WO2015093765A1 - Method for preparing aqueous binder for positive electrode active material of secondary battery - Google Patents

Method for preparing aqueous binder for positive electrode active material of secondary battery Download PDF

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Publication number
WO2015093765A1
WO2015093765A1 PCT/KR2014/011930 KR2014011930W WO2015093765A1 WO 2015093765 A1 WO2015093765 A1 WO 2015093765A1 KR 2014011930 W KR2014011930 W KR 2014011930W WO 2015093765 A1 WO2015093765 A1 WO 2015093765A1
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Prior art keywords
monomer
secondary battery
active material
aqueous binder
weight
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PCT/KR2014/011930
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French (fr)
Korean (ko)
Inventor
김동옥
김동욱
박혜란
공정호
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한화케미칼 주식회사
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Publication of WO2015093765A1 publication Critical patent/WO2015093765A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a binder for an aqueous secondary battery electrode excellent in silver conductivity, binding strength, and chemical resistance.
  • Lithium-ion secondary batteries are expanding their applications to portable electronic devices as well as power tools, automobiles, and industrial applications. Accordingly, binders are recognized as main members by requiring persistence in a much darker environment.
  • the binder is a member that binds between the active materials and bonds between the active materials and the electrodes, and has an important function of controlling the state in the manufacturing process.Binder also has excellent electrochemical properties because the binder is placed in an electrochemical harsh environment inside the battery. Properties and insolubility from the electrolyte are required.
  • a solvent-based binder in which vinylidene fluoride-based resin is largely dissolved in an organic solvent such as N-methyl-2-pyrrolidone (NMP: n-methyl-2-pyrol idne), and styrene / butadiene-based resin (SBR: Styrene-Butadiene-Rubber) or an aqueous binder in which polyacrylate is dispersed in water.
  • NMP N-methyl-2-pyrrolidone
  • SBR Styrene-Butadiene-Rubber
  • the battery performance is improved, and since the slurry can be made of water with less environmental load, the investment cost for the recovery cost of the organic solvent, the explosion-proof amount of the coating apparatus, etc. has been attracting much attention.
  • NMP Since the World Health Organization is concerned about teratogenicity and reproductive toxicity, it is considered that the development of aqueous binders is more important as it is an item that specifies the allowable concentration in lppm.
  • An object of the present invention is to provide a physical interaction or crosslinking of the binder and the positive electrode surface; And promoting physical interaction and crosslinking between the binder particles to provide a method for producing an aqueous binder for a secondary battery positive electrode active material having high binding strength and electrochemical stability with an electrode.
  • the present invention also provides a method for producing an aqueous binder for a positive electrode active material, which exhibits an inhibitory effect on the use of an emulsifier.
  • Another object of the present invention is to provide an aqueous binder for a secondary battery positive electrode active material prepared by the above method excellent in ion conductivity, binding strength and chemical resistance.
  • It provides a method of manufacturing an aqueous binder for a secondary battery positive electrode active material comprising a.
  • the polymerization of the first step and the second step may proceed in the presence of a polymerization initiator.
  • the C 1 monomer composition and the second monomer composition are each water; And emulsifiers, crosslinking agents or mixtures thereof.
  • the crosslinking agent is used in the first step and the crab step, or in the first step or Only one of twelve steps may be used.
  • the polymerization may be performed under conditions of a polymerization reaction temperature of 30 to 150 ° C. and a polymerization time of 0.1 hour to 10 hours.
  • the polymerization may proceed under conditions of a polymerization reaction temperature of 30 to 150 ° C. and a polymerization time of 0.5 hour to 24 hours.
  • the content of the acrylic monomer may be 30 to 90 parts by weight based on 100 parts by weight of the total weight of the first monomer composition or the second monomer composition, respectively.
  • the content of the ⁇ , ⁇ -saturated nitrile compound may be 1 to 50 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition or the crab dimer composition, respectively.
  • the content of the seed polymer may be 1 to 70 parts by weight based on 100 parts by weight of the layer weight of the crab dimer composition.
  • the emulsifier may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the crab monomer composition or the second monomer composition.
  • the content of the adhesion enhancing monomer may be 1 to 40 parts by weight based on 100 parts by weight of the total weight of the crab dimer composition.
  • the content of the crosslinking agent and the grafting agent may be 0.1 to 20 parts by weight based on 100 parts by weight of the layer weight of the second monomer composition.
  • the seed polymer may have a glass transition temperature (T g ) of -locrc to ioo ° c and an average particle diameter of 10 to 1500 kPa.
  • T g glass transition temperature
  • the acrylic monomer may be at least one selected from acrylic acid ester monomers having 4 to 20 carbon atoms and methacrylic acid ester monomers.
  • the ⁇ , ⁇ -unsaturated nitrile compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, nitrile chloride and nitrile fluoride.
  • the emulsifier is at least one compound selected from the group consisting of sodium 4-vinylbenzenesulfonate, sodium metaallylsulfonate, sodium allylsulfonate, sodium dodecylbenzenesulfonate and sodium vinylsulfonate, sodium lauryl Sulfate, sodium laureth sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, triethane may be one or more selected from the group consisting of amine lauryl sulfate and sodium tripolyphosphate.
  • the adhesion enhancing monomer is an unsaturated monocarboxylic acid monomer; Unsaturated dicarboxylic acid monomers; Acrylamide monomers; And it may be one or more selected from the group consisting of an epoxy monomer.
  • the crosslinking agent and the grafting agent are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate.
  • Acrylate polypropylene glycol dimethacrylate, polybutylene glycol diacrylate, 1,3-butadiol diacrylate, 1,3-butadiol dimethacrylate, 1,4-butadiol diacrylate, 1, 4-butadiol dimethacrylate, 1, 6-nucleic acid diol dimethacrylate, aryl acrylate, aryl methacrylate, triaryl isocyanurate, triaryl amine, diaryl amine, trimethylolpropane tri Methacrylate, trimethylolmethane triacrylate, styrene, ⁇ -methylstyrene, ⁇ -methyl It may be at least one selected from the group consisting of styrene, p-t'butylbutylstyrene and divinylbenzene.
  • the first monomer composition and the crab monomer composition may each further include one or more additives selected from the group consisting of a molecular weight regulator, a laxative and a wax.
  • the present invention is prepared by the above method, the glass transition temperature (Tg) is -10CTC to 10CTC, Interpenetrating Polymer Network IPN or Semi-interpenetrat ion Polymer Network (SIPN) It provides an aqueous binder for a secondary battery positive electrode active material having a structure of).
  • the aqueous binder may have an average particle diameter of 80 to 4000 nm.
  • seed polymer particles of desired physical properties are prepared through polymerization of monomer compositions including different polymers dispersed in water in the first step, and in the second step, additional monomers are provided to provide the required physical properties of the binder.
  • the present invention can make a slurry from water with a low environmental load when manufacturing an aqueous binder for a secondary battery positive electrode active material, and at the same time exhibits excellent binding capacity and electrochemical stability with an excellent electrode, which enables excellent layer discharge cycle characteristics and high capacity. Can be provided.
  • Figure 1 shows the adhesion test results of Examples 1 to 8 and Comparative Examples 1 to 3.
  • Figure 2 shows a comparison of the electrochemical life characteristics of Examples 1 to 8 and Comparative Examples 1 to 3.
  • Figure 3 shows a comparison of the electrochemical capacity characteristics of Examples 1 to 8 and Comparative Examples 1 to 3.
  • the emulsifier-free polymerization method described in the specification of this invention is a polymerization method in which an emulsifier is not used, and means the polymerization method of the monomer composition containing a polymerization initiator.
  • a method for producing an aqueous binder for a secondary battery positive electrode active material comprising; step 2 to prepare a binder particle by polymerization.
  • the first monomer composition and the crab dimer composition are each water; And emulsifiers, crosslinking agents or mixtures thereof.
  • the crosslinking agent may be used or only used to phase "and to step 21, or to any step of the steps 12 or I Step 1.
  • the present invention relates to a binder for a positive electrode active material of an aqueous secondary battery which is excellent in charge and discharge cycle characteristics and capable of high capacity, and furthermore, can be preferably used for a lithium ion secondary battery, and a novel method for producing the same.
  • the method of manufacturing an aqueous binder for a secondary battery positive electrode active material of the present invention proceeds in two steps, wherein the present invention includes preparing a seed polymer using different monomers, and growing the same to prepare aqueous binder particles. Characterized in that.
  • the present invention is to prepare the seed polymer particles of the desired physical properties through the polymerization in the first step, and in the second step to further add a monomer that provides the required physical properties of the binder to grow the seed polymer particles to finally cross-permeable polymer It characterized in that for producing the binder particles having the structure: (the SIPN semi-interpenetrat ion polymer network) -: network (Interpenetrat ing polymer network 'below IPN) or semi-cross-permeable polymer network.
  • the network structure is IPN, in which two or more polymers have a network of nets and are read from each other to create a new network. Is classified as a SIPN.
  • both the IPN and the SIPN structure may be included depending on whether the crosslinking agent is used in the first and second steps or only in one step. Therefore, in the present invention, in forming the above-described IPN or SIPN structure, the structure can be changed depending on whether the crosslinking agent is used in the first and second steps of the method for preparing the binder. For example, when both the crosslinking agent is used in the first step and the crab step of the binder manufacturing method, the IPN structure can be formed, and when the crosslinking agent is used in only one step, the SIPN structure can be formed.
  • the polymer network of the present invention has the advantage of not only having superior physical strength due to the characteristics of the molecular structure as described above, but also having the advantages and disadvantages of each polymer forming the network.
  • the water-based polymer binder according to the present invention forms a polymer network having an IPN or SIPN structure depending on the presence or absence of a crosslinking agent in the first or second stages of manufacture, and because of this structure, ion conductivity, binding strength and It can provide the effect which is excellent in chemical resistance.
  • the present invention relates to physical interaction or crosslinking of the binder and the positive electrode surface; And by promoting the physical interaction groups and crosslinking between the binder particles, it is possible to provide an aqueous binder for a secondary battery positive electrode active material having high binding strength and electrochemical stability with the electrode.
  • the present invention can also provide an inhibitory effect on the use of emulsifiers.
  • the emulsifier plays an important part in the emulsion polymerization because the emulsifier controls the particle size of the latex particles produced during the emulsion polymerization, giving colloidal stability to the polymer indenter.
  • the emulsifier when used in the aqueous binder, it is known that the emulsifier remaining after the electrode production adversely affects the battery characteristics such as poor binding force with the electrode.
  • the seed polymer and the binder are prepared by an emulsion-free polymerization method of the initiator alone, or an emulsion polymerization in which a specific additive or a general emulsifier which serves as an emulsifier is added.
  • a method capable of omitting the emulsifier in at least one of the first and second steps may be used. Therefore, when the emulsion polymerization in the present invention can be used to suppress the use of emulsifiers.
  • the present invention when the emulsifier is omitted in the first step and the crab step 2, it is possible to weed the seed polymer or binder particles through the polymerization of the monomer composition containing only the polymerization initiator.
  • the use of emulsifiers can be omitted in the crab step 1.
  • the present invention may produce seed polymers and binders through emulsion polymerization using particular additives or generally known emulsifiers that optionally act as emulsifiers.
  • the emulsion polymerization is possible, and all of the specific additives and general emulsifiers that act as emulsifiers will be described as emulsifiers.
  • the specific additive that acts as an emulsifier may be copolymerized with monomer compounds and at the same time serve as an emulsifier for emulsion polymerization.
  • Specific examples thereof include all compounds containing a salt in the terminal group, and more specific examples thereof include sodium 4-vinylbenzenesulfonate, sodium metaallylsulfonate, sodium allylsulfonate, sodium dodecylbenzenesulfonate, Sodium vinylsulfonate, and the like, but is not limited thereto.
  • the binder of the present invention using the specific additive as an emulsifier it was confirmed that compared with other binders in the prior art, more specifically, the adhesion between the electrode and the current collector and the thermal bonding property were excellent, and the battery characteristics were also excellent.
  • the general emulsifier may include all conventional components used in the emulsion polymerization, specific examples include sodium lauryl sulfate, sodium laureth sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, triethanolamine lauryl sulfate, and Selected from the group consisting of sodium tripolyphosphate
  • Such emulsifiers are used to determine the weight of the layer of the first monomer composition or the second monomer composition.
  • the first step of reaction is to prepare seed polymer particles through polymerization using an acrylic monomer and an ⁇ , ⁇ -unsaturated nitrile compound.
  • this first step includes the step of preparing a seed polymer by polymerizing a first monomer composition comprising an acrylic monomer and an ⁇ , ⁇ -unsaturated nitrile compound.
  • the emulsion-free polymerization method may be possible, and an emulsifier may be used if necessary.
  • the polymerization may be carried out in the presence of a polymerization initiator using the crab monomer monomer composition.
  • the system monomer composition is water; And emulsifiers, crosslinking agents or mixtures thereof. That is, since the present invention uses water as a reaction solvent for preparing seed polymer particles, the first monomer composition includes water.
  • the first monomer composition may be prepared by dispersing the two monomers in water and then adding an initiator dissolved in water. Therefore, the first and second emulsion-free polymerization methods described later may include a condensation polymerization method using water.
  • the crosslinking agent is used in both the first step and the second step described below.
  • the crosslinking agent when used in the first step to form the SIPN structure, the crosslinking agent may be omitted in the second step to be described later.
  • the first monomer composition may include a crosslinking agent together with water, and may optionally include an emulsifier.
  • the first step is a polymerization reaction temperature of 30 to 150 ° C, more preferably 50 to 90 ° C
  • the polymerization time is carried out under the conditions of 0.1 to 10 hours, more preferably 0.1 to 3 hours do.
  • the monomer constituting the seed polymer particles in the present invention may use a conventional monomer that can control the battery characteristics.
  • the seed polymer particles are formed by copolymerizing a monomer composition comprising an acrylic monomer and an ⁇ , ⁇ -unsaturated nitrile compound.
  • the acrylic monomer may be at least one selected from acrylic acid ester monomers having 4 to 20 carbon atoms and methacrylic acid ester monomers.
  • the acrylic ester monomer is an acrylic acid alkyl ester having 4 to 20 carbon atoms; Ether group-containing acrylic esters having 4 to 20 carbon atoms; And it may be at least one selected from the group consisting of; 4 to 20 hydroxy group containing acrylic acid ester having 4 to 20 carbon atoms.
  • the monomer of the methacrylic acid ester is methacrylic acid alkyl ester having 5 to 20 carbon atoms; Ether group-containing methacrylic acid esters having 5 to 20 carbon atoms; And it may be one or more selected from the group consisting of; hydroxy group-containing methacrylic acid ester having 5 to 20 carbon atoms.
  • acrylic ester monomer Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n -butyl acrylate, isobutyl acrylate, n- amyl acrylate, iso amyl acrylate, n-nuxyl acrylate, 2-ethylnuclear acryl
  • Acrylic acid alkyl esters such as acrylate, cyclonuclear acrylate, isopentyl acrylate, isooctyl acrylate, ibornyl acrylate, isodecyl acrylate and lauryl acrylate; Annealed ethyl acrylate, ethoxydiethylene glycol.
