Core-shell type fluororesin particles with improved fluidity and cohesiveness and production method thereof

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-based resin shell produced by the above method have the shell resin sufficiently surrounding the entire surface of the core with a uniform thickness.

[0004] Further, the core-shell type particles have a uniform particle size, and also have 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., and are used together 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, while utilizing the properties of the perfluorinated resin particles as they are and improving the surface properties, a manufacturing technique 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, in conventional core-shell particles, the cohesiveness increases rather than the dispersibility. Therefore, when actually used, the fluidity of the slurry is insufficient, and there is a limit to achieving sufficient performance due to the aggregation of particles. In addition, it is difficult to obtain a shell layer uniformly formed on the entire surface of the perfluorinated resin particles that are the core, and it is difficult to adjust the physical properties.

Summary of the Invention

Problems to be Solved by the Invention

[0008] To solve the above problems, one aspect provides core-shell particles including a perfluorinated resin core with excellent dispersibility and a polymethyl methacrylate-based resin shell. After filling a core-shell resin into a sample cylinder with a diameter of 50 mm using a Powder Rheometer FT4 from Freeman Technology, while rotating the impeller at a tip speed of 100 mm / s and descending simultaneously, the total energy is measured 11 times, and when measuring the aggregation energy while ascending, the core-shell particles are provided with a Specific energy (aggregation energy) having a value of 10 mJ / g or less and a total energy having a value of 2000 mJ or less.

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

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

[0011] Also, one aspect provides an excellent particle morphology capable of obtaining core-shell particles in which the shell layer uniformly surrounds the entire area of the core.

Means for Solving the Problems

[0012] As a result of research to achieve the above problems, in the presence of a perfluorinated polymer particle slurry, an acrylic monomer is emulsion polymerized to produce polymer particles having a core-shell and a slurry containing the same. At this time, by using a polyethylene glycol ether having a C8 or higher alkyl group substituted with one or more alkyls represented by the following Chemical Formula 1 as an emulsifier for emulsion polymerization, core-shell particles having the above physical properties, and a mixture or slurry containing the same can be produced, and the present invention has been completed.

[0013] [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.)

[0014] In one aspect, the R may be an alkyl group substituted with one or more alkyl groups of C8 to C 30 of the present invention.

[0015] In one aspect, in the Chemical Formula 1, a composite core-shell particle slurry in which 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 0.5 to 1.0 may be used.

[0016] In one aspect, the Chemical Formula 1 may be the following Chemical Formula 2.

[0017] [Chemical Formula]

[0018] In one aspect, the core-shell particles having the perfluorinated polymer core and the acrylic polymer shell can be produced by emulsion polymerizing an acrylic monomer using a polyethylene glycol ether having a C8 or higher alkyl group substituted with one or more alkyls represented by the Chemical Formula 1 as an emulsifier in a seed slurry containing perfluorinated particles (hereinafter referred to as "perfluorinated resin particle slurry").

[0019] In one aspect, the perfluorinated resin particle slurry may be a slurry containing perfluorinated resin particles mainly composed of units derived from tetrafluoroethylene.

[0020] In one aspect, the polymethyl methacrylate 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 prepared by emulsion polymerization of an acrylic monomer using a polyethylene glycol ether having a C8 or higher alkyl group substituted with one or more alkyl groups 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 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 alkyl groups, 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 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.

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

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

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

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

[0031] In one aspect, composite core-shell particles are provided, wherein the average diameter of the core of the core-shell particles is less than 50 to 500 nm and the thickness of the shell is 1 to 300 nm.

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

[0033] In one aspect, an aqueous dispersion slurry is provided, wherein the aqueous dispersion slurry further contains an electrode active material.

Advantages of the Invention

[0034] The core-shell polymerization particles composed of the perfluorinated resin core and the polymethyl methacrylate-based resin produced by the manufacturing method of one aspect have excellent dispersion characteristics and can minimize the formation of aggregates.

[0035] The core-shell type particles according to the manufacturing method of one aspect have a large particle size of 100 to 500 nm, and particles excellent in particle size uniformity can be manufactured.

