alone, or two or more thereof may be used in combination.
  • hydroxyl group-containing ethylenically unsaturated monomer examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, and one of these is used alone. It may be used in combination, or two or more kinds may be used in combination.
  • the crosslinked polymer or a salt thereof is excellent in binding properties to particles in the slurry, and thus contains (meth) acrylamide and its derivatives, a nitrile group-containing ethylenically unsaturated monomer, and an alicyclic structure-containing ethylenic property. It preferably contains structural units derived from unsaturated monomers and the like. Further, particularly in the application of a lithium ion secondary battery, when a structural unit derived from a hydrophobic ethylenically unsaturated monomer having a solubility in water of 1 g / 100 ml or less is introduced as the component (b), an electrode is used. It can exert a strong interaction with the material and can exhibit good binding property to the active material.
  • the above-mentioned "hydrophobic ethylenically unsaturated monomer having a solubility in water of 1 g / 100 ml or less" is particularly selected.
  • An alicyclic structure-containing ethylenically unsaturated monomer is preferable.
  • the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer may be contained as the component (b) in that the cycle characteristics of the obtained secondary battery are improved.
  • the structural unit is preferably contained in an amount of 0.5% by mass or more and 70% by mass or less, more preferably 2.0% by mass or more and 50% by mass or less, and 10.0% by mass or more and 50% by mass or less. It is more preferable to include it.
  • (meth) acrylic acid ester examples include (meth) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • Aromatic (meth) acrylic acid ester compounds such as (meth) phenyl acrylate, (meth) phenylmethyl acrylate, and (meth) phenylethyl acrylate; Examples thereof include (meth) acrylic acid alkoxyalkyl ester compounds such as 2-methoxyethyl (meth) acrylic acid and 2-ethoxyethyl (meth) acrylic acid, and one of these may be used alone. Two or more types may be used in combination.
  • an aromatic (meth) acrylic acid ester compound can be preferably used.
  • Compounds having an ether bond such as (meth) acrylic acid alkoxyalkyl esters such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate, from the viewpoint of further improving lithium ion conductivity and high-rate characteristics. Is preferable, and 2-methoxyethyl (meth) acrylate is more preferable.
  • nonionic ethylenically unsaturated monomers a compound having an acryloyl group is obtained in that a polymer having a long primary chain length can be obtained due to its high polymerization rate and the adhesive strength of this crosslinked polymer is improved. preferable. Further, as the nonionic ethylenically unsaturated monomer, a compound having a glass transition temperature (Tg) of a homopolymer of 0 ° C. or less is preferable in terms of improving the bending resistance of the obtained coating film.
  • Tg glass transition temperature
  • the crosslinked polymer may be in the form of a salt in which some or all of the carboxyl groups contained in the polymer are neutralized.
  • the type of salt is not particularly limited, but alkali metal salts such as lithium salt, sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and barium salt; other metal salts such as magnesium salt and aluminum salt; ammonium. Examples thereof include salts and organic amine salts.
  • alkali metal salts and magnesium salts are preferable, and alkali metal salts are more preferable, from the viewpoint that adverse effects on battery characteristics are unlikely to occur.
  • the present crosslinked polymer is a crosslinked polymer having a crosslinked structure.
  • the cross-linking method in the present cross-linked polymer is not particularly limited, and examples thereof include the following methods. 1) Copolymerization of crosslinkable monomers 2) Utilizing chain transfer to polymer chains during radical polymerization 3) After synthesizing a polymer having a reactive functional group, post-crosslinking is performed by adding a crosslinking agent as necessary.
  • the crosslinked polymer has a crosslinked structure, the crosslinked polymer or a salt thereof can have excellent adhesive strength.
  • the method by copolymerization of crosslinkable monomers is preferable because the operation is simple and the degree of crosslinking can be easily controlled.
  • crosslinkable monomer examples include a polyfunctional polymerizable monomer having two or more polymerizable unsaturated groups, a monomer having a self-crosslinkable crosslinkable functional group such as a hydrolyzable silyl group, and the like. Can be mentioned.
  • the polyfunctional polymerizable monomer is a compound having two or more polymerizable functional groups such as a (meth) acryloyl group and an alkenyl group in the molecule, and is a polyfunctional (meth) acrylate compound, a polyfunctional alkenyl compound, ( Meta) Examples thereof include compounds having both an acryloyl group and an alkenyl group. These compounds may be used alone or in combination of two or more. Among these, a polyfunctional alkenyl compound is preferable because a uniform crosslinked structure can be easily obtained, and a polyfunctional allyl ether compound having two or more allyl ether groups in the molecule is particularly preferable.
  • polyfunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.
  • Di (meth) acrylates of dihydric alcohols such as meta) acrylate; trimethylol propantri (meth) acrylate, tri (meth) acrylate of trimethyl propanethylene oxide modified product, glycerin tri (meth) acrylate, pentaerythritol tri (meth) Tri (meth) acrylates of trivalent or higher polyhydric alcohols such as meta) acrylates and pentaerythritol tetra (meth) acrylates, poly (meth) acrylates such as tetra (meth) acrylates; Bisamides and the like can be mentioned.
  • polyfunctional alkenyl compound examples include polyfunctional allyl ether compounds such as trimethylolpropanediallyl ether, trimethylolpropanetriallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxyethane, and polyallyl saccharose; diallyl phthalate and the like.
  • Polyfunctional allyl compound examples thereof include polyfunctional vinyl compounds such as divinylbenzene.