  • Ether group-containing acrylic esters such as acrylate, methoxydipropylene glycol acrylate, methoxypolyethylene glycol acrylate and phenoxyethyl acrylate; And hydroxyl group-containing acrylic esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate.
  • methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclonuclear methacrylate, 2 Methacrylic acid alkyl esters such as ethyl nucleosil methacrylate, isopentyl methacrylate, isooctyl methacrylate, isobornyl methacrylate, isodecyl methacrylate and lauryl methacrylate; Ether groups such as ethyl ethyl methacrylate, ethoxy diethylene glycol methacrylate, methoxydipropylene glycol methacrylate, methoxy polyethylene glycol, methacrylate, and phenoxyethyl methacrylate Containing methacrylic acid esters; And hydroxy group-containing methacrylic acid esters;
  • the ⁇ , ⁇ -unsaturated nitrile compound is preferably one or more selected from the group consisting of acrylonitrile, methacrylonitrile, nitrile chloride and nitrile fluoride.
  • the content of the acrylic monomer and the ⁇ , ⁇ -unsaturated nitrile compound used in the first step and the second step will be used based on the weight of the monomer composition constituting the seed polymer particles. Therefore, in the first step, the content of the acrylic monomer is 30 to 90 parts by weight, more preferably 50 to 80 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition. When the content of the acrylic monomer is less than 30 parts by weight, the binding force is lowered, and when it exceeds 80 parts by weight, the physical / chemical stability is lowered.
  • the content of the ⁇ , ⁇ -unsaturated nitrile compound is 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the layer weight of the first monomer composition. In this content range, ⁇ , ⁇ -saturated nitrile compounds should be used for excellent binding and battery characteristics of the obtained binder.
  • the polymerization initiator used in the present invention is a radical .
  • Any compound produced may be used, and specific examples thereof include, but are not limited to, ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, butyl hydroperoxide, or a combination thereof.
  • the content of the polymerization initiator is preferably used in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition.
  • the monomer component and the polymerization initiator in the first step of the reaction may be separately added to the mixture over a period of 3 hours simultaneously with the start of the total polymerization reaction time.
  • the monomer composition of the seed polymer particles may optionally contain a crosslinking agent and other monomers copolymerizable with the acrylic ester or methacrylic ester and the ⁇ , ⁇ -unsaturated nitrile compound. These may serve to adjust the gel content and molecular structure of the binder particles to increase the electrochemical stability of the binder.
  • the macromonomer composition of the present invention may further comprise the emulsifier mentioned above.
  • crosslinking agent and the grafting agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacryl. Latex, polyethylene glycol dimethacrylate, Polypropylene glycol dimethacrylate, polybutylene glycol diacrylate,
  • 1, 3-butadiol diacrylate, 1,3_butadiol dimethacrylate, 1,4-butadione diacrylate, 1,4-butadiol dimethacrylate, 1,6-nucleodiamide Acrylate, aryl acrylate, aryl methacrylate, triaryl isocyanurate, triaryl amine, diaryl amine, trimethyl to propane trimethacrylate, trimethylolmethane triacrylate, etc.
  • -Methyl styrene, ⁇ -methyl styrene, pt-butyl styrene, divinylbenzene, and the like but is not limited thereto. Moreover, these can be used individually or in combination of 2 or more types.
  • the emulsifier When the emulsifier is used in step C1, the emulsifier may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition.
  • the seed polymer particles of the present invention may use, in addition to the monomer components, a molecular weight regulator, a buffer (buf fer), a wax (wax), and the like which are conventional components known in the art as a polymerization additive. Moreover, these can be used individually or in combination of 2 or more types.
  • molecular weight modifier examples include t-dodecylmercaptan, n-dodecylmercaptan, n-octylmercaptan, and the like, but are not limited thereto.
  • the seed polymer prepared through the first step has a glass transition temperature (Tg) of -100 to 100 ° C, preferably -40 to 40 ° C.
  • Tg glass transition temperature
  • the glass transition temperature of the seed polymer affects the glass transition temperature of the binder to be produced later, the chemical stability is lower than the temperature below -40 ° C, the binding strength of the electrode is lowered above 40 ° C, peeling during electrode production Or cracks may occur.
  • the average particle diameter of the seed polymer particles is 10 to 1500 nm, more preferably 50 to 1000 nm.
  • the average particle diameter of the seed plymer also has a great influence on the average particle diameter of the aqueous binder to be produced later.
  • the second step of Banung is a step of finally producing a polymer particle having an IPN or SIPN structure by further polymerization using the seed polymer particles prepared in the above U step to be. In the second step, the polymerization proceeds after addition of the dimer composition to the seed polymer.
  • the bimer composition includes an acrylic monomer, ⁇ , ⁇ -unsaturated nitrile compound, adhesion enhancing monomer, and a crosslinking agent.
  • the macromer composition is also water; And emulsifiers, crosslinking agents or mixtures thereof.
  • the ⁇ structure can be formed.
  • an aqueous binder of SIPN structure can be prepared.
  • the second step may include an acrylic monomer, ⁇ , ⁇ -unsaturated nitrile compound, an adhesion enhancing monomer and a crosslinking agent in the seed polymer. Adding and polymerizing the composition to produce binder particles.
  • the present invention utilizes an adhesion enhancing monomer and a crosslinking agent together with two different monomers when growing the seed polymer. Physical interaction or crosslinking of the binder and the positive electrode surface; And it is possible to promote physical interaction groups and crosslinking between the binder particles, thereby improving the binding capacity of the binder with the electrode can improve the electrochemical stability of the battery.
  • the emulsion polymerization method In preparing the aqueous binder using the second monomer composition, in order to control the particle diameter of the aqueous binder polymer particles, the emulsion polymerization method is the easiest. In this case emulsifiers may be used.
  • the polymerization temperature is 30 to 150 ° C., more preferably 50 to 90 ° C.
  • the polymerization time is 0.5 to 24 hours, more preferably 1 to 12 hours.
  • the content of the seed polymer may be 1 to 70 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the layer weight of the second monomer composition.
  • the monomer used in the polymerization reaction of the second step is to satisfy the properties as a binder as mentioned in the first step, at least selected from acrylic ester monomers and methacrylic ester monomers It is made by copolymerizing at least one acrylic monomer with a monomer containing an ⁇ , ⁇ -unsaturated nitrile compound, an adhesion enhancing monomer, a crosslinking agent which forms a polymer network, and the like.
  • the acrylic monomers are the same as the monomers used in the preparation of the seed polymer, and may be used alone or in combination of two or more.
  • the content of the acrylic monomer is preferably 30 to 90 parts by weight, more preferably 40 to 80 parts by weight based on 100 parts by weight of the total weight of the second monomer composition.
  • ⁇ , ⁇ -unsaturated nitrile compound is also the same as the monomer used in the production of the seed puller particles, can be used alone or in combination of two or more.
  • the content of the ⁇ , ⁇ -unsaturated nitrile compound is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the layer increase of the crab dimer composition, In this case, the binder and the electrochemical properties of the resulting binder are excellent.
  • the adhesion enhancing monomer serves to cover the binding force between the metal used as an electrode and other subsidiary materials used in manufacturing the electrode through a functional group included in each.
  • the monomer used to increase the binding force through the ionic bond and covalent bond according to the characteristics of each functional group can be used alone or in combination of two or more.
  • the adhesion-enhancing monomer is a monomer for covering the binding force with the electrode, and specific examples thereof include acrylic acid, methacrylic acid, methylmethacrylic acid, and the like, which are unsaturated monocarboxylic acid monomers; Itaconic acid, fumaric acid, citraconic acid, metaconic acid, glutaconic acid, crotonic acid, etc. which are unsaturated dicarboxylic acid monomers; Acrylamide which is an acrylamide type monomer, (eta) -methylol acrylamide, (eta) -butoxymethyl acrylamide; Glycidyl methacrylate, which is an epoxy-based monomer, but is not limited thereto.
  • the content of the adhesion enhancing monomer is 1 to 40 parts by weight, more specifically 5 to 20 parts by weight, per 100 parts by weight of the total amount of the acrylic monomer and the ⁇ , ⁇ -unsaturated nitrile compound.
  • crosslinking agent that will form the polymer network may use the same material as the crosslinking agent used to prepare the seed polymer particles.
  • the content is preferably from 0.01 to 20 parts by weight, more specifically from 0.5 to 10 parts by weight, based on 100 parts by weight of the layer weight of the second monomer composition constituting the aqueous binder.
  • any compound that generates a radical may be used, and specific examples thereof are the same as in the first step.
  • the content of the polymerization initiator is preferably used in 0.1 to 5 parts by weight based on 100 parts by weight of the total weight of the second monomer composition.
  • the crab dimer composition may also include water.
  • the emulsifier may be the same as the material used to prepare the crab seed polymer particles, or may act as a monomer and at the same time act as an emulsifier, a compound thereof may be used.
  • the emulsifier is mixed with the monomers to prepare an emulsion, and then supply the binder for a predetermined reaction time.
  • the emulsifier When the emulsifier is used in the second step, the emulsifier may be used in 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the crab dimer composition.
  • the composition and the polymerization initiator of the reaction monomer components may be added separately.
  • the reaction component and the polymerization initiator are injected into the seed polymer at the same time, which can be dividedly added over 0.5-6 hours.
  • the second monomer composition may further include other monomers copolymerizable with the acrylic acid ester or methacrylic acid ester and ⁇ , ⁇ -unsaturated nitrile compounds, as in the case of preparing the seed polymer of the first stage.
  • the aqueous binder of the present invention may be used in addition to the monomer components, such as the crab seed seed polymer, molecular weight regulators, buf fers, waxes, and the like which are conventional components known in the art as polymerization additives. have.
  • the glass transition temperature (Tg) is ⁇ 100 ° C to 100 ° C
  • IPN Interpenetrating Polymer Network
  • SIPN semi- mutual permeability
  • Suitable glass transition temperature (Tg) of the aqueous binder of the present invention is -100 to lOCTC, more preferably -40 to 40 ° C. At this time, when the glass transition temperature of the water-based binder is less than -40 ° C, the chemical stability is lowered, and the binding force of the electrode is lowered at +40 ° C or more, which may cause peeling or cracking during electrode production.
  • the average particle diameter of the aqueous binder produced by the present invention is 80 to 4000 mm 3, more preferably 100 to 2000 nm.
  • the particle diameter of the aqueous binder has a great influence on the ionic conductivity and binding strength depending on the relative size with the size of the positive electrode active material used in electrode production.
  • the water-based binder prepared by the method of the present invention has a surface with the positive electrode surface. Interaction, crosslinking and interaction between the particles themselves, and the use of crosslinking agents and emulsifiers are suppressed to the maximum, which is suitable for use in secondary battery cathode active materials due to high binding strength and electrochemical stability.
  • crosslinking agents and emulsifiers are suppressed to the maximum, which is suitable for use in secondary battery cathode active materials due to high binding strength and electrochemical stability.
  • Distilled water 85g the reaction monomer 2- in the prepared seed polymer particles 77 g of ethyl nuclear acrylate, 12 g of acrylonitrile, 2.5 g of ethylene glycol dimethacrylate (EGDMA) and 3 g of itaconic acid (ITA), 5.5 g of acrylic acid (AA), sodium lauryl sulfate (SLA) O.lg While adding the mixed solution over 3 hours, 0.5 g of ammonium persulfate was dissolved in 20 g of distilled water.
  • EGDMA ethylene glycol dimethacrylate
  • ITA itaconic acid
  • AA acrylic acid
  • SLA sodium lauryl sulfate
  • the present invention obtained a binder of SIPN structure by using a crosslinking agent in the second step.
  • a binder was prepared by general emulsion polymerization.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Monomer Vine Vine Vine Vine Vine Vine Seed Seed Seed Seed Seed Seed Seed Seed Seed
  • APS ammonium persulfate
  • SLS sodium lauryl sulfate
  • SVS sodium 4-vinylbenzenesulfonate
  • SDBS sodium dodecylbenzenesulfonate
  • 2EHA 2-ethylnuclear chamber.
  • Acrylate BA is butyl acrylate
  • AN acrylonitrile
  • EGDMA ethylene glycol dimethacrylate
  • ITA itaconic acid
  • M acrylic acid
  • MA methacrylic acid
  • the electrode was attached to the cellophane tape in a rectangular shape having a width of 1.5 cm and a length of 21 cm. Then, the current collector was peeled off and 180 ° peel strength was measured. Evaluation was made into the average value by measuring three or more peeling strengths. The results are shown in FIG.
  • a coin-type battery was manufactured to evaluate the capacity and life characteristics of the electrodes of Examples and Comparative Examples.

Abstract

The present invention relates to a method for preparing an aqueous binder for a positive electrode active material of a secondary battery. More specifically, according to the present invention, a seed polymer is prepared while the use amount of an emulsifier is minimized, and such a seed polymer is grown to prepare polymer particles having an interpenetrating polymer network structure or a semi-interpenetrating polymer network, thereby providing an aqueous binder for a positive electrode active material of a secondary battery, which is an aqueous binder using water having a small environmental load and has more excellent binding strength and electrochemical stability.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
이차전지 양극활물질용 수계 바인더의 제조방법  Manufacturing Method of Aqueous Binder for Secondary Battery Cathode Active Material
【기술분야】  Technical Field
본 발명은 이은전도도, 결착력 및 내화학성이 우수한 수계 이차전지 전극용 바인더의 제조방법에 관한 것이다.  The present invention relates to a method for producing a binder for an aqueous secondary battery electrode excellent in silver conductivity, binding strength, and chemical resistance.
【발명의 배경이 되는 기술】  [Technique to become background of invention]
리튬이온 이차전지는 휴대형 전자기기뿐만 아니라 전동공구， 자동차 및 산업용 등으로 응용범위가 확대되고 있다. 이에 따라 훨씬 더 가흑한 환경에서의 지속성이 요구됨으로써 바인더가 주요 부재로 인식되고 있다.  Lithium-ion secondary batteries are expanding their applications to portable electronic devices as well as power tools, automobiles, and industrial applications. Accordingly, binders are recognized as main members by requiring persistence in a much darker environment.
바인더는 활물질 사이를 결착시키고 활물질과 전극 사이를 접착시키는 역할을 하는 부재이자 제조공정에서 상태를 제어하는 중요한 기능도 가지고 있다ᅳ 또한 바인더는 전지 내부에서 전기화학적으로 가혹한 환경 하에 놓이게 되기 때문에 우수한 전기화학적 특성과 전해액으로부터의 불용성이 요구된다.  The binder is a member that binds between the active materials and bonds between the active materials and the electrodes, and has an important function of controlling the state in the manufacturing process.Binder also has excellent electrochemical properties because the binder is placed in an electrochemical harsh environment inside the battery. Properties and insolubility from the electrolyte are required.
