CN114729085A - Polymer particles - Google Patents

Polymer particles Download PDF

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Publication number
CN114729085A
CN114729085A CN202180006607.9A CN202180006607A CN114729085A CN 114729085 A CN114729085 A CN 114729085A CN 202180006607 A CN202180006607 A CN 202180006607A CN 114729085 A CN114729085 A CN 114729085A
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polymer particles
acrylate
meth
particles
monomer
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今津直树
佐藤谦一
甲斐信康
杉浦美月
小田岛智幸
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Toray Industries Inc
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Toray Industries Inc
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/18—Esters containing halogen
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention provides polymer particles containing a structural unit derived from an acrylate monomer, which can form a coating film having excellent flexibility and chemical resistance by mixing a small amount of the polymer particles with other particles. The particles are made of a polymer having a glass transition temperature Tg of 20 ℃ to 80 ℃, and the elastic modulus of a particle film made of the polymer particles is 1.7GPa or less, the volume average particle diameter in water is 100 to 500nm, and the particles contain a structural unit derived from an acrylate monomer.

Description

Polymer particles
Technical Field
The present invention relates to polymer particles capable of forming a coating film having excellent flexibility and chemical resistance.
Background
The polymer particles are used for the purpose of providing adhesion by coating on various substrates for binder applications aimed at improving the battery characteristics of lithium ion 2-time batteries. Polymer particles are required to have various properties depending on the application, and various proposals have been made to satisfy such requirements (for example, see patent documents 1 to 3).
However, polymer particles that form a coating film having excellent flexibility and chemical resistance have not yet been established.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6111895
Patent document 2: japanese patent No. 6011608
Patent document 3: japanese patent No. 5698127
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide polymer particles which can be mixed in a small amount in a coating film to form a coating film having excellent flexibility and chemical resistance.
Means for solving the problems
The polymer particles of the present invention are particles made of a polymer having a glass transition temperature of 20 ℃ or higher and 80 ℃ or lower, and are characterized in that the elastic modulus of a particle film made of the polymer particles is 1.7GPa or lower, and the volume average particle diameter of the polymer particles in water is 100 to 500 nm.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymer particles of the present invention can exhibit flexibility and chemical resistance by adding a small amount of the polymer particles to a coating film.
Detailed Description
Hereinafter, preferred embodiments according to the present invention will be described in detail. The present invention is not limited to the embodiments described below, but it should be understood that the present invention also includes various modifications that can be implemented within a range not changing the gist of the present invention.
The polymer particles of the present invention are made of a polymer having a glass transition temperature (Tg) of 20 ℃ or higher and 80 ℃ or lower. When the Tg of the polymer is in the above range, fusion of the particles causes film formation of the particles, and polymer particles exhibiting adhesion due to an anchoring effect can be stably produced.
The lower limit of the glass transition temperature (Tg) of the polymer is preferably more than 20 ℃, more preferably 25 ℃ or more, further preferably 30 ℃ or more, further preferably 35 ℃ or more, and particularly preferably 40 ℃ or more. The upper limit of the glass transition temperature (Tg) of the polymer is preferably less than 80 ℃, more preferably 70 ℃ or less, still more preferably 60 ℃ or less, and still more preferably 50 ℃ or less. The glass transition temperature (Tg) of the polymer can be adjusted by changing the kind and composition ratio of the monomers.
In the present specification, the "Tg of the polymer" is a value in accordance with JIS K7121: 2012 by Differential Scanning Calorimetry (DSC).
The elastic modulus of the particle film made of the polymer particles of the present invention is 1.7GPa or less.
The elastic modulus of the particle film made of the polymer particles was measured as follows. A dispersion liquid in which polymer particles were dispersed in water so that the solid content concentration became 10 mass% was prepared, the dispersion liquid was applied to a PET substrate by a bar coater (# 3), and dried at 60 ℃ for 10 minutes to form a coating film layer, and the elastic modulus of a particle film made of the polymer particles was measured by measuring the surface elastic modulus of the coating film layer by an Atomic Force Microscope (AFM).
The lower limit of the elastic modulus of the particle film made of the polymer particles is preferably 0.1GPa or more, more preferably 0.5GPa or more, and further preferably 0.7GPa or more. The upper limit of the elastic modulus of the particle film made of the polymer particles is preferably less than 1.7GPa, more preferably 1.4GPa or less, and further preferably 1.2GPa or less. By setting the elastic modulus of the particle film made of the polymer particles to the above range, the particles are prevented from being broken by external pressure, and polymer particles having excellent flexibility can be stably produced. The elastic modulus of the particle film made of the polymer particles can be adjusted by changing the kind and composition ratio of the monomer.
