Core-shell fluorine-based resin particles having improved flowability and cohesiveness and a method for producing the same

Abstract

The present invention relates to a dispersion comprising core-shell fluorine-based resin particles having improved flowability and coaggregation. Specifically, provided are particles having a perfluorine-based polymer core and an acrylic polymer shell, a mixture or slurry (dispersion) comprising the particles, and a method for producing the same, wherein the particles are formed by adding an acrylic monomer to a dispersion of perfluorinated polymer particles.

Description

TECHNICAL FIELD

[0001] The present application relates to a dispersion containing core-shell type fluorine-based resin particles having improved flowability and coagglomeration.

[0002] An embodiment of the present application provides a particle having a perfluorinated polymer core and an acrylic polymer shell, a mixture or slurry (dispersion) containing the same, and a method for preparing the same, the particle being prepared by adding an acrylic monomer to a dispersion of perfluorinated polymer particles.

[0003] In the core-shell type particle having a perfluorinated resin core and a polymethyl methacrylate-based resin shell prepared by the method, the shell resin well coats the entire surface of the core with a uniform thickness.

[0004] In addition, the core-shell type particle is characterized by having a uniform particle size and excellent flowability and low coagglomeration, and can control the PTFE fiberization time point according to the user's intention. BACKGROUND

[0005] Perfluorinated polymers including polytetrafluoroethylene (PTFE) have the following uses: due to their electrical properties, thermal properties, and adhesive properties, etc., they are used for various adhesives, process improvers, and fluidizers, etc.; or they are used as coating materials for various substrates in semiconductor manufacturing devices, etc., and power storage devices, etc., and together with other materials as adhesive materials, etc.

[0006] However, the adhesion of the perfluorinated resin particles themselves to other materials (polymer resin films or electrodes, etc.) is still insufficient, and in order to solve this problem and improve the surface properties while properly using the properties of the perfluorinated resin particles, a preparation technique for core-shell particles in which a non-fluorinated resin shell layer is used as a surface layer of the fluorinated resin particles has been developed.

[0007] However, for the existing core-shell particles, the increase in coagglomeration is greater than the dispersibility, and thus in actual use, the flowability of the slurry is insufficient, and the performance is limited in terms of exerting sufficient performance due to coagglomeration between the particles. In addition, it is difficult to obtain a shell layer uniformly formed on the entire surface of the perfluorinated resin particles (core), and thus it is difficult to adjust the physical properties. SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] To solve the problem, an embodiment of the present application provides a core-shell particle including a perfluorinated resin core having excellent dispersibility and a polymethyl methacrylate-based resin shell, and the provided core-shell particle has a specific energy (cohesion energy) of 10 mJ / g or less and a total energy of 2000 mJ or less when measured 11 times using a Powder Rheometer FT4 of Freeman Technology, in which a sample cylinder having a diameter of 50 mm is filled with the core-shell resin, a rotor is rotated at a tip speed of 100 mm / sec while being lowered, and the cohesion energy is measured during the rising process.

[0010] Therefore, the core-shell particle of an embodiment provides a perfluorinated resin core having low cohesion between particles and a core-shell particle having an acrylic polymer shell.

[0011] In addition, the core-shell particle of an embodiment aims to provide a core-shell particle including a perfluorinated resin core and a polymethyl methacrylate-based resin shell, having a particle size of 100 nm to 500 nm.

[0012] In addition, the core-shell particle of an embodiment provides an excellent particle shape of a core-shell particle in which the entire area of the core is uniformly wrapped with a shell layer.

[0013] Means for solving the problem

[0014] As a result of research conducted to solve the problem, it was found that, in a perfluorinated polymer particle slurry, polymer particles having a core-shell structure are prepared by emulsion polymerization of an acrylic-based monomer, and a slurry including the same is prepared, and, as an emulsifier, a polyethylene glycol ether having an alkyl group of C8 or more substituted with one or more alkyl groups of Chemical Formula 1 is used as an emulsifier to perform emulsion polymerization, whereby a core-shell particle having the above-described physical properties and a mixture or slurry including the same can be prepared, thereby completing the present application.