[0036] The core-shell particles according to one aspect are obtained by using a Powder Rheometer FT4 of Freeman Technology, filling a core-shell resin into a sample cylinder with a diameter of 50 mm, and then measuring the total energy 11 times while rotating and descending the impeller at a tip speed of 100 mm / s, and measuring the aggregation energy while ascending. When the Specific energy (aggregation energy) has a value of 10 mJ / g or less and the total energy has a value of 2000 mJ or less, core-shell particles with low aggregation energy and excellent dispersibility are provided.

[0037] Therefore, when the particles are mixed with other particles, they are excellent in dispersibility and can be uniformly mixed. When the particles are used as a binder, very uniform binding characteristics can be provided, and the binding force can be easily adjusted according to its content.

[0038] In addition, core-shell particles with excellent properties can be obtained in which the shell layer uniformly surrounds the entire surface area of the core.

Brief Description of the Drawings

[0039]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0040] The particles of the present invention are core-shell type particles having a core containing a perfluoropolymer and a shell layer containing a polymethyl methacrylate resin, with a particle size of 100 to 500 nm and having low aggregation energy.

[0041] A core-shell structure including a core of a conventional perfluoropolymer and a shell of a non-fluorine resin is described, for example, in U.S. Patent No. 6,841,594. However, the particles produced by such a method have a problem that they are actually aggregated with other inorganic particles or in a slurry state due to high aggregation energy and are not sufficiently dispersed. That is, they have a characteristic of excessively high aggregation energy.

[0042] However, the core-shell particles according to this aspect can have their particle size adjusted to 100 nm to 500 nm, and the size of the produced particles is uniform. Using a Powder Rheometer FT4 from Freeman Technology, after filling a sample cylinder with a diameter of 50 mm with the core-shell resin, while rotating the impeller at a tip speed of 100 mm / s and descending simultaneously, the total energy is measured 11 times, and when measuring the aggregation energy while ascending, it is possible to provide core-shell particles having a resistance to aggregation, with a Specific energy (aggregation energy) having a value of 10 mJ / g or less and a total energy having a value of 2,000 mJ or less.

[0043] Preferably, it is possible to provide core-shell particles having a resistance to aggregation, with the Specific energy (aggregation energy) having a value of 6 mJ / g or less and a total energy having a value of 1,200 mJ or less.

[0044] Also, the core-shell particles according to one aspect can provide an excellent particle morphology capable of obtaining core-shell particles in which the shell layer uniformly surrounds the entire surface area of the core.

[0045] In one aspect, the monomer forming the core part is not particularly limited as long as it is a perfluorinated unsaturated monomer. For example, it may be a polymer produced from a monomer selected from tetrafluoroethylene (TFE), perfluoro(alkyl vinyl ether), hexafluoropropylene, etc., or one or more selected from these copolymers. The resin forming the shell may be a polymethyl methacrylate-based resin.

[0046] In one aspect, the polymer constituting the core part of the core-shell particles may be a polymer or copolymer containing 90% or more of a perfluorinated unsaturated monomer or containing all of it. The polymethyl methacrylate-based resin forming the shell may 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, 100% by weight of methyl methacrylate monomer.

[0047] Examples of the perfluorinated polymer forming the core part may be polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) / perfluoro(alkyl vinyl ether) copolymer (PFA), or TFE / hexafluoropropylene copolymer (FEP), but are not limited thereto. From the viewpoint of physical properties, a PTFE homopolymer is more preferable, but it is not limited to this.

[0048] In one aspect, the core substance may be synthesized. However, 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 carried out using the emulsifier of Chemical Formula 1, core-shell particles having significantly reduced aggregation properties and a uniform particle size of 100 to 500 nm, which are the objects of the present invention, can be obtained.

[0049] When the perfluorinated resin slurry is produced by polymerization, the perfluorinated unsaturated monomer and additives such as a polymerization initiator are appropriately mixed and can be produced by a conventional known method such as emulsion polymerization, solution polymerization, or suspension polymerization.

[0050] As the resin forming the shell, the methyl methacrylate resin is produced by 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. For example, one or more selected from acrylonitrile, vinyl acetate, styrene-based monomers, vinyl chloride, acrylate esters, vinylidene chloride, acrylic acid, methacrylic acid, etc. are preferable.

[0051] Next, the manufacturing method of the core-shell particles according to one aspect will be described.

