Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/10—Esters
• • 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
• • 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
  • 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

Definitions

• the present invention relates to polymer particles capable of forming a coating film having excellent flexibility and chemical resistance.
• the polymer particles are used as a binder for improving the battery characteristics of a lithium ion secondary battery, and for the purpose of imparting adhesion by coating on various substrates.
• Various properties are required for the polymer particles depending on the intended use, and various proposals have been made to satisfy such requirements (see, for example, Patent Documents 1 to 3).
• polymer particles that form a coating film having excellent flexibility and chemical resistance have not yet been established.
• polymer particles capable of forming a coating film having excellent flexibility and chemical resistance by mixing a small amount with other particles.
• the polymer particles of the present invention are particles made of a polymer having a softening start temperature of 20 ° C. or higher and 45 ° C. or lower, and the surface free energy of the particle film made of the polymer particles is 30 mN / m or more and 50 mN / m or less, in water. It is a polymer particle containing a structural unit derived from an acrylic acid ester monomer, characterized by having a volume average particle diameter of 100 to 500 nm.
• the polymer particles of the present invention can exhibit flexibility and chemical resistance by adding a small amount to the coating film.
• the polymer particles of the present invention are made of a polymer having a softening start temperature of 20 ° C. or higher and 45 ° C. or lower.
• a softening start temperature of 20 ° C. or higher and 45 ° C. or lower By setting the softening start temperature of the polymer in the above range, it is possible to stably produce polymer particles in which the particles are formed into a film by fusion of the particles and the adhesion due to the anchor effect is exhibited.
• the softening start temperature of the polymer particles is preferably more than 20 ° C, more preferably 22 ° C or higher, still more preferably 25 ° C or higher.
• the softening start temperature of the polymer particles is preferably less than 45 ° C, more preferably 40 ° C or lower, still more preferably 35 ° C or lower.
• the softening start temperature of the polymer can be adjusted by changing the type and composition ratio of the monomer.
• the "softening start temperature of the polymer particles” is the temperature at which the glass transition starts (external glass transition start temperature) measured by differential scanning calorimetry (DSC) in accordance with JIS K7121: 2012. be.
• the supplementary glass transition start temperature is the temperature of the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the gradient of the curve of the stepped change part of the glass transition is maximized. do.
• the surface free energy of the particle film made of the polymer particles of the present invention is 30 mN / m or more and 50 mN / m or less.
• the surface free energy of the particle film is preferably more than 30 mN / m, more preferably 35 mN / m or more, still more preferably 36 mN / m or more, still more preferably more than 38 mN / m.
• the surface free energy of the particle film is preferably less than 50 mN / m, more preferably 48 mN / m or less, still more preferably 46 mN / m or less, still more preferably 44 mN / m or less.
• the surface free energy of the particle film made of polymer particles can be adjusted by changing the type and composition ratio of the monomers of the polymer particles.
• the surface free energy of the particle film composed of polymer particles is prepared by preparing the dispersion liquid which dispersed the polymer particles in water so that the solid content concentration becomes 10% by mass, and this dispersion.
• the liquid was applied onto a PET substrate with a bar coater (# 3) and dried at 60 ° C. for 10 minutes to form a coating layer, and the coating layer was measured for contact angle using a known solvent, and Young-Dupre was performed. Obtained from the formula of.
• the volume average particle diameter of the polymer particles in water is 100 to 500 nm.
• the volume average particle size of the polymer particles in water is preferably more than 100 nm, more preferably 120 nm or more, and further preferably 150 nm or more.
• the volume average particle size of the polymer particles in water is preferably less than 500 nm, more preferably 450 nm or less, still more preferably 400 nm or less. If the volume average particle diameter is less than 100 nm, the viscosity of the dispersion liquid in which the polymer particles are dispersed in water increases, and there is a possibility that it becomes difficult to obtain an aqueous dispersion liquid having a high solid content.
• volume average particle diameter exceeds 500 nm, the storage stability of the aqueous dispersion of the polymer particles may decrease, which further causes the uniformity of the formed coating film to decrease.
• the volume average particle size of the polymer particles can be adjusted by changing the type and composition ratio of the emulsifier.
• the gel fraction is preferably 0.7 or more and 1.0 or less.
• the monomer having two or more reactive groups per molecule refers to a monomer that can form a crosslinked structure when polymerized, as described later.
• the gel fraction of the polymer particles is preferably 0.7 or more, more preferably more than 0.7, 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.
• 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. It is preferably 1.1 or less. If the particle size distribution exceeds 1.5, it causes a decrease in the uniformity of the coating film containing the polymer particles.