[0015] [Chemical Formula 1]

[0016] R-(-O-C2H4-) n -OH

[0017] (In the chemical formula, R is an alkyl group of C8 or more substituted with one or more alkyl groups, and n is an integer of 5 to 15.)

[0018] As an embodiment, R can be an alkyl group of C8 to C 30 substituted with one or more alkyl groups.

[0019] In the chemical formula 1 of an embodiment, the ratio of the molecular weight of the oxyethylene group, which is the hydrophilic group, to the total molecular weight ([molecular weight of oxyethylene chain] / [total molecular weight]) can be 0.5 to 1.0.

[0020] As an embodiment, the chemical formula 1 can be the following chemical formula 2.

[0021] [Chemical formula 2]

[0022]

[0023] As an embodiment, the core-shell particle having the perfluorinated polymer core and the acrylic polymer shell is prepared by emulsion polymerization of an acrylic-based monomer using, as an emulsifier, a polyethylene glycol ether having a C8 or more alkyl group substituted with one or more alkyl groups of the chemical formula 1 in a seed slurry (hereinafter, referred to as "perfluorinated resin particle slurry") containing perfluorinated particles.

[0024] The perfluorinated resin particle slurry of an embodiment can contain a tetrafluoroethylene-derived unit as a main component.

[0025] In the composite core-shell particle slurry of an embodiment, the poly(methyl methacrylate)-based resin shell layer can be 60% by weight or more.

[0026] In an embodiment, the core-shell particle and slurry having a perfluorinated resin core-poly(methyl methacrylate)-based resin shell can be prepared by emulsion polymerization of an acrylic-based monomer using, as an emulsifier, a polyethylene glycol ether having a C8 or more alkyl group substituted with one or more alkyl groups of the following chemical formula 1 in a perfluorinated resin particle slurry.

[0027] [Chemical formula 1]

[0028] R-(-O-C2H4-) n -OH

[0029] (where, in the chemical formula, R is a C8 or more alkyl group substituted with one or more alkyl groups, and n is an integer of 5 to 15.)

[0030] The composite core-shell particle of an embodiment can be a composite core-shell particle having a coagulation energy of 10 mJ / g or less.

[0031] In the composite core-shell particle of an embodiment, the total surface energy of the particle can be 2000 mJ or less.

[0032] In the composite core-shell particle of one embodiment, the core-shell particle can have a particle diameter of 100 nm to 500 nm.

[0033] In one embodiment, the core of the composite core-shell particle can have a weight of 50 wt% to 95 wt% of the total core-shell particle, preferably 60 wt% to 80 wt%.

[0034] In one embodiment, the core-shell slurry can be an electrode-forming slurry containing the core-shell particle and an electrode active material or a composite containing the particle.

[0035] One embodiment can also provide a battery prepared using the core-shell particle as a binder of an electrode active material.

[0036] The composite core-shell particle of one embodiment is a composite core-shell particle having a perfluorinated resin core and a polymethyl methacrylate-based resin shell, and has a coagulation energy of 10 mJ / g or less and a total surface energy of 2000 mJ or less.

[0037] In the composite core-shell particle of one embodiment, the core-shell particle can have an average diameter of 100 nm to 500 nm.

[0038] In the composite core-shell particle of one embodiment, the core of the core-shell particle can have an average diameter of 50 nm or more and less than 500 nm, and the shell can have a thickness of 1 nm to 300 nm.

[0039] One embodiment can provide a water-dispersible slurry containing the composite core-shell particle.

[0040] One embodiment can provide a water-dispersible slurry further containing an electrode active material.

[0041] Effects of Invention

[0042] The core-shell polymer particle composed of the perfluorinated resin core and the polymethyl methacrylate-based resin, which is prepared according to the preparation method of one embodiment, can have excellent dispersion properties and can minimize the generation of aggregates.

[0043] The core-shell particle according to the preparation method of one embodiment can have a large particle diameter of 100 nm to 500 nm, and the preparation method according to the present application can prepare particles having excellent particle size uniformity.

[0044] The core-shell particle of the embodiment can provide a core-shell particle having excellent dispersibility with low agglomeration energy, for which, using a rheometer (Powder Rheometer) FT4 of Freeman Technology, after filling a sample cylinder of 50 mm in diameter with the core-shell resin, the impeller is rotated at a tip speed of 100 mm / sec while descending, the total energy is measured 11 times, and when measuring the agglomeration energy during the ascending process, the specific energy (agglomeration energy) is 10 mJ / g or less, and the total energy is 2000 mJ or less.