  • Compounds having both (meth) acryloyl group and alkenyl group include allyl (meth) acrylate, isopropenyl (meth) acrylate, butenyl (meth) acrylate, pentenyl (meth) acrylate, and (meth) acrylate. 2- (2-Vinyloxyethoxy) ethyl and the like can be mentioned.
  • the monomer having a self-crosslinkable crosslinkable functional group include a hydrolyzable silyl group-containing vinyl monomer, N-methylol (meth) acrylamide, N-methoxyalkyl (meth) acrylate and the like. Can be mentioned. These compounds can be used alone or in combination of two or more.
  • the hydrolyzable silyl group-containing vinyl monomer is not particularly limited as long as it is a vinyl monomer having at least one hydrolyzable silyl group.
  • vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl methyl dimethoxysilane, vinyl dimethyl methoxysilanen; silyl such as trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, methyldimethoxysilylpropyl acrylate and the like.
  • Group-containing acrylic acid esters silyl group-containing methacrylate esters such as trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl methacrylate, dimethylmethoxysilylpropyl methacrylate; trimethoxysilylpropyl vinyl ether and the like.
  • Cyril group-containing vinyl ethers examples thereof include silyl group-containing vinyl esters such as trimethoxysilyl undecanoate vinyl.
  • the amount of the crosslinkable monomer used is the total amount of monomers other than the crosslinkable monomer (non-crosslinkable monomer). It is preferably 0.05 parts by mass or more and 5.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass or less, and further preferably 0.2 parts by mass or more with respect to 100 parts by mass. It is 4.0 parts by mass or less, more preferably 0.3 parts by mass or more and 3.0 parts by mass or less.
  • the amount of the crosslinkable monomer used is 0.05 parts by mass or more, it is preferable in that the adhesive strength and the stability of the present composition become better.
  • the amount of the crosslinkable monomer used may be 0.02 to 1.7 mol% with respect to the total amount of the monomers other than the crosslinkable monomer (non-crosslinkable monomer). It is preferably 0.10 to 1.0 mol%, more preferably 0.10 to 1.0 mol%.
  • the crosslinked polymer is a monomer component containing the above ethylenically unsaturated carboxylic acid monomer in the presence of an exchange chain transfer mechanism type control agent (hereinafter, also referred to as “the present monomer”). It is obtained by precipitation polymerization or dispersion polymerization.
  • precipitation polymerization is a method for producing a polymer by carrying out a polymerization reaction in a solvent that dissolves a monomer as a raw material but does not substantially dissolve the polymer to be produced.
  • Dispersion stabilizers can also be used to control the particle size of the polymer.
  • the secondary aggregation can also be suppressed by selecting a dispersion stabilizer, a polymerization solvent, or the like. In general, precipitation polymerization in which secondary agglutination is suppressed is also called dispersion polymerization.
  • the exchange chain transfer mechanism type control agent includes a control agent (hereinafter, also referred to as “RAFT agent”) in the reversible addition-cleaving chain transfer polymerization method (RAFT method).
  • RAFT agent a control agent in the polymerization method using an organic tellurium compound (TERP method)
  • TRIP method organic tellurium compound
  • SBRP method organic antimony compound
  • BIRP method organic bismuth compound
  • the exchange chain transfer mechanism type control agent a polymer having a polymer chain of one or more kinds of vinyl-based monomers and a living radical polymerization active unit by the exchange chain transfer mechanism (hereinafter, simply "the first polymer").
  • a control agent other than the polymer can be used, which will be described in detail in paragraphs [0052] to [0078] described later.
  • the first polymer and the control agent other than the polymer may be used alone or in combination.
  • Precipitation polymerization or dispersion polymerization of this monomer in the presence of an exchange chain transfer mechanism type control agent shortens the primary chain length, and the same chain length forms a uniform crosslinked structure. It is possible to increase the degree of water swelling of the polymer.
  • the RAFT agent and the control agent in the iodine transfer polymerization method are preferable, and the RAFT agent is more preferable, because the crosslinked structure of the present crosslinked polymer can be made more uniform.
  • RAFT agents include a first polymer having a living radical polymerization active unit by a reversible addition-cleavage chain transfer method (detailed below) and / or a RAFT agent (dithioester) other than the first polymer.
  • RAFT agent dithioester
  • Compounds, xanthate compounds, trithiocarbonate compounds, dithiocarbamate compounds, etc. can be used.
  • Specific examples of the RAFT agent other than the first polymer include 2-cyano-2-propylbenzodithioate, 2-phenyl-2-propylbenzodithioate, trithiocarbonate, and 2-cyano-.
  • 2-propyldodecyltrithiocarbonate 2- (dodecylthiocarbonothio oil thio) propionic acid, 3-((1-carboxyethylthio) carbonothio oil thio)) propionic acid, 2- (dodecylthio carbonothio oil thio) Methyl 2-methylpropanoate, 1,4-bis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene, dibenzyltrithiocarbonate, distyryltrithiocarbonate, dicumyltrithiocarbonate, cyanomethyl-N-methyl-N- Examples thereof include phenyldithiocarbamate.
  • the RAFT agents those having trithiocarbonate in the molecule are particularly preferable in that the crosslinked structure of the present crosslinked polymer can be made more uniform.
  • a first polymer having a living radical active unit by the iodine transfer polymerization method (detailed later) and / or a control agent other than the first polymer shall be used.
  • the control agent other than the first polymer include alkyl groups such as methyl iodide, methylene iodide, iodoform, carbon tetraiodide, 1-phenylethyl iodide, and benzyl iodide.
  • Examples thereof include -2-phenylacetic acid) ethylene glycol, bis (2-iodoisobutyric acid) ethylene glycol, 1,5-diiodo-2,4-dimethylbenzene, and 2-iodopropionitrile.