• the particle size distribution of the polymer particles can be adjusted by changing the monomer, the type of emulsifier, the composition ratio and the polymerization conditions.
• the average particle size and particle size distribution of the polymer particles can be measured using a particle size distribution measuring device based on the dynamic light scattering method.
• a particle size distribution measuring device examples include HORIBA LB-550, SZ-100 series (all manufactured by HORIBA, Ltd.), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) and the like.
• the polymer particles of the present invention can be mixed with water to prepare a dispersion liquid.
• this dispersion can also be mixed with inorganic particles such as alumina and titania.
• the pH of the dispersion is preferably 5 to 10, more preferably 6 to 9.5. By keeping the pH of the dispersion in such a range, the dispersion stability can be improved.
• the dispersion liquid containing the polymer particles of the present invention can be used for a film, that is, the surface characteristics of the film can be modified by applying the dispersion liquid to the film to form a coating film.
• the film is not particularly limited, and examples thereof include a plastic film, a metal film, paper, a porous film, a porous substrate, a conductive film, and the like.
• Polymer particles contain structural units derived from acrylic acid ester monomers, have a softening start temperature of 20 ° C. or higher and 45 ° C. or lower, and have a surface free energy of 30 mN / m for a particle film made of polymer particles.
• the volume average particle size in water of 50 mN / m or more and in water is not particularly limited as long as it satisfies 100 to 500 nm.
• the polymer particles include, for example, a fluorine-containing (meth) acrylic acid ester monomer (A), a (meth) acrylic acid ester monomer (B), a (meth) acrylic acid ester monomer (C) having a hydroxyl group, and the like. It is obtained by emulsion polymerization of a monomer mixture consisting of a monomer (D) having two or more reactive groups per molecule and other radically polymerizable compounds in an aqueous medium.
• the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably a hydrocarbon group having 1 to 10 carbon atoms whose ester portion contains fluorine.
• the fluorine-containing (meth) acrylic acid ester monomer (A) for example, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3- Examples thereof include pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, and the like.
• the lower limit of the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably more than 20% by mass, more preferably 22% by mass or more, still more preferably 25% by mass or more in 100% by mass of the polymer particle unit. , More preferably 30% by mass or more.
• the upper limit of the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less in 100% by mass of the polymer particle unit. , More preferably 35% by mass or less.
• the ester portion of the (meth) acrylic acid ester monomer (B) is a benzyl group or a cyclic hydrocarbon group having 5 to 10 carbon atoms.
• the (meth) acrylic acid ester monomer (B) include benzyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and the like.
• the (meth) acrylic acid ester monomer (B) excludes the above-mentioned fluorine-containing (meth) acrylic acid ester monomer (A) and the (meth) acrylic acid ester monomer (C) having a hydroxyl group.
• it is a (meth) acrylic acid ester.
• the lower limit of the (meth) acrylic acid ester monomer (B) is preferably 30% by mass or more, more preferably more than 30% by mass, still more preferably 35% by mass or more, and one layer in 100% by mass of the polymer particle unit. It is preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more.
• the upper limit of the (meth) acrylic acid ester monomer (B) is preferably 75% by mass or less, more preferably 70% by mass or less, still more preferably 68% by mass or less, based on 100% by mass of the polymer particle unit.
• the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably a hydrocarbon group having 1 to 10 carbon atoms whose ester portion contains a hydroxyl group.
• Examples of the (meth) acrylic acid ester monomer (C) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
• the lower limit of the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably more than 2% by mass, more preferably 2.5% by mass or more, more preferably more preferably 2.5% by mass or more in 100% by mass of the polymer particle unit.
• the upper limit of the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably 25% by mass or less, more preferably 20% by mass or less in 100% by mass of the polymer particle unit.
• the monomer (D) having two or more reactive groups per molecule a monomer capable of forming a crosslinked structure when polymerized can be used.
• the monomer (D) having two or more reactive groups per molecule include polyalkylene glycol di (meth) acrylate and urethane acrylate.
• the lower limit of the monomer (D) having two or more reactive groups per molecule is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 3% by mass or more in 100% by mass of the polymer particle unit. It is 5% by mass or more, particularly preferably 6% by mass or more.
• the upper limit of the monomer (D) having two or more reactive groups per molecule is preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 9% by mass or less in 100% by mass of the monomer unit. It is preferably 8% by mass or less.
• the conditions for emulsion polymerization of the monomer mixture are not particularly limited.
• the temperature is preferably about 50 to 100 ° C. for about 1 to 30 hours. You just have to react. If necessary, a chain transfer agent, a chelating agent, a pH adjuster, a solvent and the like may be added.