The volume average particle diameter of the polymer particles in water is 100 to 500 nm.
The lower limit of the volume average particle diameter of the polymer particles in water is preferably more than 100nm, more preferably 120nm or more, and further preferably 150nm or more. The upper limit of the volume average particle diameter of the polymer particles in water is preferably 500nm or less, more preferably 450nm or less, and still more preferably 400nm or less. If the volume average particle diameter is less than 100nm, there is a possibility that: the viscosity of a dispersion liquid obtained by dispersing polymer particles in water increases, and it is difficult to obtain an aqueous dispersion liquid having a high solid content. Further, if the volume average particle diameter exceeds 500nm, the storage stability of the aqueous dispersion of polymer particles may be lowered, and the uniformity of the formed coating film may be further lowered. The volume average particle diameter of the polymer particles can be adjusted by changing the kind and composition ratio of the emulsifier. In the present specification, the numerical ranges indicated by "to" mean "above" and "below".
The gel fraction of the polymer particles is preferably 0.7 or more and 1.0 or less.
Regarding the gel fraction of the polymer particles, the gel fraction was calculated from the following formula, assuming that the polymer particles were subjected to solid-liquid separation of gel components (crosslinked particles) with a filter before Gel Permeation Chromatography (GPC) analysis. Hereinafter, the monomer having 2 or more reactive groups per 1 molecule means a monomer capable of forming a crosslinked structure during polymerization, as described later.
Gel fraction ═ X-Y)/X
X: areal intensity of Polymer particles not containing monomers having more than 2 reactive groups per 1 molecule (. apprxeq.Total)
Y: GPC area intensity of filtrate of Polymer particles containing monomer having 2 or more reactive groups per 1 molecule (. apprxeq.dissolved component)
X-Y: the area intensity of the filtration residue component corresponding to the monomer having 2 or more reactive groups per 1 molecule ≈ insoluble component, gel component)
The gel fraction of the polymer particles is preferably 0.7 or more, more preferably more than 0.7, and still more preferably 0.8 or more. The gel fraction of the polymer particles is preferably 1.0 or less, more preferably less than 1.0, and even more preferably 0.9 or less. By setting the gel fraction of the polymer particles to the above range, particles which can form a coating film having excellent flexibility and chemical resistance by mixing a small amount of the polymer particles into the coating film can be stably produced. The gel fraction of the polymer particles can be adjusted by changing the kind and composition ratio of the monomers of the polymer particles.
The particle size distribution (volume average particle size/number average particle size) of the polymer particles is preferably 1.5 or less, more preferably 1.4 or less, still more preferably 1.3 or less, still more preferably 1.2 or less, and still more preferably 1.1 or less. If the particle size distribution exceeds 1.5, the uniformity of the coating film containing the polymer particles is reduced. The particle size distribution of the polymer particles can be adjusted by changing the kinds of monomers and emulsifiers, the composition ratio, and the polymerization conditions.
The average particle diameter and the particle size distribution of the polymer particles can be measured using a particle size distribution measuring apparatus based on the dynamic light scattering method. Examples of such a particle size distribution measuring apparatus include HORIBA LB-550, SZ-100 series (manufactured by HORIBA, Ltd.), FPAR-1000 (manufactured by Otsuka electronics Co., Ltd.).
The polymer particles of the present invention can be mixed with water to prepare a dispersion. The dispersion may be mixed with inorganic particles such as alumina and titania in addition to the polymer particles. The pH of the dispersion is preferably 5 to 10, more preferably 6 to 9.5. When the pH of the dispersion is in such a range, dispersion stability can be improved.
The dispersion liquid containing the polymer particles of the present invention can be used for a film, that is, applied to a film to form a coating film, thereby modifying the surface characteristics of the film. The film is not particularly limited, and examples thereof include plastic films, metal films, papers, porous films, porous substrates, and conductive films.