  • the exchange chain transfer mechanism type control agent may be a monofunctional one having one active site, or a bifunctional or more agent having two or more active sites.
  • a bifunctional or higher exchange chain transfer mechanism type control agent is one in which a polymer chain is extended in a bidirectional or higher direction. From the viewpoint of producing the present crosslinked polymer, it may be preferable to use a bifunctional or trifunctional or higher exchange chain transfer mechanism type control agent.
  • the amount of the exchange chain transfer mechanism type control agent used is 0.0001 to 0.50 mol% with respect to the total amount of the present monomer in that the crosslinked structure of the crosslinked polymer can be made more uniform. It is more preferable, it is more preferably 0.0001 to 0.40 mol%, further preferably 0.0001 to 0.30 mol%, and more preferably 0.0002 to 0.30 mol%. More preferred.
  • polymerization initiator used together with the exchange chain transfer mechanism type control agent known polymerization initiators such as azo compounds, organic peroxides, and inorganic peroxides can be used, but are not particularly limited.
  • the conditions of use can be adjusted by known methods such as heat initiation, redox initiation with a reducing agent, and UV initiation so that the amount of radicals generated is appropriate.
  • an azo compound is preferable because it is easy to handle for safety and side reactions during radical polymerization are unlikely to occur.
  • azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4-methoxy-2, 4-Dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-) Carbonitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide) and the like. Only one kind of the radical polymerization initiator may be used, or two or more kinds thereof may be used in combination.
  • the preferable amount of the polymerization initiator used is, for example, 0.001 to 2 parts by mass and, for example, 0.005 to 1 part by mass, when the total amount of the monomer components used is 100 parts by mass. Further, for example, it is 0.01 to 0.1 parts by mass.
  • the amount of the polymerization initiator used is 0.001 part by mass or more, the polymerization reaction can be stably carried out, and when it is 2 parts by mass or less, a polymer having a long primary chain length can be easily obtained.
  • the proportion of the polymerization initiator used is not particularly limited, but the amount of the polymerization initiator used per 1 mol of the exchange chain transfer mechanism type control agent is 0.5 mol from the viewpoint that the crosslinked structure of the present crosslinked polymer can be made uniform. It is preferably less than or equal to 0.2 mol or less. Further, from the viewpoint of stably performing the polymerization reaction, the lower limit of the amount of the polymerization initiator used with respect to 1 mol of the exchange chain transfer mechanism type control agent is 0.001 mol.
  • the amount of the polymerization initiator used with respect to 1 mol of the exchange chain transfer mechanism type control agent is preferably in the range of 0.001 mol or more and 0.5 mol or less, and more preferably in the range of 0.005 mol or more and 0.2 mol or less.
  • the polymerization solvent a solvent selected from water, various organic solvents and the like can be used in consideration of the type of monomer used and the like. In order to obtain a polymer having a longer primary chain length, it is preferable to use a solvent having a small chain transfer constant.
  • Specific examples of the polymerization solvent include water-soluble solvents such as methanol, t-butyl alcohol, acetone, methyl ethyl ketone, acetonitrile and tetrahydrofuran, as well as benzene, ethyl acetate, dichloroethane, n-hexane, cyclohexane and n-heptane.
  • the water-soluble solvent refers to a solvent having a solubility in water at 20 ° C. of more than 10 g / 100 ml.
  • Methyl ethyl ketone and acetonitrile are preferable because they are easy to use), a polymer having a small chain transfer constant and a large degree of polymerization (primary chain length) can be obtained, and the operation is easy during the step neutralization described later. ..
  • a highly polar solvent preferably include water and methanol.
  • the amount of the highly polar solvent used is preferably 0.05 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, still more preferably 0.1 to 5% by mass based on the total mass of the medium. It is 0.0% by mass, more preferably 0.1 to 1.0% by mass.
  • the polymerization rate is improved when a highly polar solvent is added, and it becomes easy to obtain a polymer having a long primary chain length.
  • a highly polar solvent water is particularly preferable because it has a large effect of improving the polymerization rate.
  • the reaction temperature during the polymerization reaction in the presence of the exchange chain transfer mechanism type controller is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and further preferably 50 ° C. or higher and 100 ° C. or higher. It is below ° C.
  • the reaction temperature is 30 ° C. or higher, the polymerization reaction can proceed smoothly.
  • the reaction temperature is 120 ° C. or lower, side reactions can be suppressed and restrictions on the initiators and solvents that can be used are relaxed.
  • the crosslinked polymer dispersion obtained through the polymerization step can be obtained in a powder state by subjecting the dispersion to a reduced pressure and / or heat treatment in the drying step and distilling off the solvent.
  • a solid-liquid separation step such as centrifugation and filtration, an organic solvent or an organic solvent / water. It is preferable to include a cleaning step using a mixed solvent.
  • an alkaline compound is added to the dispersion of the crosslinked polymer obtained in the polymerization step to add weight.
  • step neutralization After neutralizing the coalescence (hereinafter, also referred to as "step neutralization"), the solvent may be removed in a drying step.
  • post-neutralization an alkaline compound is added when preparing the slurry composition to neutralize the polymer (hereinafter, "post-neutralization”). It may also be called).
  • post-neutralization is added when preparing the slurry composition to neutralize the polymer. It may also be called).
  • process neutralization is preferable because the secondary aggregates tend to be easily disintegrated.