[0052] The manufacturing method of the perfluororesin core-polymethyl methacrylate shell particles according to one aspect can be manufactured by adding the emulsifier of the following Chemical Formula 1 to the perfluorinated resin slurry solution for dispersion or emulsification, and then adding MMA or a monomer composition mainly composed of MMA for emulsion polymerization.

[0053] [Chemical Formula 1] R-(-O-C2H4-) n -OH (In the above formula, R is an alkyl group having 8 or more carbon atoms substituted with one or more alkyls, and n is an integer of 5 to 15.)

[0054] In one aspect, the R may be an alkyl group substituted with one or more alkyl groups of C8~C 30 of.

[0055] In Chemical Formula 1, when the ratio of the molecular weight of the hydrophilic oxyethylene group to the total molecular weight ([molecular weight of oxyethylene chain] / [total molecular weight]) is in the range of 0.5 to 1.0, it is more preferable because it has a lower aggregation energy value, but it is not limited thereto.

[0056] As an example, Chemical Formula 1 may be the following Chemical Formula 2.

[0057]

Chemical Formula

[0058] Hereinafter, the method for producing the core-shell particles will be specifically described.

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

[0060] All of the MMA or the monomer composition containing MMA as a main component may be charged and polymerized into the perfluorinated resin slurry before the start of polymerization, or the monomer or monomer composition may be charged and polymerized continuously or stepwise. However, continuous charging and polymerization are more preferable for size homogenization.

[0061] The emulsifier of Chemical Formula 1 may be used alone or in combination with other emulsifiers. However, using it alone is more preferable from the viewpoint of the effect of reducing the aggregation energy, but in terms of appropriately adjusting it, it may be used in combination.

[0062] The emulsifier may be continuously or intermittently charged into the perfluorinated resin particle slurry together with the monomer, or the emulsifier may be put in advance and the monomer may be charged.

[0063] The content of the emulsifier of Chemical Formula 1 may be used in an amount of 0.05 to 10 parts by weight, 0.1 to 6 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by mass of the particles composed of the perfluorinated polymer, but it is not limited to this depending on the size of the particles.

[0064] Also, in one aspect, during the emulsion polymerization, a chain transfer agent, a chelating agent, a pH adjuster, etc. may be added as necessary.

[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, and may be, for example, 0.001 to 2 parts by weight with respect to 100 parts by weight of the monomer or a mixture of monomers.

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

[0067] In one aspect, the core-shell slurry polymerized in the form of the core-shell may have a solids content of 5 to 60% by weight, 10 to 50% by weight, 20 to 40% by weight, or a value between these numbers, and is not limited thereto because it can be selected as needed.

[0068] In one aspect, the core-shell slurry is preferably an aqueous slurry. Needless to say, when it only means being dispersed in water, it is more environmentally friendly, but if necessary, it may further contain a solvent miscible with water. Such a mixed solvent may include 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, but is not limited thereto.

[0069] In one aspect, 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 a size between these numbers. The particle size of the particles having the above diameter can be confirmed by diluting the latex slurry after the polymerization is completed by 1,000 times and measuring the particle size and distribution by NICOMP 380 (Entegris, dynamic light scattering method).

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

[0071] In one aspect, the thickness of the shell layer may be 1 to 300 nm. Preferably, it is 5 to 200 nm, and more preferably, it may be 10 to 150 nm. When the thickness is as described above, it is preferable that dispersibility, low aggregability, and excellent electrical characteristics when used as a battery material 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 radius of the core to the thickness of the shell may be 1:0.01 to 1, or 1:0.05 to 0.6, but it is not particularly limited as long as the object of the present invention is achieved.

[0073] The core-shell particles can also be used as an electrode binder for secondary batteries, a processing fluidizing agent, or an emulsion paint.

[0074] Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are only one example for explaining 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 physical property evaluation method is as follows.