[0045] Therefore, when the particles are mixed with other particles, since they have excellent dispersibility, uniform mixing can be achieved, when the particles are used as an adhesive, very uniform adhesive properties can be provided, and the adhesive force can also be easily adjusted according to the content thereof.

[0046] In addition, a core-shell particle having excellent properties can be obtained, in which the shell layer uniformly covers the entire area of the core. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 is a TEM / EDS image of Example 1.

[0048] Figure 2 is a TEM / EDS image of Comparative Example 2.

[0049] Figure 3 is a TEM / EDS image of Comparative Example 2. DETAILED DESCRIPTION

[0050] The particles of the present application are core-shell particles having a core comprising a perfluoropolymer and a shell layer comprising a polymethyl methacrylate-based resin, and provide a core-shell particle having a particle size of 100 nm to 500 nm while having low agglomeration energy.

[0051] For example, a core-shell structure comprising a core of a perfluoropolymer and a shell of a non-fluororesin is described in U.S. Patent No. 6,841,594, however, the particles prepared by this method have high agglomeration energy, and thus practically agglomerate in the state of other inorganic particles or slurry, thereby having a problem in that they cannot be sufficiently dispersed. That is, they exhibit the characteristics of excessively high agglomeration energy.

[0052] However, the core-shell particles of the present embodiment can adjust the size of the particles to a size of 100 nm to 500 nm and produce particles of uniform size, and can provide a core-shell particle having anti-aggregation properties, with a Specific energy (aggregation energy) of 10 mJ / g or less and a Total energy of 2000 mJ or less, when measured 11 times using a Powder Rheometer FT4 of Freeman Technology, after filling a core-shell resin in a sample cylinder of 50 mm in diameter, and rotating an impeller at a tip speed of 100 mm / sec while descending, and measuring the aggregation energy during the ascending process.

[0053] Preferably, a core-shell particle having anti-aggregation properties can be provided, with a Specific energy (aggregation energy) of 6 mJ / g or less and a Total energy of 1200 mJ or less.

[0054] Also, the core-shell particles of the present embodiment can provide an excellent particle shape in which the entire area of the core is uniformly covered with the shell.

[0055] In the present embodiment, the polymer or copolymer forming the core portion is not particularly limited as long as the monomer from which the polymer or copolymer is produced is a perfluorinated unsaturated monomer, and for example, can be produced from a monomer selected from the group consisting of tetrafluoroethylene (TFE), perfluoro(alkyl vinyl ether), and hexafluoropropylene, and the resin forming the shell can be a polymethyl methacrylate-based resin.

[0056] In the present embodiment, the polymer constituting the core portion of the core-shell particles can be a polymer or copolymer containing 90% or more or all perfluorinated unsaturated monomers, and the polymethyl methacrylate-based resin forming the shell can contain 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, or 100% by weight of methyl methacrylate monomers.

[0057] Examples of the perfluorinated polymer forming the core portion can be polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) / perfluoro(alkyl vinyl ether) copolymer (PFA), or TFE / hexafluoropropylene copolymer (FEP), but are not limited thereto, and in terms of physical properties, a PTFE homopolymer is more preferable, but is not limited thereto.

[0058] In one embodiment, the core material can be synthesized, but when a perfluorinated resin slurry such as a commercially available PTFE aqueous slurry is used, the MMA-based acrylic monomer is added and emulsion polymerization is performed using the emulsifier of Chemical Formula 1, and thus core-shell particles having a uniform particle size of 100 nm to 500 nm and a significantly reduced agglomeration property can be obtained.

[0059] When the perfluorinated resin slurry is prepared by polymerization, it can be prepared by appropriately mixing the perfluorinated unsaturated monomer and additives (polymerization initiator, etc.) and performing emulsion polymerization, solution polymerization, or suspension polymerization, etc. by a method known in the art.