Method for producing polymer particles
The polymer constituting the polymer particles is not particularly limited as long as it contains a structural unit derived from an acrylate monomer, has a glass transition temperature of 20 ℃ or higher and 80 ℃ or lower, and satisfies an elastic modulus of a particle film made of the polymer particles of 1.7GPa or lower. The polymer is obtained, for example, by emulsion-polymerizing a monomer mixture comprising the fluorine-containing (meth) acrylate monomer (a), the (meth) acrylate monomer (B), the crosslinking agent (D), the (meth) acrylate monomer (C) having a hydroxyl group as required, and another radical polymerizable compound in an aqueous medium.
The ester moiety of the fluorine-containing (meth) acrylate monomer (A) is preferably a hydrocarbon group having 1 to 10 carbon atoms and containing fluorine. Examples of the fluorine-containing (meth) acrylate monomer (a) include 2,2, 2-trifluoroethyl acrylate, 2,2, 2-trifluoroethyl methacrylate, 2,2,3,3, 3-pentafluoropropyl acrylate, and 2,2,3,3, 3-pentafluoropropyl methacrylate. The fluorine-containing (meth) acrylate monomer (A) is preferably more than 20% by mass of the total amount of the monomers.
The (meth) acrylate monomer (B) is preferably a (meth) acrylate other than the fluorine-containing (meth) acrylate monomer (A) and the (meth) acrylate monomer (C) having a hydroxyl group, which will be described later. The ester moiety of the (meth) acrylate monomer (B) is preferably a benzyl group, a cyclic hydrocarbon group having 5 to 10 carbon atoms, or a chain hydrocarbon group having 1 to 14 carbon atoms. Further, the ester portion thereof may have a hetero atom. Examples of the (meth) acrylate monomer (B) include benzyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and the like. Further, there may be mentioned, for example, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dipropylaminoethyl (meth) acrylate, 2-diphenylaminoethyl (meth) acrylate, 3- (N) acrylate, n-dimethylamino) propyl ester, and the like. Among them, methyl (meth) acrylate and n-butyl (meth) acrylate are preferable. The (meth) acrylate monomer (B) is preferably at least 30% by mass of the total amount of the monomers.
As the crosslinking agent (D), a monomer capable of forming a crosslinked structure at the time of polymerization can be used. Examples of the crosslinking agent (D) include monomers having 2 or more reactive groups per 1 molecule. More specifically, there may be mentioned a crosslinkable group having thermal crosslinking properties, a monofunctional monomer having 1 olefinic double bond per 1 molecule, and a polyfunctional monomer having 2 or more olefinic double bonds per 1 molecule. Examples of the thermally crosslinkable group contained in the monofunctional monomer include an epoxy group, an N-methylolamide group, an oxetanyl group, an acid anhydride group, a sulfonic acid anhydride group, and the like,
Figure BDA0003651382410000051
Oxazolinyl, and combinations thereof.
Examples of the crosslinking agent (D) include polyalkylene glycol di (meth) acrylate and urethane acrylate. The crosslinking agent (D) is preferably more than 7 mass% and not more than 30 mass% of the total amount of the monomers. The lower limit of the crosslinking agent (D) is more than 7% by mass, preferably 8% by mass or more, more preferably more than 10% by mass, further preferably 12% by mass or more, and further preferably 14% by mass or more, per 100% by mass of the monomer unit. The upper limit of the crosslinking agent (D) is preferably 30% by mass or less, more preferably 28% by mass or less, further preferably 26% by mass or less, and further preferably 24% by mass or less, of 100% by mass of the monomer unit. By containing the crosslinking agent (D), polymer particles having excellent flexibility and solvent resistance can be obtained.
The ester moiety of the (meth) acrylate monomer (C) having a hydroxyl group is preferably a hydrocarbon group having 1 to 10 carbon atoms and containing a hydroxyl group. Examples of the (meth) acrylate monomer (C) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. The (meth) acrylate monomer (C) having a hydroxyl group is preferably 0 mass% or more and 10 mass% or less of the total amount of the monomers.
The conditions for emulsion polymerization of the monomer mixture are not particularly limited, and for example, the reaction may be carried out in an aqueous medium in the presence of an emulsifier and a polymerization initiator, preferably at a temperature of about 50 to 100 ℃ for about 1 to 30 hours. A chain transfer agent, a chelating agent, a pH adjuster, a solvent, and the like may be added as necessary.
As the emulsifier, an anionic surfactant, a nonionic surfactant, a combination of an anionic surfactant and a nonionic surfactant, and the like can be used, and in some cases, an amphoteric surfactant and a cationic surfactant can be used.