바인더는 이차전지에서 전체■ 재료의 1 Wt . % 정도이며 제조원가 역시 전체의 1% 미만이지만， 이에 의해 전지 성능이 크게 변화한다는 사실이 최근 연구로 밝혀지고 있다. 즉 지금까지는 리튬이온 이차전지의 특성 향상을 위하여 전해액, 분리막, 양극활물질 및 음극활물질 등의 주요 4대 소재들에 대한 연구가 주를 이루고 있었으며， 이들 4대 소재들의 특성 및 조합에 따라 전지의 특성이 변화한다고 알려져 왔다. 그러나 최근의 연구에 의하면 그 동안 4대 소재들의 특성 및 조합에 따른 효과로 해석되어 왔던 많은 전지 특성들이 전해액 및 양 (음)극활물질과 바인더의 조합에 의한 효과일 수도 있다는 주장이 제기되고 있다. ■ 1 Wt binder full of materials in secondary batteries. Although it is about% and manufacturing cost is less than 1% of the total, recent research shows that the battery performance is greatly changed by this. That is, until now, research on major four materials such as electrolyte, separator, positive electrode active material and negative electrode active material has been mainly conducted to improve the characteristics of the lithium ion secondary battery, and the characteristics of the battery according to the characteristics and combination of these four materials This has been known to change. However, recent research suggests that many battery characteristics, which have been interpreted as effects of the four materials and their combinations, may be due to the combination of an electrolyte and a positive electrode active material and a binder.
상기 양극활물질용 바인더의 경우 크게 불화비닐리덴계 수지를, N-메틸- 피를리돈 (NMP : n-methyl-2-pyrol idne) 등의 유기 용매에 용해한 용제계통 바인더와, 스티렌 /부타디엔계 수지 (SBR: Styrene-Butadiene-Rubber ) 또는 폴리아크릴레이트를 물에 분산시킨 수계 바인더로 나뉜다.  In the case of the binder for the positive electrode active material, a solvent-based binder in which vinylidene fluoride-based resin is largely dissolved in an organic solvent such as N-methyl-2-pyrrolidone (NMP: n-methyl-2-pyrol idne), and styrene / butadiene-based resin (SBR: Styrene-Butadiene-Rubber) or an aqueous binder in which polyacrylate is dispersed in water.
상기 수계 바인더의 경우 전지 성능을 향상시키고 환경부하가 적은 물로 슬러리를 만들 수 있어 유기용제의 회수비용， 코팅기기의 방폭 양 등에 대한 투자비용을 감소시킬 수 있기 때문에 최근 많은 관심을 받고 있다. 특히 NMP는 세계 보건기구 등에서 최기형성과 생식독성 등을 우려하고 있어 관리 허용농도를 lppm으로 규정하고 있는 품목이기에 수계 바인더의 개발이 더욱더 중요하다고 판단된다. In the case of the water-based binder, the battery performance is improved, and since the slurry can be made of water with less environmental load, the investment cost for the recovery cost of the organic solvent, the explosion-proof amount of the coating apparatus, etc. has been attracting much attention. Especially NMP Since the World Health Organization is concerned about teratogenicity and reproductive toxicity, it is considered that the development of aqueous binders is more important as it is an item that specifies the allowable concentration in lppm.
하지만， 아직까지 전극과의 결착력과 전기화학적 성능이 모두 우수한 이차전지 양극활물질용 수계 바인더의 개발이 원활이 이루어지지 않고 있다.  However, the development of an aqueous binder for secondary battery positive electrode active materials, which is excellent in both binding capacity with electrodes and electrochemical performance, has not been made smoothly.
【발명의 내용】 [Content of invention]
【해결하고자 하는 과제】  Problem to be solved
본 발명의 목적은 바인더와 양극제 표면과의 물리적 상호 작용이나 가교; 및 바인더 입자 간의 물리적 상호 작용이나 가교를 촉진함으로써， 전극과의 결착력과 전기화학적 안정성이 높은 이차전지 양극활물질용 수계 바인더의 제조방법을 제공하는 것이다.  An object of the present invention is to provide a physical interaction or crosslinking of the binder and the positive electrode surface; And promoting physical interaction and crosslinking between the binder particles to provide a method for producing an aqueous binder for a secondary battery positive electrode active material having high binding strength and electrochemical stability with an electrode.
' 본 발명은 또한 유화제 사용의 억제 효과를 나타내는 양극활물질용 수계 바인더의 제조방법을 제공하는 것이다. The present invention also provides a method for producing an aqueous binder for a positive electrode active material, which exhibits an inhibitory effect on the use of an emulsifier.
본 발명의 다른 목적은 상기 방법으로 제조되어 이온전도도， 결착력 및 내화학성이 우수한 이차전지 양극활물질용 수계 바인더를 제공하는 것이다.  Another object of the present invention is to provide an aqueous binder for a secondary battery positive electrode active material prepared by the above method excellent in ion conductivity, binding strength and chemical resistance.
【과제의 해결 수단】 [Measures of problem]
상기 목적을 달성하기 위해ᅳ 본 발명은  In order to achieve the above object ᅳ
(a) 아크릴계 단량체 및 α β -불포화 나이트릴 화합물을 포함하는 거 U 단량체 조성물을 중합하여 시드 폴리머를 제조하는 게 1단계; 및  (a) polymerizing a U monomer composition comprising an acrylic monomer and an α β -unsaturated nitrile compound to prepare a seed polymer; And
(b) 상기 시드 폴리머에， 아크릴계 단량체， α , β -불포화 나이트릴 화합물 및 접착력 강화 단량체를 포함하는 제 2 단량체 조성물을 첨가하고 중합하여 바인더 입자를 제조하는 게 2단계 ;  (b) adding a second monomer composition comprising an acrylic monomer, an α, β-unsaturated nitrile compound, and an adhesion enhancing monomer to the seed polymer, followed by polymerization to prepare binder particles;
를 포함하는 이차전지 양극활물질용 수계 바인더의 제조방법을 제공한다. 상기 게 1 단계 및 제 2 단계의 중합은 중합 개시제의 존재 하에 진행될 수 있다.  It provides a method of manufacturing an aqueous binder for a secondary battery positive electrode active material comprising a. The polymerization of the first step and the second step may proceed in the presence of a polymerization initiator.
상기 게 1 단량체 조성물 및 제 2단량체 조성물은 각각 물; 및 유화제, 가교제 또는 이들의 흔합물；을 더 포함할 수 있다.  The C 1 monomer composition and the second monomer composition are each water; And emulsifiers, crosslinking agents or mixtures thereof.
상기 가교제는 제 1단계 및 게 2단계에서 사용되거나， 또는 제 1단계 또는 거 12단계 중 어느 한 단계에서만 사용될 수 있다. The crosslinking agent is used in the first step and the crab step, or in the first step or Only one of twelve steps may be used.
상기 게 1단계는 중합 반응 온도 30 내지 150°C 및 중합시간 0. 1시간 내지 10 시간의 조건에서 중합을 진행할 수 있다. In the first step, the polymerization may be performed under conditions of a polymerization reaction temperature of 30 to 150 ° C. and a polymerization time of 0.1 hour to 10 hours.
상기 게 2단계는 중합 반응 온도 30 내지 150 °C 및 중합시간 0.5시간 내지 24 시간의 조건에서 중합을 진행할 수 있다. In the second step, the polymerization may proceed under conditions of a polymerization reaction temperature of 30 to 150 ° C. and a polymerization time of 0.5 hour to 24 hours.
또한， 상기 게 1단계 및 게 2단계에서, 상기 아크릴계 단량체의 함량은 각각 제 1단량체 조성물 또는 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 30 내지 90 중량부일 수 있다.  In addition, in the crab step 1 and crab step 2, the content of the acrylic monomer may be 30 to 90 parts by weight based on 100 parts by weight of the total weight of the first monomer composition or the second monomer composition, respectively.
상기 제 1단계 및 제 2단계에서， 상기 α , β -블포화 나이트릴 화합물의 함량은 각각 제 1단량체 조성물 또는 게 2단량체 조성물의 층 중량의 100 중량부를 기준으로 1 내지 50 중량부일 수 있다.  In the first step and the second step, the content of the α, β-saturated nitrile compound may be 1 to 50 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition or the crab dimer composition, respectively.
상기 제 2단계에서， 상기 시드 폴리머의 함량은 게 2단량체 조성물의 층 중량의 100 중량부를 기준으로 1 내지 70 중량부일 수 있다.  In the second step, the content of the seed polymer may be 1 to 70 parts by weight based on 100 parts by weight of the layer weight of the crab dimer composition.
상기 게 1단계 및 제 2단계에서ᅳ 상기 유화제는 게 1단량체 조성물 또는 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 0.01 내지 5 중량부로 사용할 수 있다.  In the first and second steps of the crab, the emulsifier may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the crab monomer composition or the second monomer composition.
상기 접착력 강화 단량체의 함량은 게 2단량체 조성물의 충 중량의 100 중량부를 기준으로 1 내지 40 중량부일 수 있다.  The content of the adhesion enhancing monomer may be 1 to 40 parts by weight based on 100 parts by weight of the total weight of the crab dimer composition.
상기 가교제 및 그래프팅 에이전트의 함량은 제 2단량체 조성물의 층 중량의 100 중량부를 기준으로 0. 1 내지 20 중량부일 수 있다.  The content of the crosslinking agent and the grafting agent may be 0.1 to 20 parts by weight based on 100 parts by weight of the layer weight of the second monomer composition.
또한 상기 시드 폴리머는 유리전이온도 (Tg)가 -locrc 내지 ioo°c이고， 평균 입자 직경이 10 내지 1500誦일 수 있다. In addition, the seed polymer may have a glass transition temperature (T g ) of -locrc to ioo ° c and an average particle diameter of 10 to 1500 kPa.
상기 아크릴계 단량체는 탄소수 4 내지 20의 아크릴산 에스테르계 단량체 및 메타크릴산 에스테르계 단량체 중에서 선택되는 1종 이상일 수 있다.  The acrylic monomer may be at least one selected from acrylic acid ester monomers having 4 to 20 carbon atoms and methacrylic acid ester monomers.
상기 α , β -불포화 나이트릴 화합물은 아크릴로나이트릴, 메타크릴로나이트릴， 염화나이트릴 및 플루오르화나이트릴로 이루어진 군에서 선택된 1종 이상일 수 있다.  The α, β-unsaturated nitrile compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, nitrile chloride and nitrile fluoride.
상기 유화제는 소디움 4-비닐벤젠술포네이트， 소디움 메타알릴술포네이트， 소디움 알릴술포네이트， 소디움 도데실벤젠술포네이트 및 소디움 비닐술포네이트로 이루어진 군에서 선택된 1종 이상의 화합물, 소디움 라우릴 설페이트, 소디움 라우레스 설페이트， 암모늄 라우릴 설페이트， 암모늄 라우레스 설페이트， 트리에탄을아민 라우릴 설페이트 및 소디움 트라이폴리포스페이트로 이루어진 군에서 선택된 1종 이상일 수 있다. The emulsifier is at least one compound selected from the group consisting of sodium 4-vinylbenzenesulfonate, sodium metaallylsulfonate, sodium allylsulfonate, sodium dodecylbenzenesulfonate and sodium vinylsulfonate, sodium lauryl Sulfate, sodium laureth sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, triethane may be one or more selected from the group consisting of amine lauryl sulfate and sodium tripolyphosphate.
상기 접착력 강화 단량체는 불포화 모노카르본산계 단량체; 불포화 디카르본산계 단량체; 아크릴아미드계 단량체; 및 에폭시계 단량체로 이루어진 군에서 선택된 1종 이상일 수 있다.  The adhesion enhancing monomer is an unsaturated monocarboxylic acid monomer; Unsaturated dicarboxylic acid monomers; Acrylamide monomers; And it may be one or more selected from the group consisting of an epoxy monomer.
상기 가교제 및 그래프팅 에이전트는 에틸렌 글리콜 디메타크릴레이트， 디에틸렌 글리콜 디메타크릴테이트， 트리에틸렌 글리콜 디메타크릴레이트， 테트라에틸렌글리콜 디아크릴레이트， 테트라에틸렌글리콜 디메타크릴레이트， 폴리 에틸렌 글리콜 디메타크릴에이트， 폴리 프로필렌 글리콜 디메타크릴레이트， 폴리 부틸렌 글리콜 디아크릴레이트， 1 , 3-부타디을 디아크릴레이트， 1 , 3- 부타디을 디메타크릴레이트， 1 , 4-부타디올 디아크릴레이트， 1 , 4-부타디올 디메타크릴레이트， 1 , 6-핵산디올 디메타크릴레이트， 아릴 아크릴레이트， 아릴 메타크릴레이트， 트리아릴 이소시아누레이트， 트리아릴 아민, 디아릴 아민, 트리메틸올프로판 트리메타크릴레이트， 트리메틸올메탄 트리아크릴레이트， 스티렌， α -메틸스티렌， β -메틸스티렌， p-tᅳ부틸스티렌 및 디비닐벤젠으로 이루어진 군에서 선택된 1종 이상일 수 있다.  The crosslinking agent and the grafting agent are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate. Acrylate, polypropylene glycol dimethacrylate, polybutylene glycol diacrylate, 1,3-butadiol diacrylate, 1,3-butadiol dimethacrylate, 1,4-butadiol diacrylate, 1, 4-butadiol dimethacrylate, 1, 6-nucleic acid diol dimethacrylate, aryl acrylate, aryl methacrylate, triaryl isocyanurate, triaryl amine, diaryl amine, trimethylolpropane tri Methacrylate, trimethylolmethane triacrylate, styrene, α-methylstyrene, β-methyl It may be at least one selected from the group consisting of styrene, p-t'butylbutylstyrene and divinylbenzene.
상기 제 1 단량체 조성물 및 게 2 단량체 조성물은 각각 분자량 조절제, 완층제 및 왁스로 이루어진 군에서 선택된 1종 이상의 첨가제를 더 포함할 수 있다.  The first monomer composition and the crab monomer composition may each further include one or more additives selected from the group consisting of a molecular weight regulator, a laxative and a wax.
또한 본 발명은 상기 방법으로 제조되며, 유리전이온도 (Tg)가 -10CTC 내지 10CTC인， 상호 침투성 고분자 네트워크 ( Interpenetrat ing Polymer Network IPN) 또는 세미 -상호 침투성 고분자 네트워크 (Seini-interpenetrat ion Polymer Network: SIPN)의 구조를 갖는 이차전지 양극활물질용 수계 바인더를 제공한다. 상기 수계 바인더는 평균 입자 직경이 80 내지 4000nm일 수 있다.  In addition, the present invention is prepared by the above method, the glass transition temperature (Tg) is -10CTC to 10CTC, Interpenetrating Polymer Network IPN or Semi-interpenetrat ion Polymer Network (SIPN) It provides an aqueous binder for a secondary battery positive electrode active material having a structure of). The aqueous binder may have an average particle diameter of 80 to 4000 nm.