[0060] The resin forming the shell is prepared by including 50% by weight or more of a methyl methacrylate-based resin, and preferably, 70% by weight or more of a methyl methacrylate monomer, and as a copolymer including the monomer, a comonomer is not particularly limited, and for example, one or two or more selected from the group consisting of acrylonitrile, vinyl acetate, a styrene-based monomer, vinyl chloride, acrylate, vinylidene chloride, acrylic acid, and methacrylic acid, etc. is preferred.

[0061] Next, a method of preparing core-shell particles according to one embodiment will be described.

[0062] The method of preparing the perfluorinated resin core-poly(methyl methacrylate)-based shell particles according to one embodiment can be a method of adding an emulsifier of Chemical Formula 1 below to a perfluorinated resin slurry solution and dispersing or emulsifying, and then preparing by adding MMA or a monomer composition in which MMA is a main component and performing emulsion polymerization.

[0063] [Chemical Formula 1]

[0064] R-(-O-C2H4-) n -OH

[0065] (wherein, in the chemical formula, R is an alkyl group of C8 or more substituted with one or more alkyl groups, and n is an integer of 5 to 15.)

[0066] As one embodiment, the R can be an alkyl group of C8 to C 30 substituted with one or more alkyl groups.

[0067] In Chemical Formula 1, when the ratio of the molecular weight of the oxyethylene group, which is a hydrophilic 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, the agglomeration energy value is lower, and thus it is more preferred, but is not limited thereto.

[0068] An example of Chemical Formula 1 can be Chemical Formula 2 below.

[0069] [Chemical Formula 2]

[0070]

[0071] Hereinafter, the method for producing the core-shell particles will be described in detail.

[0072] As an example, the production method can be obtained by adding methyl methacrylate or a monomer containing the same as a main component to a perfluorinated resin slurry and polymerizing in the presence of the emulsifier of Chemical Formula 1.

[0073] The MMA or the monomer composition containing the MMA as a main component can be all added to the perfluorinated resin slurry before the polymerization is started and the polymerization can be performed, or the monomer or the monomer composition can be continuously or stepwise added and the polymerization can be performed, but in order to homogenize the particle size, the continuous addition polymerization can be more preferable.

[0074] The emulsifier of Chemical Formula 1 can be used alone or in combination with other emulsifiers, and although the use alone is better in terms of the effect of reducing the coagulation energy, the combination use can be adopted from the viewpoint of appropriately adjusting the coagulation energy.

[0075] The emulsifier can be continuously or intermittently added to the perfluorinated resin particle slurry together with the monomer, or the emulsifier can be added in advance and then the monomer can be added.

[0076] The content of the emulsifier of Chemical Formula 1 can be 0.05 parts by weight to 10 parts by weight, 0.1 parts by weight to 6 parts by weight, or 0.5 parts by weight to 2 parts by weight, with respect to 100 parts by weight of the particles composed of a perfluoropolymer, but can be adjusted according to the size of the particles, and is not limited thereto.

[0077] In addition, as an example, a chain transfer agent, a chelating agent, a pH adjuster, and the like can be added as needed during the emulsion polymerization.

[0078] For example, the chain transfer agent can be exemplified by n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, and the like, but is not limited thereto. The content of the chain transfer agent is not limited, but for example, 0.001 parts by weight to 2 parts by weight can be used with respect to 100 parts by weight of the monomer or the monomer mixture.

[0079] For example, the polymerization temperature during the emulsion polymerization can be, for example, 5°C to 100°C, and is preferably 30°C to 80°C, and the polymerization time can be 1 hour to 24 hours, but is not limited thereto.

[0080] As an example, the solid content of the core-shell slurry polymerized in the core-shell shape can be 5 to 60 wt%, 10 to 50 wt%, 20 to 40 wt%, or a value between these numbers, but this can be selected as needed, and thus is not limited thereto.

[0081] As an example, the core-shell slurry is preferably an aqueous slurry. Of course, when it means dispersion in water only, it is more environmentally friendly, but depending on the need, a solvent having water miscibility can also be included. Such a mixed solvent can include a mixed solvent selected from one or two or more of polar ethers (ketones, acetone, alkyl esters, N-methylpyrrolidone, and tetrahydrofuran, etc.), carbonates (diethyl carbonate, etc.), and the like, but is not limited thereto.

