Core-shell type fluoropolymer particles with improved flowability and cohesiveness, and method for producing them.

Abstract

The present invention relates to a dispersion containing core-shell type fluororesin particles with improved fluidity and cohesiveness. Specifically, by adding an acrylic monomer to a perfluoropolymer particle dispersion, particles having a perfluoropolymer core and an acrylic polymer shell, a mixture or slurry (dispersion) containing the same, and a method for producing the same are provided.

Description

Technical Field

[0001] The present invention relates to a dispersion containing core-shell type fluororesin particles with improved fluidity and cohesiveness.

[0002] One aspect provides particles having a perfluoropolymer core and an acrylic polymer shell, a mixture or slurry (dispersion) containing the same, and a method for producing the same by adding an acrylic monomer to a perfluoropolymer particle dispersion.

[0003] The core-shell type particles having a perfluorinated resin core and a polymethyl methacrylate resin shell produced by the above method have the shell resin sufficiently surrounding the entire surface of the core with a uniform thickness.

[0004] In addition, the core-shell type particles have a uniform particle size and excellent fluidity and low cohesiveness, and thus are characterized in that the timing of PTFE fibrillation can be controlled according to the intention of the user.

Background Art

[0005] Perfluoropolymers containing polytetrafluoroethylene (PTFE) are used in various applications such as various adhesives, process improvers, fluidizing agents, etc. due to their electrical properties, thermal properties, adhesive properties, etc., coatings for semiconductor manufacturing equipment, etc., and coatings for various substrates in electrical storage devices, etc., and also as adhesive materials, etc., in combination with other materials.

[0006] However, the perfluorinated resin particles themselves still lack sufficient adhesiveness to other materials such as films and electrodes of the polymer resin. In order to solve such problems and utilize the properties of the perfluorinated resin particles as they are and improve the surface properties, a manufacturing technology of core-shell particles having a surface layer of the fluorinated resin particles and a non-fluorine-based resin as a shell layer has been developed.

[0007] However, conventional core-shell particles also exhibit increased cohesiveness rather than dispersibility, resulting in insufficient slurry fluidity when actually used, and limitations in achieving sufficient performance due to particle aggregation. Furthermore, it was difficult to obtain a shell layer uniformly formed on the entire surface of the core perfluorinated resin particles, making it difficult to adjust the physical properties. [Overview of the project] [Problems that the invention aims to solve]

[0008] To solve the above problems, one embodiment provides core-shell particles comprising a perfluorinated resin core with excellent dispersibility and a polymethyl methacrylate resin shell. Using a Freeman Technology Powder Rheometer FT4, the core-shell resin is filled into a 50 mm diameter sample cylinder, and the total energy is measured 11 times while the impeller rotates at a tip speed of 100 mm / s and simultaneously descends. When the cohesive energy is measured while the impeller ascends, the core-shell particles have a specific energy (cohesive energy) of 10 mJ / g or less and a total energy of 2000 mJ or less.

[0009] Therefore, one embodiment aims to provide core-shell particles comprising a perfluorinated resin core having low cohesiveness between particles and an acrylic polymer shell.

[0010] Furthermore, one embodiment aims to provide core-shell particles comprising a perfluorinated resin core having a particle size of 100 to 500 nm and a polymethyl methacrylate-based resin shell.

[0011] Furthermore, one embodiment provides an excellent particle morphology that can obtain core-shell particles in which the shell layer uniformly surrounds the entire surface area of ​​the core. [Means for solving the problem]

[0012] As a result of research conducted to achieve the above objectives, we discovered that by emulsion polymerization of acrylic monomers in the presence of a perfluorinated polymer particle slurry to produce polymer particles having a core-shell structure and a slurry containing them, and by using polyethylene glycol ether having one or more alkyl groups substituted with C8 or more alkyl groups as shown in Chemical Formula 1 below as an emulsifier during emulsion polymerization, we were able to produce core-shell particles having the above-mentioned physical properties and a mixture or slurry containing them, thus completing the present invention.