【발명의 효과】 【Effects of the Invention】
본 발명의 방법은 제 1단계에서 물에 분산된 서로 다른 중합체를 포함한 단량체 조성물의 중합을 통하여 원하는 물성의 시드 폴리머 입자를 제조하고， 게 2단계에서는 바인더의 필요한 물성을 제공하는 단량체를 추가로 투입하여 시드 폴리머 입자를 성장시켜서 최종적으로 상호 침투성 ' 고분자 네트워크 ( Interpenetrat ing Polymer Network: IPN) 또는 세미 -상호 침투성 고분자 네트워크 (Semi-interpenetrat km Polymer Network : SIPN)의 구조를 갖는 고분자 입자를 제조한다. 이에 따라， 본 발명은 이차전지 양극활물질용 수계 바인더 제조시 환경 부하가 적은 물로 슬러리를 만들 수 있으면서, 동시에 우수한 전극과의 결착력 및 전기화학적 안정성을 나타내어 우수한 층방전 사이클 특성과 고용량화가 가능한 수계 이차전지를 제공할 수 있다. In the method of the present invention, seed polymer particles of desired physical properties are prepared through polymerization of monomer compositions including different polymers dispersed in water in the first step, and in the second step, additional monomers are provided to provide the required physical properties of the binder. Seed by Growing polymer particles by finally cross-permeable, polymer network (Interpenetrat ing Polymer Network: IPN) or semi-cross-permeable polymer network: to produce a polymer particle having a structure of (Semi-interpenetrat km Polymer Network SIPN ). Accordingly, the present invention can make a slurry from water with a low environmental load when manufacturing an aqueous binder for a secondary battery positive electrode active material, and at the same time exhibits excellent binding capacity and electrochemical stability with an excellent electrode, which enables excellent layer discharge cycle characteristics and high capacity. Can be provided.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 실시예 1 내지 8 및 비교예 1 내지 3의 접착력 테스트 결과를 나타낸 것이다.  Figure 1 shows the adhesion test results of Examples 1 to 8 and Comparative Examples 1 to 3.
도 2는 실시예 1 내지 8 및 비교예 1 내지 3의 전기화학적 수명 특성을 비교하여 나타낸 것이다.  Figure 2 shows a comparison of the electrochemical life characteristics of Examples 1 to 8 and Comparative Examples 1 to 3.
도 3은 실시예 1 내지 8 및 비교예 1 내지 3의 전기화학적 용량 특성을 비교하여 나타낸 것이다.  Figure 3 shows a comparison of the electrochemical capacity characteristics of Examples 1 to 8 and Comparative Examples 1 to 3.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
이하에서， 본 발명을 보다 상세히 설명한다.  Hereinafter, the present invention will be described in more detail.
먼저， 본 발명의 명세서에서 사용되는 기술 용어 및 과학용어에 있어서 다른 정의가 없다면， 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가진다. 또한 종래와 동일한 기술적 구성 및 작용에 대한 반복적인 설명은 생략하기로 한다.  First, unless there is another definition in the technical terms and scientific terms used in the specification of the present invention, it has a meaning commonly understood by those skilled in the art. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.
또한， 본 발명의 명세서에서 기재된 무유화제 중합방법은 유화제가 사용되지 않는 중합 방법으로서， 중합개시제를 포함한 단량체 조성물의 중합 방법을 의미한다 . 발명의 일 구현예에 따라， (a) 아크릴계 단량체 및 α , β -불포화 나이트릴 화합물를 포함하는 게 1 단량체 조성물을 중합하여 시드 폴리머를 제조하는 제 1단계; 및 (b) 상기 시드 폴리머에， 아크릴계 단량체， α , β -불포화 나이트릴 화합물 및 접착력 강화 단량체를 포함하는 게 2 단량체 조성물을 첨가하고 중합하여 바인더 입자를 제조하는 게 2단계;를 포함하는 이차전지 양극활물질용 수계 바인더의 제조방법이 제공된다. In addition, the emulsifier-free polymerization method described in the specification of this invention is a polymerization method in which an emulsifier is not used, and means the polymerization method of the monomer composition containing a polymerization initiator. According to one embodiment of the invention, (a) a first step of preparing a seed polymer by polymerizing a monomer composition comprising an acrylic monomer and α, β-unsaturated nitrile compound; And (b) an acrylic monomer, an α, β-unsaturated nitrile compound and an adhesion enhancing monomer in the seed polymer. Provided is a method for producing an aqueous binder for a secondary battery positive electrode active material comprising; step 2 to prepare a binder particle by polymerization.
상기 제 1 단량체 조성물 및 게 2단량체 조성물은 각각 물; 및 유화제， 가교제 또는 이들의 흔합물；을 더 포함할 수 있다.  The first monomer composition and the crab dimer composition are each water; And emulsifiers, crosslinking agents or mixtures thereof.
상기 가교제는 게 1단계 '및 게 2단계에서 사용되거나， 또는 게 1단계 또는 거 12단계 중 어느 한 단계에서만 사용될 수 있다. The crosslinking agent may be used or only used to phase "and to step 21, or to any step of the steps 12 or I Step 1.
_ 본 발명은 충방전 사이클 특성이 우수하고 고용량화가 가능한 수계 이차전지， 더 나아가서는 리튬 이온 이차전지에 바람직하게 사용할 수 있는 수계 이차전지의 양극 활물질용 바인더 및 신규한 그의 제조 방법에 관한 것이다. 본 발명의 이차전지 양극활물질용 수계 바인더의 제조 방법은, 2단계로 진행되며， 이때 본 발명은 서로 다른 단량체를 사용하여 시드 폴리머를 제조한 후， 이를 성장시켜 수계 바인더 입자를 제조하는 단계를 포함하는 것을 특징으로 한다.  _ The present invention relates to a binder for a positive electrode active material of an aqueous secondary battery which is excellent in charge and discharge cycle characteristics and capable of high capacity, and furthermore, can be preferably used for a lithium ion secondary battery, and a novel method for producing the same. The method of manufacturing an aqueous binder for a secondary battery positive electrode active material of the present invention proceeds in two steps, wherein the present invention includes preparing a seed polymer using different monomers, and growing the same to prepare aqueous binder particles. Characterized in that.
또한， 본 발명은 게 1단계에서 중합을 통하여 원하는 물성의 시드 폴리머 입자를 제조하고， 제 2단계에서는 바인더의 필요한 물성을 제공하는 단량체를 추가로 투입하여 시드 폴리머 입자를 성장시켜서 최종적으로 상호 침투성 고분자 네트워크 ( Interpenetrat ing Polymer Network'： 이하 IPN) 또는 세미 -상호 침투성 고분자 네트워크 (Semi-interpenetrat ion Polymer Network: 이하 SIPN)의 구조를 갖는 바인더 입자를 제조하는 것을 특징으로 한다. In addition, the present invention is to prepare the seed polymer particles of the desired physical properties through the polymerization in the first step, and in the second step to further add a monomer that provides the required physical properties of the binder to grow the seed polymer particles to finally cross-permeable polymer It characterized in that for producing the binder particles having the structure: (the SIPN semi-interpenetrat ion polymer network) -: network (Interpenetrat ing polymer network 'below IPN) or semi-cross-permeable polymer network.
고분자 입자 제조시 그 네트워크 구조는， 두 종류 또는 그 이상의 고분자가 모두 그물형의 네트워크를 가지고 서로 읽혀 새로운 네트워크를 만드는 경우인 IPN과， 하나의 고분자만이 그물형 네트워크를 가지고 서로 얽혀 새로운 네트워크를 만든 경우인 SIPN 로 분류된다.  When manufacturing polymer particles, the network structure is IPN, in which two or more polymers have a network of nets and are read from each other to create a new network. Is classified as a SIPN.
그런데, 본 발명에 따르면， 1단계 및 2단계에서 가교제가 모두 사용되는지 아니면 하나의 단계에서만 사용되는지에 따라 IPN과 SIPN 구조를 모두 포함할 수 있다. 그러므로， 본 발명은 상술한 IPN 또는 SIPN 구조를 형성하는데 있어서, 바인더의 제조 방법의 게 1단계 및 게 2단계에서 가교제의 사용여부에 따라 구조를 변경 가능하다. 예를 들어， 바인더 제조 방법의 제 1단계 및 게 2단계에서 가교제가 모두 사용될 경우 IPN 구조를 형성할 수 있고, 어느 한 단계에만 가교제가 사용될 경우에는 SIPN 구조를 형성할 수 있다. 본 발명의 고분자 네트워크는 상기와 같은 분자구조의 특징으로 인해 기존 보다 우수한 물리적 강도를 가질 뿐만 아니라， 네트워크를 형성하는 각 고분자들의 장단점이 효율적으로 보완된다는 장점이 있다. 또한 본 발명에 따른 수계 고분자 바인더는 1단계 또는 2단계 제조시의 가교제에 유무에 따라 IPN 또는 SIPN 구조의 고분자 네트워크를 형성하며， 이 구조로 인해 이차전지 양극활물질의 바인더로 사용시 이온전도도， 결착력 및 내화학성이 우수한 효과를 제공할 수 있다. However, according to the present invention, both the IPN and the SIPN structure may be included depending on whether the crosslinking agent is used in the first and second steps or only in one step. Therefore, in the present invention, in forming the above-described IPN or SIPN structure, the structure can be changed depending on whether the crosslinking agent is used in the first and second steps of the method for preparing the binder. For example, when both the crosslinking agent is used in the first step and the crab step of the binder manufacturing method, the IPN structure can be formed, and when the crosslinking agent is used in only one step, the SIPN structure can be formed. The polymer network of the present invention has the advantage of not only having superior physical strength due to the characteristics of the molecular structure as described above, but also having the advantages and disadvantages of each polymer forming the network. In addition, the water-based polymer binder according to the present invention forms a polymer network having an IPN or SIPN structure depending on the presence or absence of a crosslinking agent in the first or second stages of manufacture, and because of this structure, ion conductivity, binding strength and It can provide the effect which is excellent in chemical resistance.
특히， 본 발명은 바인더와 양극제 표면과의 물리적 상호 작용이나 가교; 및 바인더 입자 간의 물리적 상호 작용기나 가교를 촉진함으로써， 전극과의 결착력과 전기화학적 안정성이 높은 이차전지 양극활물질용 수계 바인더의 제공할 수 있다.  In particular, the present invention relates to physical interaction or crosslinking of the binder and the positive electrode surface; And by promoting the physical interaction groups and crosslinking between the binder particles, it is possible to provide an aqueous binder for a secondary battery positive electrode active material having high binding strength and electrochemical stability with the electrode.
또한 본 발명은 유화제 사용의 억제 효과도 제공할 수 있다. 구체적으로 설명하면， 일반적으로 유화제는 유화중합 시 생성되는 라텍스 입자의 입경을 제어하여， 폴리머 압자에 콜로이드 안정성을 주기 때문에 유화 중합에 중요한 부재 역할을 한다. 그러나， 수계 바인더에 유화제를 사용시， 전극 제조 후 잔존한 유화제로 인하여 전극과의 결착력이 떨어지는 등의 전지 특성에 악영향을 미치는 것으로 알려져 있다.  The present invention can also provide an inhibitory effect on the use of emulsifiers. Specifically, the emulsifier plays an important part in the emulsion polymerization because the emulsifier controls the particle size of the latex particles produced during the emulsion polymerization, giving colloidal stability to the polymer indenter. However, when the emulsifier is used in the aqueous binder, it is known that the emulsifier remaining after the electrode production adversely affects the battery characteristics such as poor binding force with the electrode.
그러므로, 본 발명에서는 상기 종래 문제점을 해결하기 위해， 개시제 단독의 무유화제 증합방법 또는 유화제 역할을 하는 특정 첨가제나 일반 유화제를 첨가한 유화 중합으로 시드 폴리머와 바인더를 제조한다. 바람직하게, 상기 게 1단계 및 제 2단계 중 적어도 한 단계에서 유화제를 생략 가능한 방법이 이용될 수 있다. 따라서， 본 발명에서 유화중합을 진행하는 경우 유화제 사용을 억제할 수 있다.  Therefore, in the present invention, in order to solve the above problems, the seed polymer and the binder are prepared by an emulsion-free polymerization method of the initiator alone, or an emulsion polymerization in which a specific additive or a general emulsifier which serves as an emulsifier is added. Preferably, a method capable of omitting the emulsifier in at least one of the first and second steps may be used. Therefore, when the emulsion polymerization in the present invention can be used to suppress the use of emulsifiers.
본 발명에서， 제 1단계 및 게 2단계 중 유화제가 생략된 경우 중합개시제만 포함된 단량체 조성물의 중합을 통해 시드폴리머나 바인더 입자를 제초할 수 있다. 바람직하게 유화제 사용은 게 1단계에서 생략 가능하다. 또한， 본 발명은 선택적으로 유화제의 역할을 하는 특정 첨가제나 일반적으로 알려진 유화제를 사용하여 유화 중합을 통해 시드 폴리머와 바인더를 제조할 수 있다.  In the present invention, when the emulsifier is omitted in the first step and the crab step 2, it is possible to weed the seed polymer or binder particles through the polymerization of the monomer composition containing only the polymerization initiator. Preferably the use of emulsifiers can be omitted in the crab step 1. In addition, the present invention may produce seed polymers and binders through emulsion polymerization using particular additives or generally known emulsifiers that optionally act as emulsifiers.
이때， 본 발명에서는 설명의 편의를 위해 유화 중합이 가능하며 유화제 역할을 하는 특정 첨가제와 일반적인 유화제를 모두 유화제로 기재하기로 한다. 상기 유화제 역할을 하는 특정 첨가제는， 단량체 화합물들과 공중합 반응이 가능하면서 동시에 유화중합에 필요한 유화제 역할을 한다. 이에 대한 구체적 예를 들면， 말단기에 염을 포함하는 화합물은 모두 가능하며， 보다 구체적인 예로는 소디움 4-비닐벤젠술포네이트， 소디움 메타알릴술포네이트， 소디움 알릴술포네이트， 소디움 도데실벤젠술포네이트， 소디움 비닐술포네이트 등이 있으나， 이에 한정되는 것은 아니다. 상기 특정 첨가제를 유화제로 사용한 본 발명의 바인더의 경우， 종래에 다른 바인더에 비해 우수한 특성， 보다 구체적으로 전극과 집전체와의 접착력 및 열접합 특성이 우수하였으며， 전지 특성 역시 우수하다는 것을 확인하였다. At this time, in the present invention, for the convenience of description, the emulsion polymerization is possible, and all of the specific additives and general emulsifiers that act as emulsifiers will be described as emulsifiers. The specific additive that acts as an emulsifier may be copolymerized with monomer compounds and at the same time serve as an emulsifier for emulsion polymerization. Specific examples thereof include all compounds containing a salt in the terminal group, and more specific examples thereof include sodium 4-vinylbenzenesulfonate, sodium metaallylsulfonate, sodium allylsulfonate, sodium dodecylbenzenesulfonate, Sodium vinylsulfonate, and the like, but is not limited thereto. In the case of the binder of the present invention using the specific additive as an emulsifier, it was confirmed that compared with other binders in the prior art, more specifically, the adhesion between the electrode and the current collector and the thermal bonding property were excellent, and the battery characteristics were also excellent.
또한 상기 일반적인 유화제는 유화중합에 사용되는 통상적인 성분을 모두 포함할 수 있으며， 구체적인 예로는 소디움 라우릴 설페이트， 소디움 라우레스 설페이트， 암모늄 라우릴 설페이트, 암모늄 라우레스 설페이트， 트리에탄올아민 라우릴 설페이트， 및 소디움 트라이폴리포스페이트로 이루어진 군에서 선택된 In addition, the general emulsifier may include all conventional components used in the emulsion polymerization, specific examples include sodium lauryl sulfate, sodium laureth sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, triethanolamine lauryl sulfate, and Selected from the group consisting of sodium tripolyphosphate
1종 이상이 있으나, 이에 한정되는 것은 아니다. There is one or more, but is not limited thereto.