[0082] As an example, the average diameter of the perfluorinated resin particles contained in the perfluorinated resin slurry forming the core can 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, and a size between the numbers. The particle size having the diameter can be determined by diluting the latex slurry completed by polymerization by 1000 and using NICOMP 380 (Entegris, dynamic light scattering method) to measure the particle size and distribution.

[0083] In an example, the core weight of the composite core-shell particle can be 50 to 95 wt% of the total core-shell particle, and preferably 60 to 80 wt%.

[0084] In an example, the thickness of the shell layer can be 1 to 300 nm. It is preferably 5 to 200 nm, and more preferably 10 to 150 nm. When in the thickness range, when used as a battery material having dispersibility and low agglomeration, excellent electrical properties, etc. can be exhibited, and thus is preferred.

[0085] The radius of the core and the thickness of the shell are not particularly limited, for example, the radius of the core and the thickness of the shell can be 1:0.01 to 1, and can be 1:0.05 to 0.6, but as long as the purpose of the present application can be achieved, it is not particularly limited.

[0086] The core-shell particle can also be used in the electrode binder or processing fluidizer or latex paint of the secondary battery.

[0087] Hereinafter, the present application will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are only examples provided to more specifically explain the present application, and the present application is not limited to the following examples and comparative examples.

[0088] The physical property evaluation method of the present application is as follows.

[0089] 1. Total solid content measurement

[0090] 15 g of the polymerized slurry was weighed in an aluminum dish, and then dried in an oven at 80°C for 24 hours, and the remaining weight was measured. The total solid content was calculated as follows: (weight after drying - weight of the dish) / initial weight x 100.

[0091] 2. Non-fluorine resin extraction method

[0092] 100 g of the polymerized slurry was placed in a 250 ml centrifuge tube and centrifuged at 9000 rpm for 30 minutes. The separated supernatant was discarded, and 100 g of acetone was added to the remaining solid, and shaken for 3 hours with a shaker to extract the non-fluorine resin with acetone. After shaking for 3 hours, it was again centrifuged at 9000 rpm for 30 minutes, and the fluorine resin was concentrated at the bottom, thereby separating the acetone supernatant in which the non-fluorine resin was dissolved. The supernatant in which the separated non-fluorine resin was dissolved was added dropwise to 400 g of methanol to obtain precipitated non-fluorine resin. The precipitated non-fluorine resin was separated using a vacuum filter, washed 3 times with methanol, and then charged into a separate beaker and dried in an oven at 80°C for 24 hours.

[0093] 3. Weight average molecular weight (Mw) [kg / mol]

[0094] In order to measure the molecular weight of the non-fluorine resin of the slurry prepared in the examples and comparative examples, 10 mg of the extracted non-fluorine resin was dissolved in 10 ml of tetrahydrofuran (THF), respectively, and then filtered using a 0.2 μm Teflon filter, and then measured using a gel permeation chromatography (GPC) of a waters company.

[0095] 4. Glass transition temperature (Tg) [°C]

[0096] The non-fluorine resin extracted from the slurry prepared in the examples and comparative examples was measured using a Q20 differential scanning calorimetry (DSC) of a TA company, at a temperature increase of 10°C per minute, after 2 cycles, and the glass transition temperature was calculated using the inflection point of the second cycle by a half conformal prediction (half CP) method.

[0097] 5. Ratio of fluorine resin to non-fluorine resin measurement

[0098] The 15 g of the polymerized slurry was put in an aluminum pan and dried in an oven at 80°C. The 10 mg of the dried powder was measured for the reduced weight by TGA with the temperature rising at 10°C per minute up to 600°C. First, the ratio of the fluorine-based resin to the non-fluorine-based resin was measured by the degree of weight loss using the characteristics of the non-fluorine-based resin decomposed by heat.

[0099] 6. Particle size measurement

[0100] The polymerized latex was diluted 1000 times, and the particle size and distribution were measured using NICOMP 380 (Entegris, dynamic light scattering).