  • first monomer a polymerized chain of one kind or two or more kinds of vinyl-based monomers (hereinafter, also simply referred to as “first monomer”)
  • first monomer a polymer (first polymer) having a living radical polymerization active unit by an exchange chain transfer mechanism and a “first polymer chain”
  • the first polymer is used as a starting point for the polymerization of the present monomer and the polymerization of the crosslinked polymer.
  • the present crosslinked polymer which can be used as a dispersion stabilizer in a solvent and has a polymer chain having a structural unit derived from the present monomer bonded to the polymer chain of the first polymer, is obtained as dispersed fine particles. Can be done. By doing so, the polymerization stability, that is, the aggregation of the present crosslinked polymer during the polymerization step is suppressed, the generation of coarse aggregated particles is suppressed, the particle size is small, and the particle size distribution is narrow. You can get coalescence.
  • the first polymer In order to make the first polymer function as a dispersion stabilizer in producing the present crosslinked polymer by polymerizing the present monomer in the presence of the first polymer, for example, the first polymer is used. , 0.3 parts by mass or more and 50 parts by mass or less can be used with respect to 100 parts by mass of the total mass of this monomer. By using it in such a range, it is possible to produce the present crosslinked polymer mainly containing the present monomer while allowing the first polymer to function as a dispersion stabilizer.
  • the amount of the first polymer is less than 0.3 parts by mass, it is difficult to obtain a sufficient dispersion stabilizing effect, and the particle size of the crosslinked polymer tends to exceed 0.3 ⁇ m, even if it exceeds 50 parts by mass. This is because it is difficult to improve the functionality as a dispersion stabilizer, and the effect of reducing the particle size of the crosslinked polymer is also reduced.
  • the first polymer can be used with respect to 100 parts by mass of the total mass of the present monomer, for example, 0.5 parts by mass or more, and for example, 1 part by mass or more. Further, the first polymer can be used, for example, 40 parts by mass or less, for example, 30 parts by mass or less, and for example, 20 parts by mass or less.
  • the range of the amount of the first polymer used with respect to 100 parts by mass of the total mass of the present monomer can be set by appropriately combining the above upper limit and lower limit.
  • the polymerization conditions for producing the first polymer are well known to those skilled in the art, and examples of the polymerization process include various processes such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Considering that it is a polymerization starting point in the production of coalescence and that it functions as a dispersion stabilizer, solution polymerization can be used, for example. Further, the polymerization conditions such as the type of the exchange chain transfer mechanism control agent, the type and amount of the polymerization initiator, the polymerization solvent, and the reaction temperature are described in the above paragraphs [0040] to [0043] and [0045] to [0049].
  • the amount of the exchange chain transfer mechanism control agent used is appropriately adjusted according to the number average molecular weight (Mn) of the target first polymer.
  • Mn number average molecular weight
  • a RAFT agent and a control agent in the iodine transfer polymerization method are preferable in that the molecular weight distribution of the first polymer can be reduced.
  • the concentration at the time of producing the first polymer is not particularly limited with respect to the total mass of the amount charged such as the polymerization solvent and the first monomer, but is, for example, 10% by mass or more and 80% by mass. % Or less, for example, 15% by mass or more and 70% by mass or less, and for example, 20% by mass or more and 70% by mass or less.
  • a living polymerization active unit is provided at the end of the first polymerization chain, and the exchange chain transfer mechanism type having two or more functionalitys is used.
  • a control agent when used, it is branched in two or more directions with the living polymerization active unit as a base point, and each of them is provided with a first polymerization chain.
  • the other polymerized chain when another polymerized chain is provided, the other polymerized chain is directly bonded to the living polymerization active unit, and the first polymerization is carried out more distally to the living polymerization active unit.
  • the first polymerized chain is bonded to the distal end of the other polymerized chain so that the chain is provided.
  • the first polymer may also include two or more types of first polymerized chains. For example, after performing living radical polymerization or the like using one or more first monomers of a certain composition, one or more first monomers of another composition are used. By carrying out living radical polymerization or the like, a first polymer having a first polymerization chain (block) having a structural unit derived from the first monomer having a different composition can be obtained.
  • the number average molecular weight (Mn) of the first polymer is not particularly limited, but is, for example, 3,000 or more, for example, 5,000 or more, and for example, 7,000 or more. Also, for example, 8,000 or more, and for example, 10,000 or more. Further, the Mn is 50,000 or less, for example, 30,000 or less, and for example, 25,000 or less, and for example, 20,000 or less, and for example, 15,000 or less. And, for example, 14,000 or less, and for example, 12,000 or less.
  • the range of Mn can be set by appropriately combining the above-mentioned lower limit and upper limit, and is, for example, 5,000 or more and 25,000 or less, and for example, 10,000 or more and 25,000 or less. For example, it is 10,000 or more and 15,000 or less, and for example, 10,000 or more and 14,000 or less.
  • the weight average molecular weight (Mw) of the first polymer is not particularly limited, but is, for example, 5,000 or more, for example, 7,000 or more, and for example, 9,000 or more. Also, for example, 10,000 or more, for example, 13,000 or more, and for example, 15,000 or more. Further, the Mw is 60,000 or less, for example, 55,000 or less, and for example, 50,000 or less, and for example, 45,000 or less, and for example, 40,000 or less. And, for example, 36,000 or less, and for example, 35,000 or less, and for example, 30,000 or less, and for example, 25,000 or less.
  • the range of Mw can be set by appropriately combining the above-mentioned lower limit and upper limit, and is, for example, 1,000 or more and 40,000 or less, and for example, 10,000 or more and 35,000 or less. For example, it is 10,000 or more and 30,000 or less, and for example, 15,000 or more and 25,000 or less.
  • Both Mw and Mn of the first polymer can be measured by gel permeation chromatography using polystyrene as a standard substance.