• an anionic surfactant As the emulsifier, an anionic surfactant, a nonionic surfactant, a combination of an anionic surfactant and a nonionic surfactant, etc. are used, and in some cases, an amphoteric surfactant and a cationic surfactant. Can also be used.
• anionic surfactant examples include alkyl sulfate ester sodium salt, alkylbenzene sulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, alkyldiphenyl ether disulfonic acid sodium salt, polyoxyethylene alkyl ether sulfate sodium salt, and polyoxyethylene.
• Alkylphenyl ether sodium sulfate and the like can be mentioned. Among these, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium lauryl sulfate and the like are preferable.
• nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like.
• polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like are used.
• amphoteric tenside examples include lauryl betaine, hydroxyethyl imidazoline sulfate sodium salt, imidazoline sulfonic acid sodium salt and the like.
• cationic surfactant examples include alkylpyridinium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride and the like.
• a fluorine-based surfactant such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester, perfluoroalkyl polyoxyethylene, perfluoroalkyl betaine, perfluoroalkoxyfluorocarboxylate ammonium, etc.
• Activators can also be used.
• reactive emulsifiers that can be copolymerized with the above-mentioned monomers, such as styrene sulfonic acid sodium salt, allylalkyl sulfonic acid sodium salt, polyoxyethylene alkyl allylphenyl ether ammonium sulfate, polyoxyethylene alkyl allylphenyl ether and the like.
• a combination of 2- (1-allyl) -4-nonylphenoxypolyethylene glycol sulfate ester ammonium salt and 2- (1-allyl) -4-nonylphenoxypolyethylene glycol is 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.
• a water-soluble polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, or hydrogen peroxide, or a redox-based polymerization initiator that combines these water-soluble polymerization initiators and a reducing agent is used.
• a reducing agent include sodium pyrobisulfite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, L-ascorbic acid or a salt thereof, sodium formaldehyde sulfoxylate, ferrous sulfate, glucose and the like.
• L-ascorbic acid or a salt thereof is preferable.
• oil-soluble polymerization initiator can also be used by dissolving it in a monomer or a solvent.
• examples of the oil-soluble polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis.
• 2,2'-azobisisobutyronitrile benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan hydroperoxide, t-butyl hydroperoxide, 3,5,5- Trimethylhexanol peroxide and t-butylperoxy (2-ethylhexanoate) are preferred.
• 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.
• chain transfer agent examples include halogenated hydrocarbons (eg, carbon tetrachloride, chloroform, bromoform, etc.), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.), xantogen.
• halogenated hydrocarbons eg, carbon tetrachloride, chloroform, bromoform, etc.
• mercaptans eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.
• Classes eg, dimethylxanthogen disulfide, diethylxantogen disulfide, diisopropylxantogen disulfide, etc.
• terpenes eg, dipentene, turpinolene, etc.
• thiuram sulfides eg, tetramethylthium monosulfide, tetraethylthiuram disulfide, tetrabutylthium disulfide, dipentamethyl, etc.
• Thiuram 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 hydrogencarbonate, ammonia and the like.
• the amount of the pH adjuster used is preferably about 0 to 3 parts by mass per 100 parts by mass of the monomer mixture.
• the monomer mixture can be added by various methods.
• a method of adding the entire amount of the monomer mixture at a time a method of charging a part of the monomer mixture and reacting it, and then continuously or dividing the remaining monomer mixture, and a reaction.
• the method of charging is preferable.
• volume average particle size and particle size distribution The volume average particle size and number average particle size of the polymer particles were measured using a particle size distribution measuring device (HORIBA LB-550, manufactured by HORIBA, Ltd.). The particle size distribution was obtained from the obtained values.
• a dispersion liquid in which polymer particles are dispersed in water so that the solid content concentration becomes 10% by mass is applied on a PET substrate with a bar coater (# 3 count) and dried at 60 ° C. for 10 minutes.
• a coating layer (particle film composed of polymer particles) was formed. The contact angle is measured using water, ethylene glycol, methylene iodide, and formamide as a solvent in the coating film layer, and the surface free energy of the particle film composed of polymer particles is obtained from the Young-Dupre formula.
• Flexibility A dispersion was prepared by dispersing the polymer particles in water so that the solid content concentration was 10% by mass. This dispersion is applied on a PET substrate with a bar coater (# 3) and dried at 60 ° C. for 10 minutes to form a coating film layer, and the surface elastic modulus of the coating film layer is measured with an atomic force microscope (AFM). The elastic modulus of the particle film made of the polymer particles was determined. If the elastic modulus of the obtained particle film is less than 1.0 GPa, it is "excellent", if it is 1.0 GPa or more and 1.7 GPa or less, it is “good”, and if it is more than 1.7 GPa and 3.0 GPa or less, it is “slightly inferior”. , If it exceeds 3.0 GPa, it is evaluated as “inferior”, and if it is 1.7 GPa or less, it is judged that the flexibility is good.