Examples of the anionic surfactant include sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenylether disulfonate, sodium polyoxyethylene alkyl ether sulfate, and sodium polyoxyethylene alkylphenyl ether sulfate. Among them, preferred are sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium lauryl sulfate and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. In general, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and the like are used.
Examples of the amphoteric surfactant include lauryl betaine, hydroxyethyl imidazoline sulfate sodium salt, imidazoline sulfonic acid sodium salt, and the like.
As the cationic surfactant, for example, alkyl pyridinium chloride is exemplified
Figure BDA0003651382410000061
Alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, and the like.
Further, as the emulsifier, a fluorine-based surfactant such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate, perfluoroalkyl polyoxyethylene, perfluoroalkyl betaine, and perfluoroalkoxy ammonium fluorocarboxylate may be used.
Further, so-called reactive emulsifiers copolymerizable with the above monomers, such as sodium styrenesulfonate, sodium allylalkylsulfonic acid, ammonium polyoxyethylene alkylallyl phenyl ether sulfate, and polyoxyethylene alkylallyl phenyl ether, can be used, and a combination of ammonium 2- (1-allyl) -4-nonylphenoxypolyethylene glycol sulfate and 2- (1-allyl) -4-nonylphenoxypolyethylene glycol is particularly preferable.
The amount of the emulsifier used is preferably about 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the monomer mixture.
As the polymerization initiator, a water-soluble polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, or hydrogen peroxide, or a redox-type polymerization initiator in which these water-soluble polymerization initiator and a reducing agent are combined can be used. Among them, potassium persulfate and ammonium persulfate are preferable. Examples of the reducing agent include sodium metabisulfite, sodium bisulfite, sodium sulfite, sodium thiosulfate, L-ascorbic acid or a salt thereof, sodium formaldehyde sulfoxylate, ferrous sulfate, and glucose. Among them, L-ascorbic acid or a salt thereof is preferable.
The oil-soluble polymerization initiator may be used by dissolving it in a monomer or a solvent. Examples of the oil-soluble polymerization initiator include, for example, 2,2 ' -azobisisobutyronitrile, 2 ' -azobis- (4-methoxy-2, 4-dimethylvaleronitrile), 2 ' -azobis-2, 4-dimethylvaleronitrile, 1 ' -azobiscyclohexane-1-carbonitrile, 2 ' -azobisisovaleronitrile, 2 ' -azobisisobutyronitrile, 2 ' -azobis (phenylisobutyronitrile), benzoyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-butyl hydroperoxide, 3,5, 5-trimethylhexanol peroxide, t-butyl peroxide (2-ethylhexanoate), and the like. Among them, 2' -azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-butyl hydroperoxide, 3,5, 5-trimethylhexanol peroxide, t-butyl peroxide (2-ethylhexanoate) are preferable.
The amount of the polymerization initiator used is preferably about 0.1 to 3 parts by mass per 100 parts by mass of the monomer mixture.
Examples of the chain transfer agent include halogenated hydrocarbons (e.g., carbon tetrachloride, chloroform, bromoform, etc.), thiols (e.g., n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan, n-hexadecylmercaptan, etc.), xanthates (e.g., dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, etc.), terpenes (e.g., dipentene, terpinolene, etc.), thiuram sulfides (e.g., tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram disulfide, etc.).
The amount of the chain transfer agent used is preferably about 0 to 10 parts by mass per 100 parts by mass of the monomer mixture.
Examples of the pH adjuster include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and ammonia. The amount of the pH adjuster is preferably about 0 to 3 parts by mass per 100 parts by mass of the monomer mixture.
When the monomer mixture is emulsion polymerized in an aqueous medium, the monomer mixture may be added by various methods. As the method of addition, there is a method of adding the total amount of the monomer mixture together; a method of continuously or separately adding the remaining monomer mixture after a part of the monomer mixture is added and allowed to react; a method of continuously or separately adding the remaining monomer mixture after adding a part of the particles obtained by the reaction; a method of continuously or successively adding the total amount of the monomer mixture in divided form, but a method of continuously or separately adding the remaining monomer mixture after a part of the monomer mixture is added and reacted, or a method of continuously or separately adding the remaining monomer mixture after a part of the particles obtained by the reaction is added, is preferable.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following description, "%" and "part" mean "% by mass" and "part by mass". The following shows the assay used in this example.