이러한 유화제는 제 1단량체 조성물 또는 제 2단량체 조성물의 층 중량의 Such emulsifiers are used to determine the weight of the layer of the first monomer composition or the second monomer composition.
100 중량부를 기준으로 0.01 내지 5 중량부로 사용할 수 있다. ' 그러면， 본 발명의 바람직한 양극 활물질용 수계 바인더의 제조방법에 대하여 하기에서 보다 구체적으로 설명하기로 한다. It can be used in 0.01 to 5 parts by weight based on 100 parts by weight. "Then, there will be described in more detail below with respect to the production method of the water-based binder for the positive electrode active material of the present preferred invention.
바람직한 일 구현예에 따른 수계 바인더의 제조방법에서， 반웅의 제 1단계는 아크릴계 단량체와 α , β -불포화 나이트릴 화합물를 사용하여 중합을 통해 시드 폴리머 입자를 제조하는 단계이다.  In the method of preparing an aqueous binder according to a preferred embodiment, the first step of reaction is to prepare seed polymer particles through polymerization using an acrylic monomer and an α, β-unsaturated nitrile compound.
구체적으로， 이러한 제 1단계는 아크릴계 단량체 및 α , β -불포화 나이트릴 화합물을 포함하는 게 1 단량체 조성물을 중합하여 시드 폴리머를 제조하는 단계를 포함한다. 상기 게 1단계는 무유화제 중합방법이 가능할 수 있고, 필요에 따라 유화제를 사용할 수 있다. 이러한 경우， 상기 제 1 단계에서 유화제가 생략된 경우 중합은 게 1단량체 조성물을 사용하여 중합 개시제의 존재 하에 진행될 수 있다.  Specifically, this first step includes the step of preparing a seed polymer by polymerizing a first monomer composition comprising an acrylic monomer and an α, β-unsaturated nitrile compound. In the first step, the emulsion-free polymerization method may be possible, and an emulsifier may be used if necessary. In this case, when the emulsifier is omitted in the first step, the polymerization may be carried out in the presence of a polymerization initiator using the crab monomer monomer composition.
상기 제 1단량체 조성물을 이용하여 시드 폴리머 입자를 제조하는 방법에서， 시드 폴리머 입자를 조절이 필요한 경우에는 유화제를 이용한 유화 중합을 이용하는 것이 시드 폴리머 입자의 입경을 조절하는데 있어 가장 용이하고 바람직하다 . In the method for producing seed polymer particles using the first monomer composition, when the seed polymer particles need to be adjusted, emulsification using an emulsifier The use of polymerization is the easiest and preferred for controlling the particle diameter of the seed polymer particles.
또한， 상기 계 1단량체 조성물은 물; 및 유화제， 가교제 또는 이들의 흔합물；을 더 포함할 수 있다. 즉， 본 발명은 시드 폴리머 입자를 제조하기 위한 반응 용매로 물을 사용하므로， 상기 제 1단량체 조성물은 물을 포함한다. 상기 제 1단량체 조성물은 상기 두 단량체를 물에 분산시킨 후， 물에 용해된 개시제를 투입하여 제조할 수 있다. 따라서， 상기 게 1단계 및 후술하는 제 2단계의 무유화제 중합 방법은 물에 의한 축중합 방법을 포함할 수 있다. 특히， 본 발명에서 IPN 구조를 제조하기 위해서는， 제 1단계 및 후술하는 계 2단계에서 모두 가교제가 사용되도록 한다. 또한, SIPN 구조 형성을 위해서 제 1단계에서 가교제가 사용될 경우， 후술하는 제 2단계에서 가교제를 생략될 수 있다. 따라서, 상기 제 1단량체 조성물은 물과 함께 가교제를 포함할 수 있고， 선택적으로 유화제를 포함할 수 있다.  In addition, the system monomer composition is water; And emulsifiers, crosslinking agents or mixtures thereof. That is, since the present invention uses water as a reaction solvent for preparing seed polymer particles, the first monomer composition includes water. The first monomer composition may be prepared by dispersing the two monomers in water and then adding an initiator dissolved in water. Therefore, the first and second emulsion-free polymerization methods described later may include a condensation polymerization method using water. In particular, in order to manufacture the IPN structure in the present invention, the crosslinking agent is used in both the first step and the second step described below. In addition, when the crosslinking agent is used in the first step to form the SIPN structure, the crosslinking agent may be omitted in the second step to be described later. Thus, the first monomer composition may include a crosslinking agent together with water, and may optionally include an emulsifier.
또한, 상기 제 1단계는 중합 반응 온도 30 내지 150°C , 보다 바람직하게 50 내지 90°C이며， 증합시간 0. 1 내지 10시간, 보다 바람직하게 0. 1 내지 3시간의 조건에서 증합을 진행한다. In addition, the first step is a polymerization reaction temperature of 30 to 150 ° C, more preferably 50 to 90 ° C, the polymerization time is carried out under the conditions of 0.1 to 10 hours, more preferably 0.1 to 3 hours do.
또한， 본 발명에서 시드 폴리머 입자를 구성하는 단량체는 전지 특성을 조절할 수 있는 통상적인 단량체를 사용할 수 있다. 예를 들어， 상기 시드 폴리머 입자는 아크릴계 단량체와 α , β - 불포화 나이트릴 화합물을 포함하는 단량체 조성물을 공중합하여 이루어진다.  In addition, the monomer constituting the seed polymer particles in the present invention may use a conventional monomer that can control the battery characteristics. For example, the seed polymer particles are formed by copolymerizing a monomer composition comprising an acrylic monomer and an α, β-unsaturated nitrile compound.
상기 아크릴계 단량체는 탄소수 4 내지 20의 아크릴산 에스테르계 단량체 및 메타크릴산 에스테르계 단량체 중에서 선택되는 1종 이상일 수 있다.  The acrylic monomer may be at least one selected from acrylic acid ester monomers having 4 to 20 carbon atoms and methacrylic acid ester monomers.
상기 아크릴산 에스테르계 단량체는 탄소수 4 내지 20의 아크릴산 알킬 에스테르; 탄소수 4 내지 20의 에테르기 함유 아크릴산 에스테르; 및 탄소수 4 내지 20의 하이드톡시기 함유 아크릴산 에스테르;로 이루어진 군에서 선택된 1종 이상일 수 있다. 상기 메타크릴산 에스테르의 단량체는 탄소수 5 내지 20의 메타크릴산 알킬 에스테르 ; .탄소수 5 내지 20의 에테르기 함유 메타크릴산 에스테르; 및 탄소수 5 내지 20의 하이드록시기 함유 메타크릴산 에스테르;로 아루어진 군에서 선택된 1종 이상일 수 있다. ' The acrylic ester monomer is an acrylic acid alkyl ester having 4 to 20 carbon atoms; Ether group-containing acrylic esters having 4 to 20 carbon atoms; And it may be at least one selected from the group consisting of; 4 to 20 hydroxy group containing acrylic acid ester having 4 to 20 carbon atoms. The monomer of the methacrylic acid ester is methacrylic acid alkyl ester having 5 to 20 carbon atoms; Ether group-containing methacrylic acid esters having 5 to 20 carbon atoms; And it may be one or more selected from the group consisting of; hydroxy group-containing methacrylic acid ester having 5 to 20 carbon atoms. '
상기 아크릴산 에스테르계 단량체의 구체적인 예로서는， 메틸아크릴레이트， 에틸아크릴레이트， 프로필아크릴레이트， 이소프로필아크릴레이트, n-부틸아크릴레이트， 이소부틸아크릴레이트， n- 아밀아크릴레이트， 아이소아밀아크릴레이트， n-핵실아크릴레이트, 2- 에틸핵실아크릴레이트， 사이클로핵실아크릴레이트， 아이소펜틸아크릴레이트， 아이소옥틸아크릴레이트， 아이오보닐아크릴레이트， 아이소데실아크릴레이트， 라우릴아크릴레이트 등의 아크릴산 알킬 에스테르; 부록시에틸아크릴레이트， 에톡시다이에틸렌 글라이콜. 아크릴레이트， 메톡시다이프로필렌 글라이콜 아크릴레이트, 메톡시폴리에틸렌 글라이콜 아크릴레이트， 페녹시에틸 아크릴레이트 등의 에테르기 함유 아크릴산 에스테르; 2- 하이드록시에틸아크릴레이트, 2-하이드록시프로필아크릴레이트， 2-하이드록시 -3- 페녹시프로필아크릴레이트 등의 하이드록시기 함유 아크릴산 에스테르 등을 들 수 있다. As a specific example of the acrylic ester monomer, Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n -butyl acrylate, isobutyl acrylate, n- amyl acrylate, iso amyl acrylate, n-nuxyl acrylate, 2-ethylnuclear acryl Acrylic acid alkyl esters such as acrylate, cyclonuclear acrylate, isopentyl acrylate, isooctyl acrylate, ibornyl acrylate, isodecyl acrylate and lauryl acrylate; Annealed ethyl acrylate, ethoxydiethylene glycol. Ether group-containing acrylic esters such as acrylate, methoxydipropylene glycol acrylate, methoxypolyethylene glycol acrylate and phenoxyethyl acrylate; And hydroxyl group-containing acrylic esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate.
상기 메타크릴산 에스테르의 구체적인 예로서는, 메틸메타크릴레이트， 에틸메타크릴레이트， 프로필메타크릴레이트， 아이소프로필메타크릴레이트， n- 부틸메타크릴레이트， 아이소부틸메타크릴레이트， 사이클로핵실메타크릴레이트， 2-에틸핵실메타크릴레이트 , 아이소펜틸메타크릴레이트， 아이소옥틸메타크릴레이트, 아이소보닐메타크릴레이트, 아이소데실메타크릴레이트， 라우릴메타크릴레이트 등의 메타크릴산 알킬 에스테르; 부특시에틸메타크릴레이트， 에특시다이에틸렌 글라이콜 메타크릴레이트， 메톡시다이프로필렌 글라이콜 메타크릴레이트， 메록시폴리에틸렌 글라이콜 , 메타크릴레이트， 페녹시에틸메타크릴레이트 등의 에테르기 함유 메타크릴산 에스테르; 2-하이드록시에틸메타크릴레이트， 2- 하이드록시프로필메타크릴레이트， 2-하이드록시 -3-페녹시프로필메타크릴레이트 등의 하이드록시기 함유 메타크릴산 에스테르 등을 들 수 있다.  Specific examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclonuclear methacrylate, 2 Methacrylic acid alkyl esters such as ethyl nucleosil methacrylate, isopentyl methacrylate, isooctyl methacrylate, isobornyl methacrylate, isodecyl methacrylate and lauryl methacrylate; Ether groups such as ethyl ethyl methacrylate, ethoxy diethylene glycol methacrylate, methoxydipropylene glycol methacrylate, methoxy polyethylene glycol, methacrylate, and phenoxyethyl methacrylate Containing methacrylic acid esters; And hydroxy group-containing methacrylic acid esters such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2-hydroxy-3-phenoxypropyl methacrylate.
상기 α , β—불포화 나이트릴 화합물은 아크릴로나이트릴， 메타크릴로나이트릴， 염화나이트릴 및 플루오르화나이트릴로 이루어진 군으로부터 선택된 1종 이상이 바람직하다.  The α, β-unsaturated nitrile compound is preferably one or more selected from the group consisting of acrylonitrile, methacrylonitrile, nitrile chloride and nitrile fluoride.
또한， 상기 게 1단계 및 후술하는 제 2단계에서 사용하는 아크릴계 단량체와 α , β -불포화 나이트릴 화합물의 함량은 시드 폴리머 입자를 구성하는 단량체 조성물의 중량을 기준으로 사용된다. 따라서, 상기 게 1단계에서， 상기 아크릴계 단량체의 함량은 제 1단량체 조성물의 층 중량의 100 중량부를 기준으로 30 내지 90 중량부이며， 보다 바람직하게 50 내지 80 중량부일 수 있다. 상기 아크릴계 단량체의 함량이 30 중량부 미만인 경우 결착력이 저하되며， 80 중량부를 초과하는 경우 물리 /화학적 안정성이 저하된다. In addition, the content of the acrylic monomer and the α, β-unsaturated nitrile compound used in the first step and the second step will be used based on the weight of the monomer composition constituting the seed polymer particles. Therefore, in the first step, the content of the acrylic monomer is 30 to 90 parts by weight, more preferably 50 to 80 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition. When the content of the acrylic monomer is less than 30 parts by weight, the binding force is lowered, and when it exceeds 80 parts by weight, the physical / chemical stability is lowered.
상기 계 1단계에서, 상기 α , β -불포화 나이트릴 화합물의 함량은 제 1단량체 조성물의 층 중량의 100 중량부를 기준으로 1 내지 50 중량부이며， 보다 바람직하게는 5 내지 40 증량부일 수 있다. 이러한 함량 범위로 α , β— 블포화 나이트릴 화합물을 사용해야 얻어지는 바인더의 결착력과 전지특성이 우수하다.  In the step 1, the content of the α, β-unsaturated nitrile compound is 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the layer weight of the first monomer composition. In this content range, α, β-saturated nitrile compounds should be used for excellent binding and battery characteristics of the obtained binder.
또한 본 발명에 사용되는 중합개시제로는 라디칼을. 생성하는 어떠한 화합물도 사용할 수 있으며, 구체적인 예로는 암모늄퍼설페이트， 포타슴퍼설페이트， 소디움퍼설페이트， 벤조일 퍼옥사이드， 부틸 하이드로퍼옥사이드 또는 이들의 흔합물 등이 있으나， 이에 한정하는 것은 아니다. In addition, the polymerization initiator used in the present invention is a radical . Any compound produced may be used, and specific examples thereof include, but are not limited to, ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, butyl hydroperoxide, or a combination thereof.
상기 중합개시제의 함량은 제 1단량체 조성물의 층 중량의 100 중량부를 기준으로 0. 1 내지 5 충량부로 사용하는 것이 바람직하다.  The content of the polymerization initiator is preferably used in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition.
또한.， 상기 제 1단계 반응시 (즉， 시드 폴리머 합성시 ) 단량체 성분과 중합개시제는， 전체 증합 반응 시간 중 시작과 동시에 내지 3 시간에 걸쳐 분할 투입될 수 있다.  In addition, the monomer component and the polymerization initiator in the first step of the reaction (that is, during the synthesis of the seed polymer) may be separately added to the mixture over a period of 3 hours simultaneously with the start of the total polymerization reaction time.