• rate of change volume average particle diameter of the sample immersed in DEC / volume average particle diameter of the sample not immersed in DEC] was calculated. If the rate of change is 1.0 or more and less than 2.0, it is “excellent”, if the rate of change is 2.0 or more and less than 4.0, it is “good”, and if the rate of change is 4.0 or more and less than 6.0, it is “good”. If it is “slightly inferior” and the rate of change is 6.0 or more (including the case where the particles are dissolved in DEC and the particle size cannot be measured), it is evaluated as “inferior”, and when the rate of change is less than 4.0, it is good. Judged as chemical resistant.
• Example 1 120 parts of ion-exchanged water and 1 part of Adecaria Sorb SR-1025 (emulsifier manufactured by Adeca Corporation) were charged into the reactor, and stirring was started. To this, 0.4 part of 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (manufactured by Wako Pure Chemical Industries, Ltd.) was added under a nitrogen atmosphere, and 2,2,2- 30 parts of trifluoroethyl methacrylate (3FMA), 49 parts of cyclohexyl acrylate (CHA), 14 parts of 4-hydroxybutyl acrylate (4HBA), polyalkylene glycol dimethacrylate (Blemmer (registered trademark) PDE-600 (manufactured by Nichiyu Co., Ltd.) ), 7 parts of this homopolymer made of Blemmer (registered trademark) PDE-600 (Tg: -34 ° C), 9 parts of Adecaria Sorb SR-1025 (e
• the mixture was continuously added dropwise at 60 ° C. over 2 hours, and the polymerization treatment was carried out for 4 hours after the completion of the addition.
• the obtained polymer particles were as 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 of each component in Table 1 and Table 2 described later have the following meanings.
• 3FMA 2,2,2-trifluoroethyl methacrylate ⁇ CHA: cyclohexyl acrylate ⁇ MMA: methyl (meth) acrylate ⁇ BA: (meth) acrylate-n-butyl ⁇ 4HBA: 4-hydroxybutyl acrylate
• 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 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 4 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 5 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 6 Monomer (B) changed to methyl (meth) acrylate (MMA) (Wako Pure Chemical Industries, Ltd.) and (meth) acrylate-n-butyl (BA) (Wako Pure Chemical Industries, Ltd.) Then, 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 7 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 8 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 9 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.
• Example 10 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.
• Example 11 The monomer (D) having two or more reactive groups per molecule was changed to urethane acrylate UF-C052 (manufactured by Kyoeisha Chemical Co., Ltd.), and the composition ratio of the monomer mixture was shown in Table 2. Polymer particles were obtained in the same manner as in Example 1 except that the above was changed to. The obtained polymer particles were as shown in Table 2.
• Example 12 Polymer particles were obtained in the same manner as in Example 11 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 1 120 parts of ion-exchanged water and 1 part of Adecaria Sorb SR-1025 (emulsifier manufactured by Adeca Corporation) were charged into the reactor, and stirring was started. To this, 0.4 part of 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (manufactured by Wako Pure Chemical Industries, Ltd.) was added under a nitrogen atmosphere, and 2,2,2- From 30 parts of trifluoroethyl methacrylate (3FMA), 68 parts of cyclohexyl acrylate (CHA), 2 parts of 4-hydroxybutyl acrylate (4HBA), 9 parts of Adecaria Sorb SR-1025 (emulsifier manufactured by Adeca Co., Ltd.), 115 parts of ion-exchanged water. The monomer mixture was continuously added dropwise at 60 ° C. over 2 hours, and the polymerization treatment was carried out for 4 hours after the completion of the addition. The obtained polymer particles were as shown in Table
• Comparative Example 2 The composition ratio of the monomer mixture was the same as that of Comparative Example 1 except that the composition was changed to the composition shown in Table 2, but stable emulsification was not possible and particles could not be obtained.
• 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 were as shown in Table 2.
• Comparative Example 4 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.
• the particles of the present invention When a small amount of the polymer particles of the present invention is added to the coating film on the film, the particles are fused with each other by heat to form a film, and thus have adhesion to other materials due to the anchor effect, and thus are flexible. , It becomes possible to provide a film forming a coating film having excellent chemical resistance with high productivity. As a result, its application is progressing as a coating agent that modifies the surface of separator films used in lithium-ion batteries in particular, and it is expected to contribute to the reduction of greenhouse gas emissions by promoting the spread of EV / PHEV.

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