[0013] [Chemical formula 1] R-(-O-C2H4-) n -OH (In the above formula, R is a C8 or greater alkyl group substituted with one or more alkyl groups, and n is an integer between 5 and 15.)

[0014] In one embodiment, R is C8~C 30 It may be an alkyl group substituted with one or more alkyl groups.

[0015] In one embodiment, the composite core-shell particle slurry may be such that the ratio of the molecular weight of the hydrophilic oxyethylene group to the total molecular weight ([molecular weight of the oxyethylene chain] / [total molecular weight]) in the chemical formula 1 is 0.5 to 1.0.

[0016] In one embodiment, the chemical formula 1 may be the following chemical formula 2.

[0017] [ka]

[0018] In one embodiment, core-shell particles having a perfluorinated polymer core and an acrylic polymer shell can be produced by emulsion polymerization of acrylic monomers in a seed slurry containing perfluorinated particles (hereinafter referred to as "perfluorinated resin particle slurry") using polyethylene glycol ether having one or more alkyl groups of C8 or higher, as defined by chemical formula 1, as an emulsifier.

[0019] In one aspect, the perfluorinated resin particle slurry may be a slurry containing perfluorinated resin particles having units derived from tetrafluoroethylene as a main component.

[0020] In one aspect, the polymethyl methacrylate-based resin shell layer may be a composite core-shell particle slurry containing 60% by weight or more of methyl methacrylate.

[0021] In one aspect, the core-shell particles and the slurry are obtained by emulsion polymerization of an acrylic monomer using a polyethylene glycol ether having a C8 or higher alkyl group substituted with one or more alkyls of the following Chemical Formula 1 as an emulsifier in the perfluorinated resin particle slurry, and may be composite core-shell particles having a perfluorinated resin core-polymethyl methacrylate-based resin shell, and a slurry containing the same.

[0022] [Chemical Formula 1] R-(-O-C2H4-) n -OH (In the above formula, R is a C8 or higher alkyl group substituted with one or more alkyls, and n is an integer of 5 to 15.)

[0023] In one aspect, the composite core-shell particles may be composite core-shell particles having an aggregation energy of 10 mJ / g or less.

[0024] In one aspect, the composite core-shell particles may be composite core-shell particles having a total surface energy of the particles of 2,000 mJ or less.

[0025] In one aspect, the composite core-shell particles may be composite core-shell particles having a particle size of the core-shell particles of 100 to 500 nm.

[0026] In one aspect, the weight of the core of the composite core-shell particles may be 50 to 95 wt%, preferably 60 to 80 wt% of the total core-shell particles.

[0027] In one embodiment, the core-shell slurry may be an electrode-forming slurry containing the core-shell particles and an electrode active material, or a formulation containing the particles.

[0028] One embodiment also provides a battery manufactured using the core-shell particles as a binder for an electrode active material.

[0029] One embodiment provides a composite core-shell particle having a perfluorinated resin core and a polymethyl methacrylate resin shell, wherein the cohesive energy is 10 mJ / g or less and the total surface energy is 2,000 mJ or less.

[0030] In one embodiment, composite core-shell particles are provided, wherein the average diameter of the core-shell particles is 100 to 500 nm.

[0031] In one embodiment, a composite core-shell particle is provided in which the average diameter of the core of the core-shell particle is less than 50 to 500 nm, and the thickness of the shell is 1 to 300 nm.

[0032] One embodiment provides an aqueous dispersion slurry containing the composite core-shell particles.

[0033] In one embodiment, the aqueous dispersion slurry further comprises an electrode active material. [Effects of the Invention]

[0034] Core-shell polymerized particles, comprising a perfluorinated resin core and a polymethyl methacrylate resin, produced by a manufacturing method according to one embodiment, have excellent dispersion properties and can minimize the formation of aggregates.