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

[0077] 2. Extraction method of non-fluorine resin 100 g of the slurry with the coincidence completed was placed in a 250 ml centrifuge tube and centrifuged at 9,000 rpm for 30 minutes. The separated supernatant was discarded, 100 g of acetone was added to the remaining solid content, and it was shaken with a shaker for 3 hours so that the non-fluorine-based resin was extracted with acetone. After shaking for 3 hours, it was further centrifuged at 9,000 rpm for 30 minutes. The fluorine-based resin was aggregated at the bottom, and the acetone supernatant in which the non-fluorine-based resin was dissolved was separated separately. The separated supernatant in which the non-fluorine-based resin was dissolved was dropped into 400 g of methanol to obtain the precipitated non-fluorine-based resin. The precipitated non-fluorine-based resin was separated by a vacuum filter, washed three times with methanol, placed in another beaker, and dried in an oven at 80 °C for 24 hours.

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

[0079] 4. Glass transition temperature (Tg) [°C] For the extracted non-fluorine-based resins of the slurries produced in the examples and comparative examples, after measuring 2 cycles under the temperature rising condition of 10 °C per minute by TA Q20 DSC (differential scanning calorimetry) respectively, the glass transition temperature was calculated by the half Cp method at the inflection point of the second cycle.

[0080] 5. Measurement of the ratio of the fluorine-based resin to the non-fluorine-based resin 15 g of the slurry with the polymerization completed was placed on an aluminum dish and dried in an oven at 80 °C. 10 mg of the dried powder was heated from room temperature to 600 °C at 10 °C per minute by TGA to measure the weight loss. Utilizing the characteristics of the non-fluorine-based resin that decomposes thermally first, the ratio of the fluorine-based resin to the non-fluorine-based resin was measured from the degree of weight loss.

[0081] 6. Measurement of Particle Size The latex after the completion of polymerization was diluted 1,000 times, and the particle size and distribution were measured by NICOMP 380 (Entegris, dynamic light scattering method).

[0082] 7. Measurement of Total Energy and Specific Energy of Fluidity The slurry after the completion of polymerization was freeze-dried and obtained in a powder state. The fluidity and agglomeration energy were measured by a powder rheometer FT4 of Freeman Technology. After filling the resin into a sample cylinder with a diameter of 50 mm, the total energy was measured 11 times while the impeller rotated and descended at a tip speed of 100 mm / s, and the agglomeration energy was measured while ascending. 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; when it was more than 10, it was judged as high cohesion. Both the total energy and specific energy were averaged from the measurement results up to 8 times as long as the equipment was operating normally.

[0083] 8. Analysis of Particle Structure (TEM / EDS) After plasma treatment on the grid for a transmission electron microscope (TEM), one drop of the slurry was dropped and then dried at room temperature. The dried sample was analyzed for its structure at an acceleration voltage of 200 kV by TEM / EDS (TECNAI TF20 of FEI).

[0084] [Example 1] A PTFE aqueous dispersion 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 was prepared. Next, 2448.0 g of the PTFE dispersion and 48.96 g of a 90% aqueous solution of polyethylene glycol trimethylnonyl ether with a molecular weight of 384 g / mol for the ethylene glycol repeating unit showing hydrophilicity were placed in a 4-liter reactor, and while stirring at a speed of 350 rpm, the temperature was raised to 75 °C while performing nitrogen bubbling.

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

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

[0087] The size of the white emulsion was analyzed by NiCOMP and described in Table 1, and the particle structure analysis results are shown in Figure 1. As shown in Figure 1, it can be seen that a polymethyl methacrylate shell is uniformly formed on the entire surface of the core, and the particle size is also very uniformly produced.

[0088] Also, the white powder was obtained by freeze-drying the emulsion under the conditions of -60 °C and 10 mTorr for 72 hours, and the measurement results of total energy and specific energy using it are described in Table 1. As a result, it can be seen that the Specific Energy (mJ / g) is 5.8, which is very low, and the total energy also shows 1150 mJ, which is very low compared to less than 2000 mJ, indicating that it is very excellent.

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

[0090] [Comparative Example 2] In Example 1, it was carried out using the same content except that sodium dodecyl benzene sulfonate was used as the emulsifier. TEM electron micrographs of the resulting aggregates are shown in Figures 2 and 3. As shown in Figure 2, particles were observed in an irregular form that did not surround the entire surface of the fluoropolymer with polymethyl methacrylate as the core, rather than in a core-shell form. Also, as shown in Figure 3, the particle size was irregular and not uniform, and the particle size was small. The results of analyzing the properties are shown in Table 1 below.