또한, 상기 시드 폴리머 입자의 단량체 조성물은 경우에 따라 상기 아크릴산 에스테르 또는 메타크릴산 에스테르 및 α , β -불포화 나이트릴 화합물과 공중합 가능한 다른 단량체와 가교제를 포함하고 있을 수도 있다. 이들은 바인더 입자의 겔 함량 및 분자구조를 조절하는 역할을 하여 바인더의 전기화학적 안정성을 높이는 역할을 할 수 있다. 또한， 본 발명의 상기 거 u단량체 조성물은 상기에서 언급된 유화제를 더 포함할 수 있다.  In addition, the monomer composition of the seed polymer particles may optionally contain a crosslinking agent and other monomers copolymerizable with the acrylic ester or methacrylic ester and the α, β-unsaturated nitrile compound. These may serve to adjust the gel content and molecular structure of the binder particles to increase the electrochemical stability of the binder. In addition, the macromonomer composition of the present invention may further comprise the emulsifier mentioned above.
상기 가교제 및 그래프팅 에이전트의 역할을 수행하는 구체적인 예로는 에틸렌 글리콜 디메타크릴레이트， 디에틸렌 글리콜 디메타크릴테이트， 트리에틸렌 글리콜 디메타크릴레이트， 테트라에틸렌글리콜 디아크릴레이트， 테트라에틸렌글리콜 디메타크릴레이트, 폴리 에틸렌 글리콜 디메타크릴에이트， 폴리 프로필렌 글리콜 디메타크릴레이트， 폴리 부틸렌 글리콜 디아크릴레이트,Specific examples of the role of the crosslinking agent and the grafting agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacryl. Latex, polyethylene glycol dimethacrylate, Polypropylene glycol dimethacrylate, polybutylene glycol diacrylate,
1 , 3—부타디올 디아크릴레이트， 1，3_부타디올 디메타크릴레이트, 1 , 4-부타디을 디아크릴레이트， 1， 4-부타디올 디메타크릴레이트， 1 , 6-핵산디을 디메타크릴레이트， 아릴 아크릴레이트， 아릴 메타크릴레이트， 트리아릴 이소시아누레이트, 트리아릴 아민， 디아릴 아민， 트리메틸을프로판 트리메타크릴레이트， 트리메틸올메탄 트리아크릴레이트 등 및 비닐계 단량체인 스티렌， α -메틸스티렌， β -메틸스티렌， p-t—부틸스티렌 및 디비닐벤젠 등이 있으나， 이에 한정되는 것은 아니다. 또한， 이들은 단독 또는 2종 이상 흔합 사용이 가능하다. 1, 3-butadiol diacrylate, 1,3_butadiol dimethacrylate, 1,4-butadione diacrylate, 1,4-butadiol dimethacrylate, 1,6-nucleodiamide Acrylate, aryl acrylate, aryl methacrylate, triaryl isocyanurate, triaryl amine, diaryl amine, trimethyl to propane trimethacrylate, trimethylolmethane triacrylate, etc. -Methyl styrene, β-methyl styrene, pt-butyl styrene, divinylbenzene, and the like, but is not limited thereto. Moreover, these can be used individually or in combination of 2 or more types.
게 1단계에서 유화제가 사용되는 경†, 상기 유화제는 제 1단량체 조성물의 층 중량의 100 증량부를 기준으로 0.01 내지 5 중량부로 사용할 수 았다.  When the emulsifier is used in step C1, the emulsifier may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition.
또한， 본 발명의 시드 폴리머 입자는 상기 단량체 성분들 이외에， 중합첨가제로서 당 분야에 알려진 통상적인 성분인 분자량 조절제， 완충제 (buf fer ) , 왁스 (wax) 등을 사용할 수 있다. 또한， 이들은 단독 또는 2종 이상 흔합 사용이 가능하다.  In addition, the seed polymer particles of the present invention may use, in addition to the monomer components, a molecular weight regulator, a buffer (buf fer), a wax (wax), and the like which are conventional components known in the art as a polymerization additive. Moreover, these can be used individually or in combination of 2 or more types.
상기 분자량 조절제의 구체적인 예로는 t-도데실머캡탄， n—도데실머캡탄， n-옥틸머캡탄 등이 있으나， 이에 한정되는 것은 아니다.  Specific examples of the molecular weight modifier include t-dodecylmercaptan, n-dodecylmercaptan, n-octylmercaptan, and the like, but are not limited thereto.
또한 제 1단계를 통해 제조된 시드 폴리머는 유리전이온도 (Tg)가 -100 내지 100°C , 바람직하게 -40 내지 40°C이다. 또한 시드 폴리머의 유리전이온도는 이후 제조되는 바인더의 유리전이온도에 영향을 주며， 그 온도가 -40°C 미만에서는 화학적 안정성이 떨어지고， 40 °C 이상에서는 전극의 결착력이 저하되어 전극 제조시 박리되거나 크랙이 발생하는 경우가 있다. In addition, the seed polymer prepared through the first step has a glass transition temperature (Tg) of -100 to 100 ° C, preferably -40 to 40 ° C. In addition, the glass transition temperature of the seed polymer affects the glass transition temperature of the binder to be produced later, the chemical stability is lower than the temperature below -40 ° C, the binding strength of the electrode is lowered above 40 ° C, peeling during electrode production Or cracks may occur.
또한, 상기 시드 폴리머 입자의 평균 입자 직경은 10 내지 1500 nm, 보다 바람직하게는 50 내지 1000 nm이다. 상기 시드 플리머의 평균 입자 직경도 이후 제조되는 수계 바인더의 평균 입자 직경에 큰 영향을 미친다. 한편， 본 발명의 바인더의 제조방법에서， 반웅의 제 2단계는 상기 거 U단계에서 제조된 시드 폴리머 입자를 이용하여， 추가적인 중합을 진행함으로써 최종적으로 IPN 또는 SIPN 구조를 갖는 폴리머 입자를 제조하는 단계이다. 상기 제 2단계는 시드 폴리머에 게 2단량체 조성물을 첨가후 중합을 진행한다ᅳ 이때， 상기 게 2단량체 조성물은 아크릴계 단량체, α , β -불포화 나이트릴 화합물， 접착력 강화 단량체 및 가교제를 포함한다. 또한， 상기 거 12단량체 조성물도 물; 및 유화제， 가교제 또는 이들의 흔합물；을 더 포함할 수 있다. In addition, the average particle diameter of the seed polymer particles is 10 to 1500 nm, more preferably 50 to 1000 nm. The average particle diameter of the seed plymer also has a great influence on the average particle diameter of the aqueous binder to be produced later. On the other hand, in the manufacturing method of the binder of the present invention, the second step of Banung is a step of finally producing a polymer particle having an IPN or SIPN structure by further polymerization using the seed polymer particles prepared in the above U step to be. In the second step, the polymerization proceeds after addition of the dimer composition to the seed polymer. In this case, the bimer composition includes an acrylic monomer, α, β-unsaturated nitrile compound, adhesion enhancing monomer, and a crosslinking agent. In addition, the macromer composition is also water; And emulsifiers, crosslinking agents or mixtures thereof.
이때， 상술한 바대로 본 발명에서는 제 1단계와 제 2단계에서 가교제가 모두 사용되면 ΙΡΝ 구조를 형성할 수 있다. 또한 제 1단계 또는 제 2단계의 어느 한 단계에서만 가교제가 사용될 경우， SIPN 구조의 수계 바인더를 제조할 수 있다.  At this time, as described above, in the present invention, if both crosslinking agents are used in the first step and the second step, the ΙΡΝ structure can be formed. In addition, when the crosslinking agent is used in only one step of the first step or the second step, an aqueous binder of SIPN structure can be prepared.
바람직한 일 구현예에 있어, 게 2단계에서 가교제가 포함되는 경우， 상기 제 2단계는 상기 시드 폴리머에, 아크릴계 단량체, α , β -불포화 나이트릴 화합물， 접착력 강화 단량체 및 가교제를 포함하는 게 2 단량체 조성물을 첨가하고 중합하여 바인더 입자를 제조하는 단계를 포함한다.  In a preferred embodiment, in the case where the crosslinking agent is included in the crab step 2, the second step may include an acrylic monomer, α, β-unsaturated nitrile compound, an adhesion enhancing monomer and a crosslinking agent in the seed polymer. Adding and polymerizing the composition to produce binder particles.
본 발명은 시드 폴리머를 성장시킬 때 두 종류의 서로 다른 단량체와 함께 접착력 강화 단량체와 가교제를 사용함으로써，. 바인더와 양극제 표면과의 물리적 상호 작용이나 가교; 및 바인더 입자 간의 물리적 상호 작용기나 가교를 촉진할 수 있고, 이에 따라 바인더가 전극과의 결착력이 향상되어 전지의 전기화학적 안정성을 높일 수 있다.  The present invention utilizes an adhesion enhancing monomer and a crosslinking agent together with two different monomers when growing the seed polymer. Physical interaction or crosslinking of the binder and the positive electrode surface; And it is possible to promote physical interaction groups and crosslinking between the binder particles, thereby improving the binding capacity of the binder with the electrode can improve the electrochemical stability of the battery.
상기 제 2 단량체 조성물을 이용하여 수계 바인더를 제조시， 수계 바인더 폴리머 입자의 입경을 조절하는데 있어서는 유화 중합법이 가장 용이하다. 이러한 경우 유화제가 사용될 수 있다.  In preparing the aqueous binder using the second monomer composition, in order to control the particle diameter of the aqueous binder polymer particles, the emulsion polymerization method is the easiest. In this case emulsifiers may be used.
상기 게 2단계는 중합 반응 온도는 30 내지 150 °C , 보다 적절하게는 50 내지 90°C이며， 중합시간은 0.5 내지 24 시간， 보다 적절하게 1 내지 12시간의 조건에서 진행된다. In the second step, the polymerization temperature is 30 to 150 ° C., more preferably 50 to 90 ° C., and the polymerization time is 0.5 to 24 hours, more preferably 1 to 12 hours.
상기 계 2단계에서， 상기 시드 폴리머의 함량은 제 2단량체 조성물의 층 중량의 100 중량부를 기준으로 1 내지 70 중량， 보다 바람직하게 5 내지 30 중량부일 수 있다.  In the second step, the content of the seed polymer may be 1 to 70 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the layer weight of the second monomer composition.
상기 제 2단계의 중합 반웅에 사용되는 단량체는 상기 제 1단계에서 언급한 바와 같은 바인더로서의 특성을 잘 만족시켜줄 수 있는 것으로서， 아크릴산 에스테르계 단량체 및 메타크릴산 에스테르계 단량체 중에서 선택되는 적어도 1종 이상의 아크릴계 단량체와 α , ρ - 불포화 나이트릴 화합물을 포함하는 단량체, 접착력 강화 단량체， 고분자 네트워크를 형성하게 되는 가교제 등을 공중합하여 이루어진다. The monomer used in the polymerization reaction of the second step is to satisfy the properties as a binder as mentioned in the first step, at least selected from acrylic ester monomers and methacrylic ester monomers It is made by copolymerizing at least one acrylic monomer with a monomer containing an α, ρ-unsaturated nitrile compound, an adhesion enhancing monomer, a crosslinking agent which forms a polymer network, and the like.
상기 아크릴계 단량체의 구체적인 예는， 상기 시드 폴리머 제조 시 사용되는 단량체와 동일하며， 1종 단독으로 또는 2종 이상을 조합시켜 사용할 수 있다. 또한， 상기 제 2단계에서， 상기 아크릴계 단량체의 함량은 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 30 내지 90 중량부가 바람직하며， 보다 바람직하게는 40 내지 80 중량부이다ᅳ Specific examples of the acrylic monomers are the same as the monomers used in the preparation of the seed polymer, and may be used alone or in combination of two or more. In addition, in the second step, the content of the acrylic monomer is preferably 30 to 90 parts by weight, more preferably 40 to 80 parts by weight based on 100 parts by weight of the total weight of the second monomer composition.
또한， α , β -불포화 나이트릴 화합물 역시 상기 시드 풀리머 입자 제조 시 사용되는 단량체와 동일하며， 1종 단독으로 또는 2종 이상을 조합시켜 사용할 수 있다. 상기 제 2단계에서， 상기 α , β -불포화 나이트릴 화합물의 함량은 게 2단량체 조성물의 층 증량의 100 중량부를 기준으로 1 내지 50 중량부가 바람직하며， 보다 바람직하게는 5 내지 40 중량부이며， 이러한 경우 얻어지는 바인더의 결착력과 전기화학적 특성이 우수하다. In addition, α, β-unsaturated nitrile compound is also the same as the monomer used in the production of the seed puller particles, can be used alone or in combination of two or more. In the second step, the content of the α , β-unsaturated nitrile compound is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the layer increase of the crab dimer composition, In this case, the binder and the electrochemical properties of the resulting binder are excellent.
상기 접착력을 강화 단량체는 각각이 포함하고 있는 작용기를 통하여 전극으로 사용되는 금속 및 전극제조 시 사용되는 다른 부재료들과의 결착력을 을려주는 역할을 수행한다. 이때 사용되는 단량체는 각 작용기의 특성에 따라 이온결합 및 공유결합을 통하여 결착력을 올려주며， 1종 단독으로 또는 2종 이상을 조합시켜 사용할 수 있다.  The adhesion enhancing monomer serves to cover the binding force between the metal used as an electrode and other subsidiary materials used in manufacturing the electrode through a functional group included in each. At this time, the monomer used to increase the binding force through the ionic bond and covalent bond according to the characteristics of each functional group, can be used alone or in combination of two or more.
따라서， 상기 접착력 강화 단량체는 전극과의 상기 결착력을 을려주는 단량체로서， 구체적인 예를 들면, 불포화 모노카르본산계 단량체인 아크릴산， 메타크릴산， 메틸메타크릴산 등; 불포화 디카르본산계 단량체인 이타콘산, 푸마르산， 시트라콘산, 메타콘산， 글루타콘산， 크로톤산 등; 아크릴아미드계 단량체인 아크릴아미드， η-메틸올아크릴아미드, η-부톡시메틸아크릴아미드 등; 에폭시계 단량체인 글리시딜 메타크릴레이트 등이 있으나， 이에 한정되는 것은 아니다. 상기 접착력 강화 단량체의 함량은 아크릴계 단량체와 α , β -불포화 나이트릴 화합물의 총합 100 중량부 당 1 내지 40 중량부， 보다 구체적으로 5 내지 20 중량부가 바람직하다.  Therefore, the adhesion-enhancing monomer is a monomer for covering the binding force with the electrode, and specific examples thereof include acrylic acid, methacrylic acid, methylmethacrylic acid, and the like, which are unsaturated monocarboxylic acid monomers; Itaconic acid, fumaric acid, citraconic acid, metaconic acid, glutaconic acid, crotonic acid, etc. which are unsaturated dicarboxylic acid monomers; Acrylamide which is an acrylamide type monomer, (eta) -methylol acrylamide, (eta) -butoxymethyl acrylamide; Glycidyl methacrylate, which is an epoxy-based monomer, but is not limited thereto. The content of the adhesion enhancing monomer is 1 to 40 parts by weight, more specifically 5 to 20 parts by weight, per 100 parts by weight of the total amount of the acrylic monomer and the α, β-unsaturated nitrile compound.