[0035] The core-shell type particles produced by one embodiment of the manufacturing method have a large particle size of 100 to 500 nm and can be manufactured with excellent uniformity of particle size.

[0036] In one embodiment, the core-shell particles are provided that have low cohesive energy and excellent dispersibility, when the total energy is measured 11 times while the impeller is rotating at a tip speed of 100 mm / s and simultaneously descending using a Freeman Technology Powder Rheometer FT4, and the cohesive energy is measured while the impeller is ascending, with a specific energy (cohesive energy) of 10 mJ / g or less and a total energy of 2000 mJ or less.

[0037] Therefore, when the particles are mixed with other particles, they exhibit excellent dispersibility and uniform mixing is possible. When the particles are used as a binder, they can provide very uniform binding characteristics, and the binding force can be easily adjusted by their content.

[0038] Furthermore, it is possible to obtain core-shell particles with excellent properties in which the shell layer uniformly surrounds the entire surface area of ​​the core. [Brief explanation of the drawing]

[0039] [Figure 1] This is a TEM / EDS image from Example 1. [Figure 2] This is the TEM / EDS image of Comparative Example 2. [Figure 3] This is the TEM / EDS image of Comparative Example 2. [Modes for carrying out the invention]

[0040] The present invention provides core-shell particles having a core containing a perfluorinated polymer and a shell layer containing a polymethyl methacrylate resin, wherein the particle size is 100 to 500 nm and the cohesive energy is low.

[0041] A core-shell structure, for example, comprising a core of a conventional perfluorinated polymer and a shell of a non-fluorinated resin, is described in U.S. Patent No. 6,841,594. However, particles produced by such methods have a problem in that they have high cohesive energy and therefore actually aggregate with other inorganic particles in a slurry state, and are not sufficiently dispersed. In other words, they have the characteristic of having excessively high cohesive energy.

[0042] However, the core-shell particles according to this embodiment have a particle size that can be adjusted from 100 nm to 500 nm, the size of the manufactured particles is uniform, and when the total energy is measured 11 times while the impeller is rotating at a tip speed of 100 mm / s and simultaneously descending using a Freeman Technology Powder Rheometer FT4, and the cohesive energy is measured while the impeller is ascending, the specific energy (cohesive energy) is 10 mJ / g or less and the total energy is 2,000 mJ or less, thus providing core-shell particles that have resistance to cohesiveness.

[0043] Preferably, core-shell particles with resistance to aggregation can be provided, having a specific energy (cohesive energy) of 6 mJ / g or less and a total energy of 1,200 mJ or less.

[0044] Furthermore, the core-shell particle according to one embodiment can provide an excellent particle morphology in which a shell layer uniformly surrounds the entire area of ​​the core.

[0045] In one embodiment, the monomer forming the core portion is not particularly limited as long as it is a perfluorinated unsaturated monomer, but may be one or more selected from polymers made from monomers selected from, for example, tetrafluoroethylene (TFE), perfluoro(alkyl vinyl ether), hexafluoropropylene, etc., or copolymers thereof, and the resin forming the shell may be a polymethyl methacrylate resin.

[0046] In one embodiment, the polymer constituting the core portion of the core-shell particle may be a polymer or copolymer containing 90% or more, or all, of perfluorinated unsaturated monomers, and the polymethyl methacrylate resin forming the shell may contain 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% by weight of methyl methacrylate monomers.

[0047] Examples of the perfluorinated polymer forming the core portion include polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) / perfluoro(alkyl vinyl ether) copolymer (PFA), or TFE / hexafluoropropylene copolymer (FEP), but are not limited to these. From a physical property standpoint, PTFE homopolymer is more preferred, but is not limited to this.