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

[0092] [Comparative Example 4] In Example 1, it was carried out in the same manner except that an emulsifier with a repeating unit of 3 for the ethylene glycol unit was used instead of the 90% aqueous solution of polyethylene glycol trimethyl nonyl ether mainly having a molecular weight of 384 g / mol for the ethylene glycol repeating unit. The results are shown in Table 1.

[0093]

Table 1

[0094] As can be seen from the above analysis results, in the case of the present invention, Example 1 has uniform particles as shown in FIG. 1 while having a particle size with a diameter of 260 nm, and it can be seen that the Specific Energy (mJ / g) is very low at 5.8. Also, the total energy is 1,150 mJ, which is very low compared to 2,000 mJ or less, indicating that it is very excellent.

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

Claims

1. To the perfluorinated resin particle slurry, a polyethylene glycol ether having an alkyl group of C or more substituted with one or more alkyls of the following chemical formula 1 is used as an emulsifier, and an acrylic monomer is emulsion polymerized to produce a composite core-shell particle slurry having a perfluorinated resin core-polymethyl methacrylate resin shell layer. ８ A composite core-shell particle slurry having a perfluorinated resin core-polymethyl methacrylate resin shell layer, which is produced by emulsion polymerization of an acrylic monomer using a polyethylene glycol ether having an alkyl group of C or more substituted with one or more alkyls of the following chemical formula 1 as an emulsifier. [Chemical formula 1] R-( -O-C ２ H ４ -) ｎ -OH (In the above formula, R is C substituted with one or more alkyls ８ alkyl groups or more, and n is an integer of 5 to 15.)

2. In the chemical formula 1, the ratio of the molecular weight of the oxyethylene group, which is a hydrophilic group, to the total molecular weight ([molecular weight of oxyethylene chain] / [total molecular weight]) is 0.5 to 1.

0. The composite core-shell particle slurry according to Claim 1.

3. The chemical formula 1 is an emulsifier of the following chemical formula 2. The composite core-shell particle slurry according to Claim 1. 【Chemical 1】

4. The perfluorinated resin particles are perfluorinated resin particles mainly composed of units derived from tetrafluoroethylene. The composite core-shell particle slurry according to Claim 1.

5. To a perfluorinated resin particle slurry, a polyethylene glycol ether having an alkyl group of C or more substituted with one or more alkyls of the following chemical formula 1 is used as an emulsifier, and an acrylic monomer is emulsion polymerized to produce a composite core-shell particle having a perfluorinated resin core-polymethyl methacrylate resin shell. ８ A composite core-shell particle having a perfluorinated resin core-polymethyl methacrylate resin shell, which is produced by emulsion polymerization of an acrylic monomer using a polyethylene glycol ether having an alkyl group of C or more substituted with one or more alkyls of the following chemical formula 1 as an emulsifier. [Chemical formula 1] R-( -O-C ２ H ４ -) ｎ -OH (In the above formula, R is C substituted with one or more alkyls ８ or more alkyl groups, and n is an integer of 5 to 15.)

6. The aggregation energy is 10 mJ / g or less. The composite core-shell particles according to Claim 5.

7. The total surface energy of the composite core-shell particles is 2,000 mJ or less. The composite core-shell particles according to Claim 5.

8. The average diameter of the core-shell particles is 100 to 500 nm. The composite core-shell particles according to Claim 5.

9. The weight of the core is 50 to 95 wt% of the total core-shell particles. The composite core-shell particles according to Claim 5.

10. An electrode produced from a formulation containing the core-shell particles according to any one of Claims 5 to 9 and an electrode active material.

11. A battery containing the core-shell particles according to any one of Claims 5 to 9 as a binder.

12. The composite core-shell particles having a perfluorinated resin core - polymethyl methacrylate-based resin shell have an aggregation energy of 10 mJ / g or less and a total surface energy of 2,000 mJ or less. The composite core-shell particles according to Claim 5.

13. The average diameter of the composite core-shell particles is 100 to 500 nm. The composite core-shell particles according to Claim 12.

14. The average diameter of the core of the composite core-shell particles is less than 50 to 500 nm, and the thickness of the shell is 1 to 300 nm. The composite core-shell particles according to Claim 13.

15. A formulation containing the particles according to any one of Claims 13 to 14.

16. A formulation according to Claim 15 containing an electrode active material.

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