[0101] 7. Measurement of flowability total energy and cohesion energy (specific energy)

[0102] The polymerized slurry was freeze-dried to obtain in powder form, and the flowability and cohesion energy were measured by the FT4 Rheometer of Freeman Technology. After the resin was filled into a sample cylinder with a diameter of 50 mm, the impeller was rotated at a tip speed of 100 mm / sec while descending, and the total energy was measured 11 times, and the cohesion energy was measured during the ascending process. When the specific energy value was less than 5, it was judged as low cohesion, when it was more than 5 and less than 10, it was judged as moderate cohesion, and when it was more than 10, it was judged as high cohesion. The measurement results of the total energy and the specific energy were averaged 8 times under the premise that the equipment was normally operated.

[0103] 8. Particle structure analysis (TEM / EDS)

[0104] After plasma treatment on the TEM filter, a drop of slurry was dropped, and then dried at room temperature. The dried sample was analyzed for its structure using TEM / EDS (TECNAI TF20 of FEI) at an acceleration voltage of 200 kV.

[0105] [Example 1]

[0106] An aqueous PTFE dispersion having an average particle diameter of 0.21 μm, a solid concentration of 30%, and a standard specific gravity (SSG) of 2.16 to 2.22 was prepared. Next, in a 4 liter reactor, 2448.0 g of the PTFE dispersion and 48.96 g of a 90% aqueous solution of polyethylene glycol trimethylnonyl ether having a molecular weight of 384 g / mol of the repeating unit of ethylene glycol showing hydrophilicity were added, and nitrogen bubbling was performed while stirring at 350 RPM and the temperature was raised to 75°C.

[0107] After the polymerization temperature reached 75°C, the nitrogen bubbling was stopped, and after 15 minutes, 183.86 g of a monomer mixture solution composed 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 a period of 15 minutes.

[0108] After 15 minutes from the addition of the monomer mixture solution, 68.4 g of distilled water and 0.92 g of an aqueous solution of potassium persulfate were added dropwise to the reactor over a period of about 10 minutes. After the addition of the potassium persulfate was completed, the polymerization reaction was performed for 3 hours, and then cooled to 30°C to obtain a white emulsion.

[0109] The white emulsion was subjected to size analysis by NiCOMP and is shown in Table 1, and the results of the particle structure analysis are shown in Figure 1 As shown in Figure 1 , it was found that a polymethyl methacrylate shell was uniformly formed on the entire surface of the core, and the size of the particles was also very uniformly formed.

[0110] In addition, a white powder was obtained by freeze-drying the emulsion at -60°C and 10 mTorr for 72 hours, and the results of the total energy and specific energy determined using this are shown in Table 1. The results show that the specific energy (mJ / g) was very low, at 5.8, and the total energy exhibited was also very excellent, at 1150 mJ (less than 2000 mJ).

[0111] [Comparative Example 1]

[0112] The aqueous PTFE slurry used in Example 1 was directly freeze-dried without additional polymerization, and then the total energy and specific energy were determined using the FT4 of Rigaku, and the results are shown in Table 1 andFigure 2 The freeze-dried product of the PTFE aqueous dispersion was discontinued due to excessive load under the set test conditions, and thus the data was calculated using the value of one measurement. The results are shown in Table 1.

[0113] [Comparative Example 2]

[0114] The same content was used except that sodium dodecyl benzene sulfonate was used instead of the emulsifier in Example 1. The results of the TEM electron microscope of the aggregates are shown in Figure 2 and Figure 3 As shown in Figure 2 , it was observed that the particles were not in a core-shell shape, but rather an irregular shape, in which the polymethyl methacrylate failed to cover the entire surface of the fluoropolymer as the core, and as shown in Figure 3 , the particle size was also irregular and uneven, and the particle size was also small. The results of the analysis characteristics are shown in Table 1 below.

[0115] [Comparative Example 3]

[0116] In Example 1, the same was done except that 48.96 g of a 90% aqueous solution of polyethylene glycol n-nonyl ether having a molecular weight of 384 g / mol of ethylene glycol repeating units was added as an emulsifier. As a result, aggregates were observed, and the results of the analysis characteristics are shown in Table 1 below.

[0117] [Comparative Example 4]

[0118] In Example 1, the same was done except that a 90% aqueous solution of polyethylene glycol trimethyl nonyl ether having a molecular weight of 384 g / mol of ethylene glycol repeating units was used instead of the ethylene glycol repeating unit having a molecular weight of 384 g / mol of ethylene glycol repeating units. The results are shown in Table 1.