[0048] In one embodiment, the core material may be synthesized, but when the MMA-based acrylic monomer is added to a perfluorinated resin slurry such as a commercially available PTFE aqueous solution slurry and emulsion polymerization is performed using the emulsifier of chemical formula 1, core-shell particles of 100 to 500 nm with significantly reduced aggregation characteristics and uniform particle size, which is the objective of the present invention, can be obtained.

[0049] When producing the aforementioned perfluorinated resin slurry by polymerization, it can be produced by conventional known methods such as emulsion polymerization, solution polymerization, or suspension polymerization, by appropriately mixing the perfluorinated unsaturated monomer with additives such as polymerization initiators.

[0050] The resin used to form the shell is a methyl methacrylate resin, which is manufactured containing 50% by weight or more, preferably 70% by weight or more, of methyl methacrylate monomer. In the case of a copolymer containing a comonomer, the comonomer is not particularly limited, but one or more selected from, for example, acrylonitrile, vinyl acetate, styrene monomer, vinyl chloride, acrylic acid ester, vinylidene chloride, acrylic acid, methacrylic acid, etc., is preferred.

[0051] Next, a method for producing core-shell particles according to one embodiment will be described.

[0052] In one embodiment, a method for producing the perfluororesin core-polymethyl methacrylate shell particles can be used by adding an emulsifier of the following chemical formula 1 to a perfluororesin slurry solution and dispersing or emulsifying it, and then adding MMA or a monomer composition mainly composed of MMA and performing emulsion polymerization.

[0053] [Chemical formula 1] R-(-O-C2H4-) n -OH (In the above formula, R is a C8 or greater alkyl group substituted with one or more alkyl groups, and n is an integer between 5 and 15.)

[0054] In one embodiment, R is C8~C 30 It may be an alkyl group substituted with one or more alkyl groups.

[0055] In the aforementioned chemical formula 1, it is more preferable, but not limited to, when the ratio of the molecular weight of the hydrophilic oxyethylene group to the total molecular weight ([molecular weight of the oxyethylene chain] / [total molecular weight]) is in the range of 0.5 to 1.0, because it has an even lower cohesive energy value.

[0056] The aforementioned chemical formula 1 may, for example, be the following chemical formula 2.

[0057] [ka]

[0058] The method for producing the aforementioned core-shell particles will be described in detail below.

[0059] In one embodiment, the manufacturing method can be carried out by adding methyl methacrylate or a monomer containing it as a main component to a perfluorinated resin slurry and polymerizing it in the presence of the emulsifier of chemical formula 1.

[0060] The perfluorinated resin slurry may be polymerized by adding all of the MMA or monomer composition mainly composed of MMA before the start of polymerization, or the monomer or monomer composition may be added continuously or stepwise during polymerization, but polymerization by adding continuously is more preferable for uniform particle size.

[0061] The emulsifier of chemical formula 1 may be used alone or in combination with other emulsifiers. Using it alone is more preferable in terms of reducing the cohesive energy, but it may also be used in combination with other emulsifiers to appropriately adjust it.

[0062] The emulsifier may be added to the perfluorinated resin particle slurry continuously or intermittently together with the monomer, or the emulsifier may be added beforehand and then the monomer may be added.

[0063] The content of the emulsifier of chemical formula 1 may be 0.05 to 10 parts by weight, 0.1 to 6 parts by weight, or 0.5 to 2 parts by weight per 100 parts by weight of particles made of perfluorinated polymer, but is not limited to these amounts depending on the particle size.

[0064] In one embodiment, during emulsion polymerization, chain transfer agents, chelating agents, pH adjusters, etc., may be added as needed.

[0065] Examples of the chain transfer agent include, but are not limited to, mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and tert-dodecyl mercaptan. The content of the chain transfer agent is not particularly limited, but may be, for example, 0.001 to 2 parts by weight per 100 parts by weight of monomer or mixture of monomers.

[0066] The polymerization temperature during emulsion polymerization is, for example, 5 to 100°C, preferably 30 to 80°C, and the polymerization time may be 1 to 24 hours, but is not limited thereto.