  • the details of the chromatography conditions the conditions disclosed in the subsequent examples can be adopted.
  • the molecular weight distribution (Mw / Mn) of the first polymer is not particularly limited, but is, for example, 2.5 or less, for example, 2.4 or less, and for example, 2.3 or less. Yes, for example 2.0 or less, and for example 1.6 or less, and for example 1.5 or less, and for example 1.4 or less, and for example 1.3 or less. be. Further, the molecular weight distribution is, for example, 1.1 or more, for example, 1.2 or more, and for example, 1.3 or more, and for example, 1.4 or more, and for example, 1.5 or more. Is.
  • the range of the molecular weight distribution can be set by appropriately combining the above-mentioned lower limit and upper limit. For example, 1.1 or more and 2.5 or less, for example, 1.1 or more and 2.4 or less, and for example, 1 It can be 1 or more and 2.3 or less, and for example, 1.1 or more and 2.0 or less.
  • the molecular weight distribution is preferably 2.4 or less, and in order to obtain the present crosslinked polymer having a smaller particle size, it is preferably 1.7 or less, and more preferably 1. It is 6 or less, and more preferably 1.4 or less.
  • first monomer examples include styrenes, (meth) acrylonitrile compounds, maleimide compounds, unsaturated acid anhydrides and unsaturated carboxylic acid compounds. One or a combination of two or more of these can be used.
  • Styrenes include styrene and its derivatives. Specific compounds include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, and m-.
  • styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene are preferable from the viewpoint of polymerizable property.
  • Examples of the (meth) acrylonitrile compound include (meth) acrylonitrile, acrylonitrile, ⁇ -methylacrylonitrile, and the like.
  • acrylonitrile is used.
  • the maleimide compound includes a maleimide and an N-substituted maleimide compound.
  • the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, and N-tert-butyl.
  • N-alkyl-substituted maleimide compounds such as maleimide, N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide, etc.
  • N-Cycloalkyl-substituted maleimide compounds N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-acetylphenyl) maleimide, N- (4-methoxyphenyl) maleimide, N- (4-ethoxy) Examples thereof include N-aryl-substituted maleimide compounds such as phenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, and N-benzylmaleimide, and one or more of these. Can be used. For example, N-phenylmaleimide is used.
  • examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and one or more of these can be used.
  • unsaturated carboxylic acid compounds include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, silicic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, and anhydrous.
  • unsaturated dicarboxylic acids such as itaconic acid and citraconic anhydride, and monoalkyl esters of unsaturated dicarboxylic acids, and one or more of them can be used.
  • the first monomer preferably contains, for example, at least styrenes.
  • styrenes are easy to carry out in the living room and can impart appropriate hydrophobicity and affinity to organic solvents. It is possible to impart hydrophobicity or affinity to an organic solvent to the first polymerized chain.
  • the first polymer tends to be present on the surface layer of the crosslinked polymer, and the crosslinked polymer is produced. Dispersion stability is improved.
  • Styrene is, for example, 20% by mass or more of the total mass of the first monomer. This is because if the content is 20% by mass or more, the living polymerization is facilitated, and an appropriate hydrophobicity and an affinity for an organic solvent can be appropriately imparted. Further, for example, it is 30% by mass or more, and for example, 35% by mass or more, and for example, 40% by mass or more, and for example, 50% by mass or more, and for example, 60% by mass or more. Further, for example, it is 65% by mass or more, for example, 70% by mass or more, and for example, 75% by mass or more.
  • the styrenes are 100% by mass or less of the total mass, and are, for example, 95% by mass or less, and are, for example, 90% by mass or less, and are, for example, 85% by mass or less, and are, for example,. It is 80% by mass or less, and for example, 75% by mass or less.
  • the range of the styrenes with respect to the total mass can be set by appropriately combining the above-mentioned lower limit and upper limit, and is, for example, 20% by mass or more and 95% by mass or less, and for example, 30% by mass or more and 75% by mass or more. And, for example, 35% by mass or more and 85% by mass or less.
  • the (meth) acrylonitrile compound, maleimide compound, acid anhydride and unsaturated carboxylic acid compound can be used alone, and it is preferable to use one or more of these four types in combination with styrenes. This is because all of these four types can maintain, regulate or impart the hydrophobicity or organic solvent affinity of the first polymerized chain.
  • one or more of (meth) acrylonitrile compounds such as acrylonitrile, maleimide compounds such as N-phenylmaleimide, and acid anhydrides.
  • a combination of styrene and acrylonitrile, styrene and N-phenylmaleimide and the like is preferable.
  • the unsaturated carboxylic acid compound is preferable in that the polarity of the first polymer can be easily changed.
  • the total amount of these one or more first monomers other than styrenes is the first monomer for polymerizing the first polymerized chain (first). It is, for example, 20% by mass or more of the total mass of the first monomer unit of the polymerized chain). Further, for example, it is 25% by mass or more, and for example, 30% by mass or more, and for example, 35% by mass or more, and for example, 40% by mass or more, and for example, 50% by mass or more. Further, for example, it is 60% by mass or more.
  • the (meth) acrylonitrile compound is 80% by mass or less of the total mass, and is, for example, 75% by mass or less, and is, for example, 70% by mass or less, and is, for example, 65% by mass or less. Further, for example, it is 60% by mass or less, for example, 55% by mass or less, and for example, 50% by mass or less.
  • the range of the styrenes with respect to the total mass can be set by appropriately combining the above lower limit and upper limit, and is, for example, 20% by mass or more and 65% by mass or less, and for example, 25% by mass or more and 50% by mass or more. It is as follows.