(1) Volume average particle diameter and particle size distribution
A sample liquid obtained by dispersing 0.3g of polymer particles in water so that the solid content concentration became 0.01% by mass was measured for the volume average particle diameter (dw) and the number average particle diameter (dn) by Dynamic Light Scattering (DLS), and the volume average particle diameter (unit: nm) and the particle size distribution (dw/dn) in water were determined.
(2) Glass transition temperature
As the glass transition temperature (Tg) of the polymer particles, a glass transition temperature (Tg) of the polymer particles was measured in a range based on "JIS K7121: 2012 プラスチック in the predetermined Differential Scanning Calorimetry (DSC) of the temperature-sensing method (plastic transition temperature measurement method) ", an intersection point of a line extending from a base line on the low temperature side to the high temperature side at the 2 nd temperature rise after the first temperature rise and the cooling and a tangent line drawn from a point where the slope of the curve in the stepwise change portion of the glass transition becomes maximum is measured.
(3) Heating the residual components
The residual content of the polymer particles in the aqueous dispersion after heating was measured in accordance with JIS K5601-1-2: 2008.
(4)pH
The pH of a dispersion liquid in which the polymer particles were dispersed in water so that the solid content concentration became 10 mass% was measured.
(5) Flexibility (modulus of elasticity of particle film)
A dispersion was prepared by dispersing polymer particles in water so that the solid content concentration became 10 mass%. The dispersion was applied to a PET substrate by a bar coater (# No. 3), dried at 60 ℃ for 10 minutes to form a coating film layer, and the surface elastic modulus of the coating film layer was measured by an Atomic Force Microscope (AFM). The film was evaluated as "good" if the elastic modulus of the particle film made of the polymer particles was less than 1.0GPa, as "good" if the elastic modulus was 1.0GPa or more and 1.7GPa or less, as "slightly poor" if the elastic modulus exceeded 1.7GPa and 3.0GPa or less, as "poor" if the elastic modulus exceeded 3.0GPa, and as good flexibility if the elastic modulus was 1.7GPa or less.
(6) Chemical resistance
A sample liquid obtained by dispersing 0.3g of polymer particles in water so that the solid content concentration became 0.01 mass% was analyzed for the volume average particle diameter by Dynamic Light Scattering (DLS). On the other hand, 0.3g of the polymer particles were immersed in 0.1g of diethyl carbonate (hereinafter, referred to as "DEC") and left to stand for 12 hours. Then, the sample solution was diluted with water to a solid content concentration of 0.01 mass%, and the volume average particle diameter was analyzed by Dynamic Light Scattering (DLS). The change rate of the volume average particle diameter dw before and after DEC immersion [ change rate ═ volume average particle diameter of sample immersed in DEC/volume average particle diameter of sample not immersed in DEC ] was calculated. The chemical resistance was evaluated as "good" if the change rate was 1.0 or more and less than 2.0, "good" if the change rate was 2.0 or more and less than 4.0, "slightly poor" if the change rate was 4.0 or more and less than 6.0, "poor" if the change rate was 6.0 or more (including the case where the particles were dissolved in DEC and the particle size could not be measured), and good chemical resistance was judged if the change rate was less than 4.0.
(7) Fraction of gel
Assuming that the polymer particles were subjected to solid-liquid separation with a filter before Gel Permeation Chromatography (GPC) analysis to obtain gel components (═ crosslinked particles), the gel fraction was calculated from the following formula. The crosslinking agent is a monomer capable of forming a crosslinked structure during polymerization, and means a monomer having 2 or more reactive groups per 1 molecule.
Gel fraction ═ X-Y)/X
X: areal Strength (. apprxeq.Total) of Polymer particles not containing a crosslinking agent (monomers having more than 2 reactive groups per 1 molecule)
Y: areal strength of GPC of filtrate of Polymer particles containing crosslinking agent (monomer having 2 or more reactive groups per 1 molecule) (≈ dissolved component)
X-Y: the area intensity corresponding to the filtration residue component with a crosslinking agent (monomer having 2 or more reactive groups per 1 molecule) ≈ insoluble component, gel component)
The crosslinked particles were evaluated as "good" if the gel fraction was 0.8 or more and 1.0 or less, as "good" if the gel fraction was 0.7 or more and less than 0.8, as "slightly poor" if the gel fraction was 0.4 or more and less than 0.7, as "poor" if the gel fraction was less than 0.4, and as good when the gel fraction was 0.7 or more.