[0067] In one embodiment, the core-shell slurry polymerized in the core-shell form may have a solid content of 5-60% by weight, 10-50% by weight, 20-40% by weight, or a value between these figures, but is not limited to these values ​​as it can be selected as needed.

[0068] In one embodiment, the core-shell slurry is preferably an aqueous slurry. Needless to say, when referring only to a dispersion in water, it is even more environmentally friendly and preferable, but it may further contain a solvent that is miscible with water as needed. Such a mixed solvent may include, but is not limited to, one or more mixed solvents selected from ketones, acetone, alkyl esters, polar ethers such as N-methylpyrrolidone and tetrahydrofuran, and carbonate esters such as diethylene carbonate.

[0069] In one embodiment, the average diameter of the perfluorinated resin particles contained in the perfluorinated resin slurry forming the core portion may be 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, less than 500 nm, or any size between these numbers. The particle size of the particles having the above diameters can be confirmed by diluting the polymerized latex slurry 1,000 times and measuring the size and distribution of the particles using NICOMP 380 (Entegris, dynamic light scattering method).

[0070] In one embodiment, the composite core-shell particles may have a core weight of 50 to 95 wt%, preferably 60 to 80 wt%, of the total core-shell particles.

[0071] In one embodiment, the thickness of the shell layer may be 1 to 300 nm. Preferably, it is 5 to 200 nm, and more preferably, 10 to 150 nm. When the thickness is as described above, it is preferable that dispersibility, low cohesiveness, and excellent electrical properties when used in battery materials can be exhibited.

[0072] The radius of the core and the thickness of the shell are not particularly limited; for example, the ratio of the core radius to the shell thickness may be 1:0.01 to 1, or 1:0.05 to 0.6, but are not particularly limited as long as the objective of the present invention is achieved.

[0073] The aforementioned core-shell particles can also be used as electrode binders for secondary batteries, as well as in processing fluidizers or emulsion coatings.

[0074] The present invention will be described in more detail below based on examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for illustrating the present invention in more detail, and the present invention is not limited to the following examples and comparative examples.

[0075] In the present invention, the method for evaluating physical properties is as follows.

[0076] 1. Measurement of total solids content After weighing 15g of the polymerization-completed slurry into an aluminum dish, it was dried in an 80°C oven for 24 hours, and the remaining weight was measured. The total solids content was calculated using the formula: (weight after drying - weight of dish) / initial weight x 100.

[0077] 2. Extraction method for non-fluorinated resins 100 g of the polymerization slurry was placed in a 250 ml centrifuge tube and centrifuged at 9,000 rpm for 30 minutes. The separated supernatant was discarded, and 100 g of acetone was added to the remaining solids. The mixture was shaken in a shaker for 3 hours to extract the non-fluorinated resin with acetone. After 3 hours of shaking, the mixture was centrifuged again at 9,000 rpm for 30 minutes. The fluorinated resin aggregated at the bottom, and the acetone supernatant containing the dissolved non-fluorinated resin was separated. The supernatant containing the dissolved non-fluorinated resin was added dropwise to 400 g of methanol to obtain the precipitated non-fluorinated resin. The precipitated non-fluorinated resin was separated using a vacuum filter, washed three times with methanol, and then dried in a separate beaker in an oven at 80°C for 24 hours.

[0078] 3. Weight average molecular weight (Mw) [kg / mol] To measure the molecular weight of the non-fluorinated resin in the slurries produced in the examples and comparative examples, 10 mg of the extracted non-fluorinated resin was dissolved in 10 ml of tetrahydrofuran (THF), filtered through a 0.2 μm Teflon filter, and then measured by Waters GPC (Gel Permeation Chromatography).