고분자 네트워크를 형성하게 되는 가교제의 구체적인 예는 상기 시드 폴리머 입자 제조 시 사용되는 가교제와 동일한 물질을 사용할 수 있다. 또한， 그 함량은 수계 바인더를 구성하는 제 2단량체 조성물의 층 중량의 100 중량부를 기준으로 0. 1 내지 20 중량부， 보다 구체적으로 0.5 내지 10 중량부가 바람직하다. Specific examples of the crosslinking agent that will form the polymer network may use the same material as the crosslinking agent used to prepare the seed polymer particles. Also, The content is preferably from 0.01 to 20 parts by weight, more specifically from 0.5 to 10 parts by weight, based on 100 parts by weight of the layer weight of the second monomer composition constituting the aqueous binder.
상기 제 2단계에서 사용되는 증합개시제로는 라디칼을 생성하는 어떠한 화합물도 사용할 수 있으며， 구체적인 예는 상기 1단계와 동일하다. 상기 중합개시제의 함량은 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 0. 1 내지 5 중량부로 사용하는 것이 바람직하다.  As the polymerization initiator used in the second step, any compound that generates a radical may be used, and specific examples thereof are the same as in the first step. The content of the polymerization initiator is preferably used in 0.1 to 5 parts by weight based on 100 parts by weight of the total weight of the second monomer composition.
또한， 본 발명은 수계 바인더 입자를 제조하기 위한 반웅 용매로 물을 사용하므로， 상기 게 2단량체 조성물도 물을 포함할 수 있다.  In addition, since the present invention uses water as a reaction solvent for preparing the aqueous binder particles, the crab dimer composition may also include water.
상기 유화제는 게 1단계 시드 폴리머 입자를 제조할 때 사용되었던 물질과 동일하거나 또는 단량체로 작용하면서 동시에 유화제 역할을 하.는 화합물이 사용 가능하고， 이들의 흔합물도 사용 가능하다. 상기 유화제는 상기 단량체들과 흔합하여 에멀견을 제조한 후 일정 반웅시간 동안 공급함으로써 바인더를 제조한다.  The emulsifier may be the same as the material used to prepare the crab seed polymer particles, or may act as a monomer and at the same time act as an emulsifier, a compound thereof may be used. The emulsifier is mixed with the monomers to prepare an emulsion, and then supply the binder for a predetermined reaction time.
제 2단계에서 유화제가 사용되는 경우， 상기 유화제는 게 2단량체 조성물의 충 중량의 100 중량부를 기준으로 0.01 내지 5 중량부로 사용할 수 있다.  When the emulsifier is used in the second step, the emulsifier may be used in 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the crab dimer composition.
또한， 반응 단량체 성분들과 중합개시제를 포함한 제 2 단량체 조성물을 이용하여 바인더 입자를 제조시， 상기 반웅 단량체 성분들의 조성과 중합개시제는 분할하여 투입할 수 있다.  In addition, when preparing the binder particles using the second monomer composition including the reaction monomer components and the polymerization initiator, the composition and the polymerization initiator of the reaction monomer components may be added separately.
예를 들어， 제 2단계 제조 시 반웅 단량체 성분과 중합개시제는 동시에 시드 폴리머에 주입되는데， 이때 이들은 0.5~6시간에 걸쳐 분할 투입될 수 있디- . 또한 상기 제 2 단량체 조성물은， 게 1단계의 시드 폴리머 제조와 같이 경우에 따라 상기 아크릴산 에스테르 또는 메타크릴산 에스테르 및 α , β - 불포화 나이트릴 화합물과 공중합 가능한 다른 단량체를 더 포함할 수 있다. 또한 본 발명의 수계 바인더는 게 1단계의 시드 폴리머와 같이 상기 단량체 성분들 이외에， 중합첨가제로서 당 분야에 알려진 통상적인 성분인 분자량 조절제 및 완층제 (buf fer) , 왁스 (wax) 등을 사용할 수 있다.  For example, in the second stage of preparation, the reaction component and the polymerization initiator are injected into the seed polymer at the same time, which can be dividedly added over 0.5-6 hours. In addition, the second monomer composition may further include other monomers copolymerizable with the acrylic acid ester or methacrylic acid ester and α, β-unsaturated nitrile compounds, as in the case of preparing the seed polymer of the first stage. In addition, the aqueous binder of the present invention may be used in addition to the monomer components, such as the crab seed seed polymer, molecular weight regulators, buf fers, waxes, and the like which are conventional components known in the art as polymerization additives. have.
한편， 본 발명의 다른 구현예에 따라， 상기 방법으로 제조되며， 유리전이온도 (Tg)가 ᅳ 100 °C 내지 100°C인， 상호 침투성 고분자 네트워크 ( Interpenetrat ing Polymer Network： IPN) 또는 세미—상호 침투성 고분자 네트워크 (Semi -interpenetrat ion Polymer Network: SIPN)의 구조를 갖는 이차전지 양극활물질용 수계 바인더가 제공된다. On the other hand, according to another embodiment of the present invention, prepared by the above method, the glass transition temperature (Tg) is ᅳ 100 ° C to 100 ° C, Interpenetrating Polymer Network (IPN) or semi- mutual permeability An aqueous binder for a secondary battery cathode active material having a structure of a semi-interpenetrat ion polymer network (SIPN) is provided.
본 발명의 수계 바인더의 적정 유리전이온도 (Tg)는 -100 내지 lOCTC , 보다 바람직하게는 -40 내지 40 °C이다. 이때, 수계 바인더의 유리전이온도가 -40°C 미만에서는 화학적 안정성이 떨어지며， +40 °C 이상에서는 전극의 결착력이 저하되어 전극 제조시 박리되거나 크택이 발생하는 경우가 있다. Suitable glass transition temperature (Tg) of the aqueous binder of the present invention is -100 to lOCTC, more preferably -40 to 40 ° C. At this time, when the glass transition temperature of the water-based binder is less than -40 ° C, the chemical stability is lowered, and the binding force of the electrode is lowered at +40 ° C or more, which may cause peeling or cracking during electrode production.
본 발명으로 제조된 수계 바인더의 평균 입자 직경은 80 내지 4000讓， 보다 바람직하게는 100 내지 2000nm이다. 수계 바인더의 입자 직경은 전극 제조시 사용되는 양극활물질의 크기와의 상대적 크기에 따라 이온전도도 및 결착력에 큰 영향을 미친다. The average particle diameter of the aqueous binder produced by the present invention is 80 to 4000 mm 3, more preferably 100 to 2000 nm. The particle diameter of the aqueous binder has a great influence on the ionic conductivity and binding strength depending on the relative size with the size of the positive electrode active material used in electrode production.
이러한 본 발명의 방법으로 제조된 수계 바인더는 양극제 표면과의 . 상호작용， 가교 및 바인더 자체 입자간 상호작용， 및 가교제와 유화제 사용을 최대한 억제하여 결착력과 전기화학적 안정성이 높아 이차전지 양극활물질에 사용되기에 적합하다. 이하 본 발명의 바람직한 실시예에 대한 구성 및 작용을 상세히 설명한다 . 다만 이러한 설명은 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시하게 하기 위함이지， 이로써 본 발명의 권리범위가 한정되는 것은 아니다.  The water-based binder prepared by the method of the present invention has a surface with the positive electrode surface. Interaction, crosslinking and interaction between the particles themselves, and the use of crosslinking agents and emulsifiers are suppressed to the maximum, which is suitable for use in secondary battery cathode active materials due to high binding strength and electrochemical stability. Hereinafter, the configuration and operation of the preferred embodiment of the present invention will be described in detail. However, this description is intended to be easily carried out by those skilled in the art, the scope of the present invention is not limited thereto.
[실시예 1] Example 1
( 1) 시드 폴리머 제조  (1) seed polymer production
질소 기류하의 반웅기에 증류수 85g을 넣고 온도를 75°C로 유지시켰다. 유화제인 소디움 라우릴 설페이트 (SLS) O . lg을 투입한 후， 반웅 단량체인 2- 에틸핵실아크릴레이트 (2EHA) 8g 과 아크릴로나이트릴 (AN) 2g을 투입하고 단량체가 잘 분산될 수 있도록 교반하였다. 이후， 중합개시제인 암모늄퍼설페이트 O . lg을 증류수 4g에 용해시켜 투입하고， 20분간 반웅을 진행하여 시드 폴리머 입자 제조를 완성하였다. 85 g of distilled water was added to a reaction vessel under a nitrogen stream, and the temperature was maintained at 75 ° C. Sodium Lauryl Sulfate (SLS), which is an emulsifier. After lg was added, 8 g of 2-ethylnucleosil acrylate (2EHA) and 2 g of acrylonitrile (AN) as reaction monomers were added and stirred to disperse the monomer well. After that, ammonium persulfate O. After dissolving lg in 4 g of distilled water and reacting for 20 minutes, seed polymer particles were prepared.
(2) 수계 바인더 제조  (2) Aqueous Binder Manufacturing
상기 제조된 시드 폴리머 입자에 증류수 85g , 반응 단량체인 2- 에틸핵실아크릴레이트 77g, 아크릴로나이트릴 12g, 에틸렌 글리콜 디메타크릴레이트 (EGDMA) 2.5g과 이타콘산 (ITA) 3g, 아크릴산 (AA) 5.5g, 유화제인 소디움 라우릴 설페이트 (SLA) O.lg을 흔합한 용액을 3시간에 걸쳐서 투입하면서， 암모늄퍼설페이트 0.5g을 증류수 20g에 용해시켜 마찬가지로 Distilled water 85g, the reaction monomer 2- in the prepared seed polymer particles 77 g of ethyl nuclear acrylate, 12 g of acrylonitrile, 2.5 g of ethylene glycol dimethacrylate (EGDMA) and 3 g of itaconic acid (ITA), 5.5 g of acrylic acid (AA), sodium lauryl sulfate (SLA) O.lg While adding the mixed solution over 3 hours, 0.5 g of ammonium persulfate was dissolved in 20 g of distilled water.
3시간에 걸쳐서 투입하였다. 추가로 75°C로 3시간 반응 시킨 후 수산화 나트륨을 사용하여 pH 7이 되도록 중화하여 수계 바인더 제조를 완성하였다. 본 발명은 제 2단계에서 가교제를 사용함으로써， SIPN구조의 바인더를 얻었다. Injected over 3 hours. After further reacting at 75 ° C for 3 hours to neutralize to pH 7 using sodium hydroxide to complete the preparation of the aqueous binder. The present invention obtained a binder of SIPN structure by using a crosslinking agent in the second step.
[실시예 2~8 및 비교예 1] [Examples 2 to 8 and Comparative Example 1]
상기 실시예 1과 동일한 방법으로 제조하되， 투입하는 단량체의 조성은 하기 표 1 및 2와 같다.  Prepared in the same manner as in Example 1, the composition of the monomer to be added are as shown in Tables 1 and 2.
[비교예 2 및 3] [Comparative Examples 2 and 3]
단량체 조성물로서 표 2에 나타내는 조성올 이용하며， 시드 폴리머 입자를 이용한 상호 침투성 고분자 네트워크 (Interpenetrating Polymer Network:  Interpenetrating Polymer Network using the composition shown in Table 2 as the monomer composition, and using the seed polymer particles (Interpenetrating Polymer Network:
IPN)를 형성하는 것이 아닌， 일반적인 유화중합을 이용하여 바인더를 제조하였다. Rather than forming IPN), a binder was prepared by general emulsion polymerization.
[표 1]  TABLE 1
실시예 1 실시예 2 실시예 3 실시예 4 실시예 5 실시예 6 단량체 바인 바인 바인 바인 바인 바인 시드 시드 시드 시드 시드 시드 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Monomer Vine Vine Vine Vine Vine Vine Seed Seed Seed Seed Seed
(g) 더 더 더 더 더 더(g) more more more more more
APS 0.1 0.5 0.2 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1 0.5APS 0.1 0.5 0.2 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1 0.5
SLS 0.1 0.1 0.1 0.1 0.4 0.1 0.4 0.1 0.4 0.1 0.4SLS 0.1 0.1 0.1 0.1 0.4 0.1 0.4 0.1 0.4 0.1 0.4
SVS 0.19 SVS 0.19
SDBS  SDBS
2EHA 8 77 8 77 8 77 8 77 8 77 8 77 2EHA 8 77 8 77 8 77 8 77 8 77 8 77
BABA
AN 2 12 2 12 2 12 2 12 2 12 2 12AN 2 12 2 12 2 12 2 12 2 12 2 12
EGDMA 2.5 2.5 2.5 2.5 2.5 ᅳ 2ᅳ.— 5—EGDMA 2.5 2.5 2.5 2.5 2.5 ᅳ 2 ᅳ .— 5—
ITA 3 3 1 1 1ITA 3 3 1 1 1
AA 5.5 5.5 5.5 7.5 5.5 MA 2 8.5AA 5.5 5.5 5.5 7.5 5.5 MA 2 8.5
GMA 2GMA 2
NMAA NMAA
[표 2] TABLE 2
Figure imgf000020_0001
상기 표 1 및 2에 있어서, APS는 암모늄퍼설페이트를， SLS는 소디움 라우릴 설페이트를， SVS는 소디움 4-바이닐벤젠술포네이트를, SDBS는 소디움 도데실벤젠술포네이트를， 2EHA는 2-에틸핵실아크릴레이트를, BA는 부틸아크릴레이트를， AN은 아크릴로나이트릴을， EGDMA는 에틸렌 글리콜 디메타크릴레이트를， ITA는 이타콘산을， M는 아크릴산을， MA는 메타크릴산
Figure imgf000020_0001
In Tables 1 and 2, APS is ammonium persulfate, SLS is sodium lauryl sulfate, SVS is sodium 4-vinylbenzenesulfonate, SDBS is sodium dodecylbenzenesulfonate, and 2EHA is 2-ethylnuclear chamber. Acrylate, BA is butyl acrylate, AN is acrylonitrile, EGDMA is ethylene glycol dimethacrylate, ITA is itaconic acid, M is acrylic acid, MA is methacrylic acid
GMA는 글리시딜 메타크릴레이 를_，ᅳ NMM는 _ r ^ᅵ -틸-을의" -릴—。 -미 를——작 -작一 나타낸다. [실험예] GMA stands for glycidyl methacrylate, and NMM stands for "tilt-". Experimental Example
1. 접착력 평가  1. Evaluation of adhesion
본 발명의 실시예 1 내지 8과 비교예 1 내지 3의 바인더를 이용하여 제조된 전극에서 활물질과 집전체와의 접착력을 평가하기 위해서， 하기와 같은 실험을 실시하였다.  In order to evaluate the adhesion between the active material and the current collector in the electrode manufactured using the binders of Examples 1 to 8 and Comparative Examples 1 to 3 of the present invention, the following experiment was performed.
셀로판 테이프에 전극을 폭 1.5cm , 길이 21cm의 직사각형으로 베어 부착시킨 다음， 집전체를 벗겨내며 180° 벗김 강도를 측정하였다. 평가는 3개 이상의 벗김 강도를 측정하여 평균값으로 정하였다. 이의 결과는 도 1에 나타내었다. The electrode was attached to the cellophane tape in a rectangular shape having a width of 1.5 cm and a length of 21 cm. Then, the current collector was peeled off and 180 ° peel strength was measured. Evaluation was made into the average value by measuring three or more peeling strengths. The results are shown in FIG.