Example 1
120 parts of ion-exchanged water and 1 part of アデカリアソーブ SR-1025 (emulsifier manufactured by アデカ Co., Ltd.) were charged into the reactor, and stirring was started. To this solution, 0.4 part of 2, 2' -azobis (2- (2-imidazolin-2-yl) propane) (Wako pure chemical industries, Ltd.) was added under a nitrogen atmosphere, and a mixture was prepared from 30 parts of 2,2, 2-trifluoroethyl methacrylate (3FMA), 54 parts of cyclohexyl acrylate (CHA) and 2 parts of 4-hydroxybutyl acrylate (4HBA), UF-C052 (polyethylene glycol dimethacrylate, Kyoeisha chemical Co., Ltd., the polyethylene glycol dimethacrylate UF-C052 polymerized polymer Tg: -44 ℃)14 parts, アデカリアソーブ SR-1025(アデカ manufactured emulsifier) 9 parts, ion exchange water 115 parts of the monomer mixture at 60 ℃ for 2 hours were continuously added dropwise, after the completion of the addition, polymerization was carried out for 4 hours. The obtained polymer particles are shown in table 1. The composition ratio of the monomers shown in table 1 is the ratio of each component to the total amount of the monomer components.
The abbreviations for the components in table 1 have the following meanings.
3 FMA: 2,2, 2-Trifluoroethyl methacrylate
CHA: acrylic acid cyclohexyl ester
MMA: (meth) acrylic acid methyl ester
BA: n-butyl (meth) acrylate
4 HBA: acrylic acid 4-hydroxybutyl ester
Example 2
Polymer particles were obtained in the same manner as in example 1, except that the composition ratio of the monomer mixture was changed to the composition shown in table 1. The obtained polymer particles were as shown in table 1.
Example 3
Polymer particles were obtained in the same manner as in example 1 except that the crosslinking agent (D) was changed to polyalkylene glycol dimethacrylate PDE-600 (manufactured by Nichikoku corporation, Tg: -34 ℃ of a polymer obtained by polymerizing polyalkylene glycol dimethacrylate PDE-600), and the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles are shown in table 1.
Example 4
Polymer particles were obtained in the same manner as in example 3, except that the composition ratio of the monomer mixture was changed to the composition shown in table 1. The obtained polymer particles are shown in table 1.
Example 5
Polymer particles were obtained in the same manner as in example 3, except that the composition ratio of the monomer mixture was changed to the composition shown in table 1. The obtained polymer particles were as shown in table 1.
Example 6
Polymer particles were obtained in the same manner as in example 1 except that the crosslinking agent (D) was changed to polyalkylene glycol diacrylate ADP-400 (Tg: -9 ℃ C., of a polymer obtained by polymerizing polyalkylene glycol diacrylate ADP-400, manufactured by Nichigan oil Co., Ltd.). The obtained polymer particles are shown in table 1.
Example 7
Polymer particles were obtained in the same manner as in example 6, except that the composition ratio of the monomer mixture was changed to the composition shown in table 1. The obtained polymer particles are shown in table 1.
Example 8
Polymer particles were obtained in the same manner as in example 3, except that the composition ratio of the monomer mixture was changed to the composition shown in table 1. The obtained polymer particles are shown in table 1.
Example 9
Polymer particles were obtained in the same manner as in example 3, except that the monomer (B) was changed to methyl (meth) acrylate (MMA) (Wako pure chemical industries, Ltd.) and n-butyl (meth) acrylate (BA) (Wako pure chemical industries, Ltd.), and the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The obtained polymer particles are shown in table 2.
Example 10
Polymer particles were obtained in the same manner as in example 9, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles are shown in table 2.
Example 11
Polymer particles were obtained in the same manner as in example 3, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles are shown in table 2.
Example 12
Polymer particles were obtained in the same manner as in example 3, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles are shown in table 2.