[0079] 4. Glass transition temperature (Tg) [°C] For the non-fluorinated resin extracted from the slurries produced in the examples and comparative examples, measurements were taken for two cycles using a TA Q20 DSC (differential scanning calorimetry) under a heating condition of 10°C per minute. The glass transition temperature was then calculated using the half-Cp method based on the inflection point of the second cycle.

[0080] 5. Measurement of the ratio of fluoropolymers to non-fluoropolymers 15 g of the polymerization slurry was placed on an aluminum dish and dried in an oven at 80°C. 10 mg of the dried powder was heated by TGA at a rate of 10°C per minute up to 600°C, and the weight loss was measured. Utilizing the properties of the non-fluorinated resin, which decomposes first, the ratio of fluorinated resin to non-fluorinated resin was determined from the degree of weight loss.

[0081] 6. Measurement of particle size The polymerized latex was diluted 1,000-fold, and the particle size and distribution were measured using NICOMP 380 (Entegris, dynamic light scattering method).

[0082] 7. Measurement of total energy and specific energy of fluidity After the polymerization slurry was freeze-dried, it was obtained in powder form, and its flowability and cohesive energy were measured using a Freeman Technology FT4 powder rheometer. After filling a 50mm diameter sample cylinder with the resin, the total energy was measured 11 times while the impeller rotated at a tip speed of 100mm / s and simultaneously descended, and the cohesive energy was measured while it ascended. A specific energy value of less than 5 was classified as low cohesion, greater than 5 but less than 10 as moderate cohesion, and greater than 10 as high cohesion. Both the total energy and specific energy were averaged from up to 8 measurements, provided the equipment was functioning normally.

[0083] 8. Particle structure analysis (TEM / EDS) After plasma treatment of a grid for a transmission electron microscope (TEM), a drop of slurry was placed on it and dried at room temperature. The dried sample was then analyzed for structure using TEM / EDS (TECNAI TF20 from FEI) at an acceleration voltage of 200kV.

[0084] [Example 1] An aqueous PTFE dispersion was prepared with an average particle diameter of 0.21 μm, a solid content concentration of 30%, and an SSG (Standard Specific Gravity) of 2.16-2.22. Next, 2448.0 g of the PTFE dispersion and 48.96 g of a 90% aqueous solution of polyethylene glycol trimethyl nonyl ether, in which the hydrophilic ethylene glycol repeating units have a molecular weight of 384 g / mol, were placed in a 4-liter reactor. The mixture was stirred at a speed of 350 rpm while simultaneously raising the temperature to 75°C with nitrogen bubbling.

[0085] After reaching the polymerization temperature of 75°C, nitrogen bubbling was stopped, and 15 minutes later, 183.86 g of monomer mixture consisting of 146.88 g of methyl methacrylate (MMA), 36.72 g of butyl acrylate (nBA), and 0.26 g of n-octyl mercaptan was added dropwise to the reactor over 15 minutes.

[0086] Fifteen minutes after adding the monomer mixture, an aqueous solution of 68.4 g of distilled water and 0.92 g of potassium persulfate was added dropwise to the reactor over approximately 10 minutes. After the polymerization reaction proceeded for 3 hours following the completion of potassium persulfate addition, the mixture was cooled to 30°C to obtain a white emulsion.

[0087] The size of the particles in the white emulsion was analyzed using NiCOMP and is listed in Table 1. The results of the particle structure analysis are shown in Figure 1. As shown in Figure 1, a polymethyl methacrylate shell is uniformly formed across the entire surface of the core, and the particle size is also very uniform.

[0088] Furthermore, the emulsified liquid was freeze-dried for 72 hours under conditions of -60°C and 10 mTorr to obtain a white powder, and the results of measuring the total energy and specific energy using this powder are shown in Table 1. As a result, it was found that the Specific Energy (mJ / g) was 5.8, which is very low, and the total energy was also very low at 1,150 mJ, which is below 2,000 mJ, indicating excellent performance.