  • the first polymerized chain may be a polymerized chain containing only the first monomer described above, but if necessary, other vinyl-based monomers other than the above may be used as the first monomer. be able to.
  • known vinyl-based monomers such as (meth) acrylic acid esters such as (meth) acrylic acid and alkyl (meth) acrylic acid can be used.
  • these other monomers are, for example, 10% by mass or less, for example, 5% by mass or less, for example, 3% by mass or less, or, for example, the total mass of the monomers constituting the first polymerized chain. 1, 1% by mass or less, and for example, 0.5% by mass or less.
  • the first polymer may include a block (another polymer chain) different from that of the first polymer chain.
  • Such other polymerized chains may be added, for example, in another synthetic step after the formation of the first polymerized chain.
  • a radical polymerization initiator and another vinyl-based monomer are continuously or newly supplied to the first polymer having the first polymer chain to have a composition different from that of the first polymer chain. It is possible to obtain a first polymer having another polymer chain (block) composed of units derived from a monomer other than the first monomer.
  • a part of the monomer common to the present monomer used in the present crosslinked polymer can be partially linked in advance. It can be provided in the first polymer.
  • the first polymer has a living radical polymerization active unit by an exchange chain transfer mechanism, it can be used as a solubility or dispersion stabilizer in the polymerization solvent of the first polymer in the precipitation polymerization or dispersion polymerization of this monomer.
  • Various monomers can be selected for the function of.
  • RAFT method reversible addition-cleavage chain transfer polymerization method
  • iodine transfer polymerization method a polymerization method using an organic tellurium compound
  • TMP method a polymerization method using an organic tellurium compound
  • SBRP method organic antimony compound
  • BIRP method organic bismuth compound
  • the RAFT method and the iodine transfer polymerization method are preferable, and the RAFT method is more preferable, because the particle size of the crosslinked polymer can be reduced.
  • the crosslinked polymer or a salt thereof preferably has a viscosity of 100 mPa ⁇ s or more in a 2% by mass aqueous solution thereof.
  • the viscosity of the 2% by mass aqueous solution is 100 mPa ⁇ s or more
  • the composition containing the crosslinked polymer has high storage stability and can exhibit excellent adhesive strength.
  • the viscosity of the 2 mass% concentration aqueous solution may be 1,000 mPa ⁇ s or more, 10,000 mPa ⁇ s or more, or 50,000 mPa ⁇ s or more.
  • This crosslinked polymer absorbs water and becomes swollen in water.
  • the crosslinked polymer has an appropriate degree of crosslinkage, the larger the amount of hydrophilic groups contained in the crosslinked polymer, the easier it is for the crosslinked polymer to absorb water and swell.
  • the degree of cross-linking the lower the degree of cross-linking, the easier it is for the cross-linked polymer to swell.
  • the number of cross-linking points is the same, the larger the molecular weight (primary chain length), the more cross-linking points that contribute to the formation of the three-dimensional network, so that the cross-linked polymer is less likely to swell.
  • the viscosity of the crosslinked polymer aqueous solution can be adjusted by adjusting the amount of hydrophilic groups of the crosslinked polymer, the number of crosslinked points, the primary chain length, and the like.
  • the number of the cross-linking points can be adjusted by, for example, the amount of the cross-linking monomer used, the chain transfer reaction to the polymer chain, the post-crosslinking reaction, and the like.
  • the primary chain length of the polymer can be adjusted by setting conditions related to the amount of radicals generated such as the initiator and the polymerization temperature, and selecting the polymerization solvent in consideration of chain transfer and the like.
  • the crosslinked polymer does not exist as a mass (secondary agglomerate) having a large particle size, but is well dispersed as water-swelled particles having an appropriate particle size. Is preferable because it can exhibit good adhesive strength.
  • the particle size (water-swelling particle size) when a crosslinked polymer having a degree of neutralization based on a carboxyl group of 80 to 100 mol% is dispersed in water is a volume-based median diameter. It is preferably in the range of 0.1 ⁇ m or more and 5.0 ⁇ m or less.
  • the more preferable range of the particle size is 0.1 ⁇ m or more and 4.0 ⁇ m or less, the more preferable range is 0.1 ⁇ m or more and 3.0 ⁇ m or less, and the more preferable range is 0.2 ⁇ m or more and 3.0 ⁇ m or less. Yes, and even more preferable ranges are 0.3 ⁇ m or more and 3.0 ⁇ m or less.
  • the composition When the particle size is in the range of 0.1 ⁇ m or more and 5.0 ⁇ m or less, the composition is uniformly present in a suitable size in the present composition, so that the present composition is highly stable and exhibits excellent adhesive strength. It becomes possible. If the particle size exceeds 5.0 ⁇ m, the adhesive strength may be insufficient as described above. In addition, there is a risk that the coatability will be insufficient because it is difficult to obtain a smooth coated surface. On the other hand, when the particle size is less than 0.1 ⁇ m, there is concern from the viewpoint of stable manufacturability.
  • acid groups such as a carboxyl group derived from an ethylenically unsaturated carboxylic acid monomer are neutralized so that the degree of neutralization is 20 mol% or more in the present composition, and the mode of the salt is It is preferable to use as.
  • the degree of neutralization is more preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 75 mol% or more, still more preferably 80 mol% or more, and particularly preferably. It is 85 mol% or more.
  • the upper limit of the degree of neutralization is 100 mol%, and may be 98 mol% or 95 mol%.