2. 전지 성능 평가 2. Battery Performance Evaluation
본 발명에 따라 제조된 바인더를 이용한 리튬 이차 전지의 특성을 평가하기 위해， 코인형 전지를 제조하여 실시예 및 비교예의 전극의 용량 및 수명 특성을 평가하였다.  In order to evaluate the characteristics of the lithium secondary battery using the binder prepared according to the present invention, a coin-type battery was manufactured to evaluate the capacity and life characteristics of the electrodes of Examples and Comparative Examples.
수명 특성의 경우 25 °C에서 0. 1C의 정전류법에 의해 충방전을 반복하여 10사이클째부터 50사이클째의 방전용량을 측정하였다. 실시예 1 내지 7 및 비교예 1 내지 3의 수명 특성 평가 결과는 도 2에 나타내었다. In the case of the life characteristics, charging and discharging were repeated by a constant current method of 0.1 C at 25 ° C., and the discharge capacity of the 10th to 50th cycles was measured. The life characteristics evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in FIG. 2.
용량 특성은 수명특성과 마찬가지로 하여 2.0V로부터 4.5V까지 층방전 속도에 따른 방전용량을 측정하였다. 실시예 1 내지 7 및 비교예 1 내지 3의 용량 특성 평가 결과는 도 3에 나타내었다.  The capacity characteristics were measured in the same manner as the life characteristics, and the discharge capacity was measured according to the layer discharge rate from 2.0V to 4.5V. Capacity characteristics evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in FIG. 3.
상기 실시예 및 비교예의 분석 결과와 같이， 본 발명의 수계 바인더의 경우 결착력 및 전기화학적 특성이 매우 우수함을 알 수 있다.  As shown in the analysis results of the examples and comparative examples, it can be seen that the binding and electrochemical properties of the aqueous binder of the present invention are very excellent.

Claims

【특허청구범위】 【Patent Claims】
【청구항 1】 【Claim 1】
( a) 아크릴계 단량체 및 α , β -불포화 나이트릴 화합물를 포함하는 제 1 단량체 조성물을 중합하여 시드 폴리머를 제조하는 게 1단계 ; 및 (a) Step 1: preparing a seed polymer by polymerizing a first monomer composition containing an acrylic monomer and an α, β-unsaturated nitrile compound; and
(b) 상기 시드 폴리머에， 아크릴계 단량체， α , β -불포화 나이트릴 화합물 및 접착력 강화 단량체를 포함하는 제 2 단량체 조성물을 첨가하고 중합하여 바인더 입자를 제조하는 제 2단계; (b) a second step of preparing binder particles by adding and polymerizing a second monomer composition containing an acrylic monomer, an α, β-unsaturated nitrile compound, and an adhesion enhancing monomer to the seed polymer;
를 포함하는 이차전지 양극활물질용 수계 바인더의 제조방법. A method of manufacturing an aqueous binder for a secondary battery cathode active material comprising.
【청구항 2】 【Claim 2】
제 1 항에 있어서， 상기 게 1 단계 및 제 2 단계의 중합은 중합 개시제의 존재 하에 진행되는, 이차전지 양극활물질용 수계 바인더의 제조방법. . The method of claim 1, wherein the first and second polymerization steps are carried out in the presence of a polymerization initiator. .
【청구항 3】 【Claim 3】
제 1항에 있어서， In clause 1,
상기 제 1 단량체 조성물 및 제 2단량체 조성물은 각각 물; 및 유화거)， 가교제 또는 이들의 흔합물；을 더 포함하는, 이차전지 양극활물질용 수계 바인더의 제조방법 . The first monomer composition and the second monomer composition each contain water; and emulsifying agent), a crosslinking agent, or a mixture thereof; a method for producing an aqueous binder for a secondary battery cathode active material.
【청구항 4】 【Claim 4】
제 3항에 있어서， 상기 가교제는 제 1단계 및 게 2단계에서 사용되거나， 또는 제 1단계 또는 제 2단계 중 어느 한 단계에서만 사용되는， 이차전지 양극활물질용 수계 바인더의 제조방법. The method of claim 3, wherein the crosslinking agent is used in the first step and the second step, or is used only in one of the first step and the second step.
【청구항 5】 - 거 U항에 있어서， 【Claim 5】 - In clause U,
상기 제 1단계는 중합 반응 온도 30 내지 150°C 및 중합시간 0 JL시간 내지 10 시간의 조건에서 증합을 진행하는, 이차전지 양극활물질용 수계 바인더의 제조방법. The first step is a method of producing an aqueous binder for a secondary battery cathode active material, wherein the polymerization is carried out under the conditions of a polymerization reaction temperature of 30 to 150 ° C and a polymerization time of 0 JL hours to 10 hours.
【청구항 6】 【Claim 6】
제 1항에 있어서， . In paragraph 1, .
상기 제 2단계는 중합 반웅 온도 30 내지 150 °C 및 증합시간 0.5시간 내지 24 시간의 조건에서 중합을 진행하는， 이차전지 양극활물질용 수계 바인더의 제조방법. The second step is a method of producing an aqueous binder for a secondary battery cathode active material, in which polymerization is carried out under the conditions of a polymerization reaction temperature of 30 to 150 ° C and a polymerization time of 0.5 hours to 24 hours.
【청구항 7】 【Claim 7】
제 1항에 있어서， In clause 1,
상기 제 1단계 및 게 2단계에서， 상기 아크릴계 단량체의 함량은 각각 제 1단량체 조성물 또는 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 30 내지 90 중량부인， 이차전지 양극활물질용 수계 바인더의 제조방법. In the first step and the second step, the content of the acrylic monomer is 30 to 90 parts by weight based on 100 parts by weight of the total weight of the first monomer composition or the second monomer composition, respectively. Production of an aqueous binder for a secondary battery cathode active material method.
【청구항 8】 【Claim 8】
제 1항에 있어서， In clause 1,
상기 제 1단계 및 게 2단계에서, 상기 α , β -불포화 나이트릴 화합물의 In the first step and the second step, the α, β -unsaturated nitrile compound
"함량은 각각 제 1단량체 조성물 또는 제 2단량체 조성물의 층 중량의 100 중량부를 기준으로 당 1 내지 50 중량부인， 이차전지 양극활물질용 수계 바인더의 제조방법. " A method for producing an aqueous binder for a secondary battery cathode active material, wherein the content is 1 to 50 parts by weight based on 100 parts by weight of the layer weight of the first monomer composition or the second monomer composition, respectively.
【청구항 9】 【Claim 9】
제 1항에 있어서, According to clause 1,
상기 제 2단계에서， 상기 시드 폴리머의 함량은 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 1 내지 70 중량부인， 이차전지 양극활물질용 수계 바인더의 제조방법 . In the second step, the content of the seed polymer is 1 to 70 parts by weight based on 100 parts by weight of the second monomer composition, a method for producing an aqueous binder for a secondary battery positive electrode active material.
【청구항 10] [Claim 10]
제 3 항에 있어서， According to clause 3,
상기 유화제는 제 1단량체 조성물 또는 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 0.01 내지 5 중량부로 사용하는 이차전지 양극활물질용 수계 바인더의 제조방법 . The emulsifier is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the first monomer composition or the second monomer composition.
【청구항 11】 【Claim 11】
제 1항에 있어서, According to clause 1,
상기 접착력 강화 단량체의 함량은 제 2단량체 조성물의 충 중량의 100 중량부를 기준으로 1 내지 40 중량부인， 이차전지 양극활물질용 수계 바인더의 제조방법. The content of the adhesion-enhancing monomer is 1 to 40 parts by weight based on 100 parts by weight of the second monomer composition, a method for producing an aqueous binder for a secondary battery cathode active material.
【청구항 12] [Claim 12]
제 1항에 있어서, According to clause 1,
상기 가교제의 함량은 게 2단량체 조성물의 충 중량의 100 중량부를 기준으로 0. 1 내지 20 중량부인， 이차전지 양극활물질용 수계 바인더의 제조방법. The content of the cross-linking agent is 0.1 to 20 parts by weight based on 100 parts by weight of the crab bimonomer composition, a method for producing an aqueous binder for a secondary battery positive electrode active material.
【청구항 13】 【Claim 13】
제 1항에 있어서， In clause 1,
상기 시드 폴리머는 유리전이온도 (Tg)가 -i(xrc 내지 lcxrc이고, 평균 입자 직경이 10 내지 1500 nm인， 이차전지 양극활물질용 수계 바인더의 제조방법. The seed polymer has a glass transition temperature (T g ) of -i(xrc to lcxrc) and an average particle diameter of 10 to 1500 nm. A method of producing an aqueous binder for a secondary battery cathode active material.
【청구항 14】 【Claim 14】
제 1항에 있어서, According to clause 1,
상기 아크릴계 단량체는 탄소수 4 내지 20의 아크릴산 에스테르계 단량체 및 메타크릴산 에스테르계 단량체 중에서 선택되는 1종 이상인， 이차전지 양극활물질용 수계 바인더의 제조방법. The acrylic monomer is a method of producing an aqueous binder for a secondary battery positive electrode active material, wherein the acrylic monomer is at least one selected from acrylic acid ester monomer and methacrylic acid ester monomer having 4 to 20 carbon atoms.
【청구항 15】 【Claim 15】
제 1항에 있어서， In clause 1,
상기 α , β -불포화 나이트릴 화합물은 아크릴로나이트릴， 메타크릴로나이트릴， 염화나이트릴 및 플루오르화나이트릴로 이루어진 군에서 선택된 1종 이상인 이차전지 양극활물질용 수계 바인더의 제조방법. The α, β-unsaturated nitrile compound is a method of producing an aqueous binder for a secondary battery cathode active material, wherein the α, β-unsaturated nitrile compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, nitrile chloride, and nitrile fluoride.
【청구항 16】 제 3 항에 있어서, 상기 유화제는 【Claim 16】 The method of claim 3, wherein the emulsifier is
소디움 4-비닐벤젠술포네이트, 소디움 메타알릴술포네이트， 소디움 알릴술포네이트， 소디움 도데실벤젠술포네이트 및 소디움 비닐술포네이트로 이루어진 군에서 선택된 1종 이상의 화합물， 소디움 라우릴 설페이트， 소디움 라우레스 설페이트， 암모늄 라우릴 설페이트, 암모늄 라우레스 설페이트， 트리에탄을아민 라우릴 설페이트 및 소디움 트라이폴리포스페이트로 이루어진 군에서 선택된 1종 이상인， 이차전지 양극활물질용 수계 바인더의 제조방법. Sodium 4-vinylbenzenesulfonate, sodium methallylsulfonate, sodium allylsulfonate, at least one compound selected from the group consisting of sodium dodecylbenzenesulfonate and sodium vinylsulfonate, sodium lauryl sulfate, sodium laureth sulfate, A method for producing an aqueous binder for a secondary battery positive electrode active material, which is at least one selected from the group consisting of ammonium lauryl sulfate, ammonium laureth sulfate, triethane amine lauryl sulfate, and sodium tripolyphosphate.
【청구항 17】 【Claim 17】
제 1항에 있어서， In clause 1,
상기 접착력 강화 단량체는 불포화 모노카르본산계 단량체; 불포화 디카르본산계 단량체; 아크릴아미드계 단량체; 및 에폭시계 단량체로 이루어진 군에서 선택된 1종 이상인 이차전지 양극활물질용 수계 바인더의 제조방법. The adhesion enhancing monomer is an unsaturated monocarboxylic acid monomer; Unsaturated dicarboxylic acid monomer; Acrylamide-based monomer; and a method for producing an aqueous binder for a secondary battery cathode active material, which is at least one selected from the group consisting of epoxy-based monomers.
【청구항 18】 【Claim 18】
제 1항에 있어서， In clause 1,
상기 가교제 및 그래프팅 에이전트는 에틸렌 글리콜 디메타크릴레이트， 디에틸렌 글리콜 디메타크릴테이트, 트리에틸렌 글리콜 디메타크릴레이트， 테트라에틸렌글리콜 디아크릴레이트, 테트라에틸렌글리콜 디메타크릴레이트， 폴리 에틸렌 글리콜 디메타크릴에이트， 폴리 프로필렌 글리콜 디메타크릴레이트, 폴리 부틸렌 글리콜 디아크릴레이트， 1，3-부타디을 디아크릴레이트， 1 , 3- 부타디올 디메타크릴레이트， 1， 4ᅳ부타디을 디아크릴레이트， 1 , 4—부타디을 디메타크릴레이트， 1 , 6-헥산디올 디메타크릴레이트， 아릴 아크릴레이트， 아릴 메타크릴레이트, 트리아릴 이소시아누레이트， 트리아릴 아민， 디아릴 아민， 트리메틸을프로판 트리메타크릴레이트， 트리메틸을메탄 트리아크릴레이트， 스티렌， α -메틸스티렌， -메틸스티렌， p— t—부틸스티렌 및 디비닐벤젠으로 이루어진 군에서 선택된 1종 이상인 이차전지 양극활물질용 수계 바인더의 제조방법. The crosslinking agent and grafting agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. Crylate, polypropylene glycol dimethacrylate, polybutylene glycol diacrylate, 1,3-butadiol diacrylate, 1,3-butadiol dimethacrylate, 1,4-butadiol diacrylate, 1, 4—butadyl dimethacrylate, 1,6-hexanediol dimethacrylate, aryl acrylate, aryl methacrylate, triaryl isocyanurate, triaryl amine, diaryl amine, trimethylpropane trimethylamine Method for producing an aqueous binder for a secondary battery cathode active material selected from the group consisting of methacrylate, trimethylmethane triacrylate, styrene, α-methylstyrene, -methylstyrene, p—t—butylstyrene, and divinylbenzene. .
【청구항 19】 제 1항에 있어서' 【Claim 19】 In paragraph 1'
상기 제 1 단량체 조성물 및 게 2 단량체 조성물은 각각 분자량 조절제， 완충제 및 왁스로 이루어진 군에서 선택된 1종 이상의 첨가제를 더 포함하는， 이차전지 양극활물질용 수계 바인더의 제조방법. The first monomer composition and the second monomer composition each further include one or more additives selected from the group consisting of molecular weight regulators, buffers, and waxes.
【청구항 20】 【Claim 20】
제 1항에 따른 방법으로 제조되며， 유리전이은도 (Tg)가 ᅳ ioo°c 내지 It is manufactured by the method according to claim 1, and has a glass transition (Tg) of ᅳ ioo°c to
100 °C인， 상호 침투성 고분자 네트워크 ( Interpenetrat ing Polymer Network : IPN) 또는 세미 -상호 침투성 고분자 네트워크 (Semi-interpenetrat i on Polymer Network: SIPN)의 구조를 갖는 이차전지 양극활물질용 수계 바인더 . An aqueous binder for secondary battery cathode active materials having the structure of an interpenetrating polymer network (IPN) or semi-interpenetrating polymer network (SIPN) at 100 ° C.
【청구항 21】 【Claim 21】
제 20항에 있어서， In clause 20,
평균 입자 직경이 80 내지 4000nm인 이차전지 양극활물질용 수계 바인더. An aqueous binder for secondary battery cathode active material with an average particle diameter of 80 to 4000 nm.
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