Comparative example 1
120 parts of ion-exchanged water and 1 part of アデカリアソーブ SR-1025 (emulsifier manufactured by アデカ Co., Ltd.) were charged into the reactor, and stirring was started. To this solution, 0.4 part of 2, 2' -azobis (2- (2-imidazolin-2-yl) propane) (Wako pure chemical industries, Ltd.) was added under a nitrogen atmosphere, and a monomer mixture comprising 30 parts of 2,2, 2-trifluoroethyl methacrylate (3FMA), 68 parts of cyclohexyl acrylate (CHA), 2 parts of 4-hydroxybutyl acrylate (4HBA), 9 parts of アデカリアソーブ SR-1025 (emulsifier manufactured by アデカ Co., Ltd.) and 115 parts of ion-exchanged water was continuously added dropwise at 60 ℃ for 2 hours, followed by polymerization treatment over 4 hours after completion of the dropwise addition. The obtained polymer particles are shown in table 2.
Comparative example 2
Polymer particles were obtained in the same manner as in example 1, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles were as shown in table 2.
Comparative example 3
Polymer particles were obtained in the same manner as in comparative example 1, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles are shown in table 2.
Comparative example 4
Polymer particles were obtained in the same manner as in example 3, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles are shown in table 2.
Comparative example 5
Polymer particles were obtained in the same manner as in example 9, except that the composition ratio of the monomer mixture was changed to the composition shown in table 2. The obtained polymer particles are shown in table 2.
[ Table 1]
Figure BDA0003651382410000141
[ Table 2]
Figure BDA0003651382410000151
Industrial applicability
The polymer particles of the present invention are added to a coating film in a small amount on the film, and are added to the coating film in a small amount, whereby the particles are fused to each other by heat to increase the film, and have adhesion to other materials by an anchor effect, and therefore, a film forming a coating film excellent in flexibility and chemical resistance can be provided with high productivity. Thus, the application of the coating agent for modifying the surface of a separator used in a lithium ion battery is advanced, and a contribution to reduction in global greenhouse gas emission due to promotion of popularization of EV/PHEV is expected.

Claims (2)

1. A polymer particle comprising a structural unit derived from an acrylate monomer, characterized in that the particle is a particle made of a polymer having a glass transition temperature of 20 ℃ or higher and 80 ℃ or lower, the elastic modulus of a particle film made of the polymer particle is 1.7GPa or lower, and the volume average particle diameter of the polymer particle in water is 100 to 500 nm.
2. The polymer particle according to claim 1, wherein the polymer particle has a gel fraction of 0.7 or more and 1.0 or less.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1130640A (en) * 1994-10-18 1996-09-11 埃勒夫阿托化学有限公司 Fluorinated acrylic and methacrylic latices and mixtures thereof, processes for manufacturing them and their application in field of hydrophobic coatings
JP2008056900A (en) * 2006-07-31 2008-03-13 Dainippon Ink & Chem Inc Water-based resin dispersion for coating paper-made tatami mat facing and paper-made tatami facing coated therewith
JP2012201862A (en) * 2011-03-28 2012-10-22 Sekisui Plastics Co Ltd Polymer particle and application of the same
CN105683324A (en) * 2013-12-27 2016-06-15 积水化学工业株式会社 Optical adhesive, optical adhesive tape, and layered body
WO2019230956A1 (en) * 2018-06-01 2019-12-05 積水化学工業株式会社 Adhesive sheet

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6011608B2 (en) 1978-09-29 1985-03-27 日精樹脂工業株式会社 Purging method for injection molding machine
JPS577829A (en) 1980-06-18 1982-01-16 Toshiba Ceramics Co Ltd Colored quartz glass tube as heating element for heating
JP3592959B2 (en) * 1999-06-14 2004-11-24 株式会社日本触媒 Method for producing aqueous resin dispersion
JP5698127B2 (en) 2008-07-07 2015-04-08 アーケマ・インコーポレイテッド Fluoropolymer aqueous hybrid composition with improved film formation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1130640A (en) * 1994-10-18 1996-09-11 埃勒夫阿托化学有限公司 Fluorinated acrylic and methacrylic latices and mixtures thereof, processes for manufacturing them and their application in field of hydrophobic coatings
JP2008056900A (en) * 2006-07-31 2008-03-13 Dainippon Ink & Chem Inc Water-based resin dispersion for coating paper-made tatami mat facing and paper-made tatami facing coated therewith
JP2012201862A (en) * 2011-03-28 2012-10-22 Sekisui Plastics Co Ltd Polymer particle and application of the same
CN105683324A (en) * 2013-12-27 2016-06-15 积水化学工业株式会社 Optical adhesive, optical adhesive tape, and layered body
WO2019230956A1 (en) * 2018-06-01 2019-12-05 積水化学工業株式会社 Adhesive sheet

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