  • the range of the degree of neutralization may be appropriately combined with the above lower limit value and upper limit value, and may be, for example, 50 mol% or more and 100 mol% or less, or 75 mol% or more and 100 mol% or less. , 80 mol% or more and 100 mol% or less.
  • the degree of neutralization is 20 mol% or more, the water swelling property is good and the dispersion stabilizing effect is easily obtained, which is preferable.
  • the degree of neutralization can be calculated by calculation from the charged values of a monomer having an acid group such as a carboxyl group and a neutralizing agent used for neutralization.
  • the crosslinked polymer or a salt thereof preferably has a water swelling degree of 20 or more and 80 or less at pH 8.
  • the degree of water swelling is within the above range, the crosslinked polymer or a salt thereof swells appropriately in an aqueous medium, so that a sufficient adhesion area to the particles in the slurry and the substrate is secured when forming the coating film. It becomes possible to do so, and the binding property tends to be good.
  • the degree of water swelling may be, for example, 21 or more, 23 or more, 25 or more, 27 or more, or 30 or more.
  • the degree of water swelling is 20 or more, the crosslinked polymer or a salt thereof spreads on the surface of the particles or the base material in the slurry, and a sufficient adhesive area can be secured, so that good binding property can be obtained.
  • the upper limit of the degree of water swelling at pH 8 may be 75 or less, 70 or less, 65 or less, 60 or less, or 55 or less. If the degree of water swelling exceeds 80, the viscosity of the present composition tends to increase, and as a result of insufficient uniformity of the mixture layer, sufficient binding force may not be obtained. In addition, the coatability of the present composition may decrease.
  • the range of the degree of water swelling at pH 8 can be set by appropriately combining the above upper limit value and lower limit value, and is, for example, 23 or more and 70 or less, and for example, 25 or more and 65 or less, and for example, 25. It is 55 or less.
  • the degree of water swelling at pH 8 can be obtained by measuring the degree of swelling of the crosslinked polymer or a salt thereof in water at pH 8.
  • the pH at the time of measurement is, for example, in the range of 8.0 ⁇ 0.5, preferably in the range of 8.0 ⁇ 0.3, more preferably in the range of 8.0 ⁇ 0.2, and further. It is preferably in the range of 8.0 ⁇ 0.1.
  • a person skilled in the art can adjust the degree of water swelling by controlling the composition and structure of the crosslinked polymer.
  • the degree of water swelling can be increased by introducing an acidic functional group or a highly hydrophilic structural unit into the crosslinked polymer. Further, by lowering the degree of cross-linking of the cross-linked polymer, the degree of water swelling is usually increased.
  • the measuring device is shown in FIG.
  • the measuring device is composed of ⁇ 1> to ⁇ 3> in FIG. ⁇ 1> It is composed of a burette 1, a pinch cock 2, a silicon tube 3 and a polytetrafluoroethylene tube 4 having a branch tube for venting air.
  • a support cylinder 8 having a large number of holes on the bottom surface is installed on the funnel 5, and a filter paper 10 for an apparatus is installed on the support cylinder 8.
  • the measuring method will be described below.
  • the pinch cock 2 in ⁇ 1> is removed, ion-exchanged water is poured from the upper part of the burette 1 through the silicon tube 3, and the burette 1 to the filter paper 10 for the device are filled with the ion-exchanged water 12.
  • the pinch cock 2 is closed, and air is removed from the polytetrafluoroethylene tube 4 connected to the burette branch pipe with a rubber stopper. In this way, the ion-exchanged water 12 is continuously supplied from the burette 1 to the filter paper 10 for the apparatus.
  • the reading (a) of the scale of the burette 1 is recorded.
  • the particle size distribution of the hydrogel was measured with a laser diffraction / scattering particle size distribution meter (Microtrack MT-3300EXII, manufactured by Microtrac Bell) using ion-exchanged water as a dispersion medium.
  • a laser diffraction / scattering particle size distribution meter Microtrack MT-3300EXII, manufactured by Microtrac Bell
  • the particle size distribution shape measured after several minutes became stable.
  • the particle size distribution was measured to obtain a volume-based median diameter (D50) as a representative value of the particle size.
  • a hydrogel fine particle dispersion in which the polymer salt was swollen in water was prepared. After adjusting each of the obtained hydrogel fine particle dispersions to 25 ° C. ⁇ 1 ° C., the viscosity at a rotor speed of 12 rpm was measured using a B-type viscometer (TVB-10 manufactured by Toki Sangyo Co., Ltd.).
  • the reaction rate of the obtained polymer 1 was 72%.
  • the molecular weight of the polymer 1 was Mn11,900, Mw15,500, and Mw / Mn was 1.30. Styrene and acrylonitrile correspond to the first monomer.
  • the molecular weight of the first polymer was measured by gel permeation chromatography (GPC). That is, a polystyrene-equivalent number average molecular weight (Mn) and a weight average molecular weight (Mw) were obtained by THF-based GPC. Moreover, the molecular weight distribution (Mw / Mn) was calculated from the obtained values.
  • GPC gel permeation chromatography
  • LiOH / H 2 O lithium hydroxide / monohydrate
  • the obtained polymerization reaction solution was centrifuged to settle the polymer particles, and then the supernatant was removed. Then, after redispersing the precipitate in acetonitrile having the same weight as the polymerization reaction solution, the washing operation of precipitating the polymer particles by centrifugation to remove the supernatant was repeated twice.
  • the precipitate was recovered and dried at 80 ° C. for 3 hours under reduced pressure conditions to remove volatile components to obtain a powder of the carboxyl group-containing polymer salt R-1. Since the carboxyl group-containing polymer salt R-1 has hygroscopicity, it was stored in a container having a water vapor barrier property.