[0089] [Comparative Example 1] The PTFE aqueous slurry used in Example 1 was freeze-dried without additional polymerization, and the total energy and specific energy were measured using Freeman Technology's FT4, as shown in Table 1 and Figure 2. Since the freeze-dried PTFE aqueous dispersion was interrupted due to high load under the set test conditions, data was calculated using only one measurement. The results are shown in Table 1.

[0090] [Comparative Example 2] In Example 1, the same content was used, except that sodium dodecyl benzene sulfonate was used as the emulsifier. TEM electron microscope images of the resulting aggregates are shown in Figures 2 and 3. As shown in Figure 2, the particles were observed to have an irregular morphology where the polymethyl methacrylate core did not surround the entire surface of the fluorine polymer, rather than a core-shell configuration. Furthermore, as shown in Figure 3, the particle size was irregular and non-uniform, and the particle size was also small. The results of the property analysis are shown in Table 1 below.

[0091] [Comparative Example 3] The procedure was carried out in the same manner as in Example 1, except that 48.96 g of a 90% aqueous solution of polyethylene glycol n-nonyl ether, with a molecular weight of 384 g / mol of ethylene glycol repeating units, was added as an emulsifier. As a result, aggregates were observed. The results of the analysis of the properties are shown in Table 1 below.

[0092] [Comparative Example 4] The procedure was carried out similarly to Example 1, except that instead of using a 90% aqueous solution of polyethylene glycol trimethylnonyl ether, in which the molecular weight of the ethylene glycol repeating units is mainly 384 g / mol, an emulsifier with 3 repeating units of the ethylene glycol was used. The results are shown in Table 1.

[0093] [Table 1]

[0094] As can be seen from the analysis results above, in the case of the present invention, Example 1 has a particle size with a diameter of 260 nm, yet as shown in Figure 1, it has uniform particles, and its Specific Energy (mJ / g) is very low at 5.8. Furthermore, the total energy is also very low at 1,150 mJ, which is below 2,000 mJ, demonstrating its excellent performance.

[0095] However, when the substance of the present invention was not used as an emulsifier (Comparative Examples 2 and 3), or when the structure deviated from that defined in the present invention (Comparative Example 4), or when the repeating units of ethylene glycol were short as in Example 2, the Specific Energy (mJ / g) was 10 or more and 15 or more, indicating poor performance. Furthermore, the total energy was 2,000 mJ or more, 3,000 mJ or more, and 4,000 mJ or more, indicating very low dispersibility.

Claims

1. A composite core-shell particle having a perfluorinated resin core and a polymethyl methacrylate resin shell, produced by emulsion polymerization of a methyl methacrylate monomer using polyethylene glycol ether of the following chemical formula 1 as an emulsifier in a perfluorinated resin particle slurry, An electrode manufactured from a compound containing an electrode active material. [Chemical formula 1] R-(-O-C 2 H 4 -) n -OH (In the above formula, R is C 8 The alkyl groups are as described above, and n is an integer between 5 and 15.

2. The electrode according to claim 1, wherein the cohesive energy is 10 mJ / g or less.

3. The electrode according to claim 1, wherein the total fluid energy of the composite core-shell particles is 2,000 mJ or less.

4. The electrode according to claim 1, wherein the average diameter of the core-shell particles is 100 to 500 nm.

5. The electrode according to claim 1, wherein the weight of the core is 50 to 95 wt% of the total core-shell particles.

6. A battery having the electrode described in claim 1.

7. The electrode according to claim 1, wherein the composite core-shell particle having a perfluorinated resin core and a polymethyl methacrylate resin shell has an aggregation energy of 10 mJ / g or less and a total flow energy of 2,000 mJ or less.

8. The electrode according to claim 7, wherein the average diameter of the composite core-shell particles is 100 to 500 nm.

9. The electrode according to claim 8, wherein the average diameter of the core of the composite core-shell particles is 50 to less than 500 nm, and the thickness of the shell is 1 to 300 nm.

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