[0119] Table 1

[0120]

[0121]

[0122] From the analysis results, as shown in Figure 1 , the particle size of Example 1 of the present application was 260 nm and had uniform particles, the specific energy (mJ / g) was very low at 5.8, and it was known that a very excellent total energy of 1150 mJ (less than 2000 mJ) was also exhibited.

[0123] On the contrary, it was known that in the case where the material of the present application was not used as an emulsifier (Comparative Example 2 and Comparative Example 3) or the repeating unit of ethylene glycol of Example 2 was short in the structure defined in the present application (Comparative Example 4), the specific energy (mJ / g) was deteriorated to be 10 or more and 15 or more, and the total energy was 2000 mJ or more, 3000 mJ or more, 4000 mJ or more, i.e., very low dispersibility was exhibited.

Claims

1. A slurry of composite core-shell particles, wherein, the composite core-shell particles have a perfluorinated resin core-poly(methyl methacrylate)-based resin shell layer, the slurry of the composite core-shell particles is prepared by emulsion polymerization of an acrylic monomer using, in a perfluorinated resin particle slurry, a polyethylene glycol ether having a C8 or more alkyl group substituted with one or more alkyl groups of the following Chemical Formula 1 as an emulsifier, [Chemical Formula 1] R-(-O-C2H4-) n -OH in the chemical formula, R is a C8 or more alkyl group substituted with one or more alkyl groups, and n is an integer of 5 to 15.

2. The slurry of composite core-shell particles according to claim 1, wherein, in the Chemical Formula 1, the ratio of the molecular weight of oxyethylene group to the total molecular weight, i.e., [molecular weight of oxyethylene chain] / [total molecular weight] of the hydrophilic group is 0.5 to 1.

0.

3. The slurry of composite core-shell particles according to claim 1, wherein, the Chemical Formula 1 is an emulsifier of the following Chemical Formula 2, [Chemical Formula 2] 4. The slurry of composite core-shell particles according to claim 1, wherein, the perfluorinated resin particles are perfluorinated resin particles having tetrafluoroethylene-derived units as a main component.

5. The slurry of composite core-shell particles according to claim 1, wherein, the poly(methyl methacrylate)-based resin shell layer can contain 60% by weight or more.

6. A composite core-shell particle, wherein, the composite core-shell particle has a perfluorinated resin core-poly(methyl methacrylate)-based resin shell, the composite core-shell particle is prepared by emulsion polymerization of an acrylic monomer using, in a perfluorinated resin particle slurry, a polyethylene glycol ether having a C8 or more alkyl group substituted with one or more alkyl groups of the following Chemical Formula 1 as an emulsifier, [Chemical Formula 1] R-(-O-C2H4-) n -OH in the chemical formula, R is a C8 or more alkyl group substituted with one or more alkyl groups, and n is an integer of 5 to 15.

7. The composite core-shell particle according to claim 6, wherein, the composite core-shell particle has a coagulation energy of 10 mJ / g or less.

8. The composite core-shell particle according to claim 6, wherein, the composite core-shell particle has a total surface energy of 2000 mJ or less.

9. The composite core-shell particle according to claim 6, wherein, the core-shell particle has an average diameter of 100 nm to 500 nm.

10. An electrode, wherein, the electrode is prepared from a composite containing the composite core-shell particle according to any one of claims 6 to 9 and an electrode active material.

11. A battery, wherein, the composite core-shell particle according to any one of claims 6 to 9 is contained as a binder.

12. The composite core-shell particle according to claim 6, wherein, the composite core-shell particle having a perfluorinated resin core-poly(methyl methacrylate)-based resin shell has a coagulation energy of 10 mJ / g or less and a total surface energy of 2000 mJ or less.

13. The composite core-shell particle according to claim 12, wherein, the composite core-shell particle has an average diameter of 100 nm to 500 nm.

14. The composite core-shell particle according to claim 12, wherein, The average diameter of the core of the composite core-shell particle is 50 nm or more and less than 500 nm, and the thickness of the shell is 1 nm to 300 nm.

15. A composite, wherein, comprising the particle of any one of claims 12 to 14.

16. The composite according to claim 15, wherein, The composite comprises an electrode active material.

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