  • the degree of water swelling was 36.4, the particle size in the aqueous medium was 1.72 ⁇ m, and the viscosity of the 2% by mass aqueous solution was 9,110 mPa ⁇ s.
  • Examples 2 to 15 and Comparative Examples 1 to 2 Production of carboxyl group-containing crosslinked polymer salts R-2 to R-17
  • the same operation as in Production Example 1 was carried out except that the amounts of the monomer, the crosslinkable monomer and the neutralizing agent were as shown in Table 1, and the carboxyl group-containing crosslinked polymer salts R-2 to R were carried out.
  • a polymerization reaction solution containing -17 was obtained.
  • the same operations as in Production Example 1 were carried out for each polymerization reaction solution to obtain powdery carboxyl group-containing crosslinked polymer salts R-2 to R-17.
  • Each carboxyl group-containing crosslinked polymer salt was sealed and stored in a container having a water vapor barrier property.
  • Table 1 shows the degree of water swelling of R-2 to R-17, the particle size in the aqueous medium, and the viscosity of the 2% by mass aqueous solution.
  • the particle diameter in an aqueous medium of R-3 (degree of neutralization 70 mol%) was measured after adjusting the neutralization degree of 90 mol% by LiOH ⁇ H 2 O.
  • NMP N-methylpyrrolidone
  • 100 parts of lithium iron phosphate (LFP) as the positive electrode active material 100 parts of lithium iron phosphate (LFP) as the positive electrode active material, 0.2 parts of carbon nanotubes as the conductive agent, 2 parts of Ketjen black, and vapor layer carbon fiber (VGCF).
  • VGCF vapor layer carbon fiber
  • PVDF polyvinylidene fluoride
  • the mixture was punched 3 cm square to obtain a positive electrode plate.
  • a lithium ion secondary battery of a laminated cell was produced.
  • the electrolytic solution one in which LiPF 6 was dissolved at a concentration of 1.0 mol / liter in a mixed solvent containing ethylene carbonate (EC) and ethyl methyl carbonate (DEC) at a volume ratio of 25:75 was used.
  • the performance of the coating film obtained from the above slurry composition was evaluated by measuring the cycle characteristics of the lithium ion secondary battery.
  • the lithium-ion secondary battery of the laminated cell produced by the above procedure is charged / discharged at a charge / discharge rate of 0.2 C under the condition of 2.7 to 3.4 V by CC discharge, and the initial capacity is increased. C0 was measured. Further, charging and discharging were repeated in an environment of 25 ° C., and the capacity C50 after 50 cycles was measured.
  • the cycle characteristic ( ⁇ C) calculated by the following formula was 91.8%, and the cycle characteristic based on the following criteria was evaluated as “ ⁇ ”. The higher the value of ⁇ C, the better the cycle characteristics.
  • ⁇ C C50 / C0 ⁇ 100 (%) ⁇ Evaluation criteria> ⁇ : Charge / discharge capacity retention rate is 95.0% or more ⁇ : Charge / discharge capacity retention rate is 90.0% or more and less than 95.0% ⁇ : Charge / discharge capacity retention rate is 85.0% or more and less than 90.0% ⁇ : Charge / discharge capacity retention rate is less than 85.0%
  • Examples 2 to 15 and Comparative Examples 1 to 2 Evaluation of a composition containing carboxyl group-containing crosslinked polymer salts R-2 to R-17
  • a slurry composition was prepared by performing the same operation as in Example 1 except that the carboxyl group-containing crosslinked polymer salt was as shown in Table 1, and the viscosity of the composition was measured.
  • the coatability of the composition and the cycle characteristics of the secondary battery obtained by using the composition were evaluated. The results are shown in Table 1.
  • the composition containing the carboxyl group-containing crosslinked polymer or a salt thereof obtained by the production method of the present invention is excellent in both coatability and coating performance, it is a thickener for cosmetics, a viscosity modifier, and non-water. It is expected to be applied to various applications such as binders for electrolyte secondary battery electrodes, sedimentation inhibitors for pigments, and dispersion stabilizers for metal powders.

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Abstract

La présente invention concerne un procédé de production d'un polymère réticulé, contenant un groupe carboxyle, ou d'un sel de celui-ci, grâce auquel il est possible d'obtenir un bon équilibre entre l'aptitude au revêtement et les performances en termes de film de revêtement d'une composition qui contient ce polymère réticulé ou un sel de celui-ci.　Ce procédé de production d'un polymère réticulé, contenant un groupe carboxyle, ou d'un sel de celui-ci comprend une étape consistant à polymériser des composants monomères comprenant un monomère acide carboxylique éthyléniquement insaturé par polymérisation par précipitation ou par polymérisation par dispersion en présence d'un agent de régulation de type à mécanisme d'échange par transfert de chaîne. L'agent de régulation de type à mécanisme d'échange par transfert de chaîne est un polymère comportant un motif actif de polymérisation radicalaire vivante issu d'un mécanisme d'échange par transfert de chaîne avec une ou plusieurs chaînes polymères de monomères à base de vinyle, et/ou un polymère autre que ledit polymère.
PCT/JP2021/015808 2020-04-23 2021-04-19 Procédé de production d'un polymère réticulé, contenant un groupe carboxyle, ou d'un sel de celui-ci WO2021215381A1 (fr)

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WO2022131239A1 (fr) * 2020-12-18 2022-06-23 東亞合成株式会社 Liant pour électrode de batterie rechargeable et son procédé de production, composition de couche de mélange d'électrode de batterie rechargeable, électrode de batterie rechargeable et batterie rechargeable

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