Hydrogenated nitrile-based latex, manufacturing method therefor, and conductive material dispersion

Abstract

The present invention relates to a hydrogenated nitrile-based latex comprising a hydrogenated nitrile-based copolymer having low molecular weight characteristics, excellent processability, and superb wettability and dispersibility with respect to a conductive material, a manufacturing method therefor, and a conductive material dispersion, and provides a hydrogenated nitrile-based latex comprising a hydrogenated nitrile-based copolymer having an oxime content of 0.1 wt% to 6.5 wt%, a manufacturing method therefor, and a conductive material pre-dispersion.

Description

Hydrogenated nitrile latex, its manufacturing method and conductive dispersion

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0032865, filed March 7, 2024, the entire contents of which are incorporated herein by reference.

[0003] [Technical Field]

[0004] The present invention relates to a hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer having low molecular weight characteristics, excellent processability, and excellent wettability and dispersibility for a conductive material, a method for producing the same, and a conductive material dispersion comprising the hydrogenated nitrile copolymer.

[0005]

[0006] Secondary batteries are batteries that can be used repeatedly through a discharge process in which chemical energy is converted into electrical energy and a charge process in the reverse direction. Secondary batteries are composed of a positive electrode, a negative electrode, an electrolyte, and a separator. The positive and negative electrodes are generally composed of an electrode current collector and an electrode active material layer formed on the electrode current collector. The electrode active material layer is manufactured by applying an electrode slurry composition containing an electrode active material, a conductive material, a binder, etc., onto the electrode current collector, drying it, and then rolling it.

[0007] Although various materials can be used as the above-mentioned conductive material, technology that uses carbon nanotubes as conductive material to maximize conductivity has recently been attracting attention.

[0008] However, since carbon nanotubes are not uniformly dispersed in electrode slurry and easily aggregate, there is a problem in that the conductive material is not evenly distributed within the electrode active material layer when forming an electrode using them. To solve this problem, a method has been developed in which a conductive material dispersion is first prepared by mixing the conductive material dispersion with a solvent together with a dispersant such as polyvinyl pyrrolidone (PVP), hydrogenated acrylonitrile-butadiene rubber, etc., and then applying the conductive material dispersion to the electrode slurry.

[0009] However, since the viscosity of the conductive dispersion using the PVP dispersant increases rapidly as the conductive content increases, there is a limit to increasing the conductive content, and thus the improvement in electrical conductivity is limited.

[0010] In addition, when using a general hydrogenated acrylonitrile-butadiene rubber, there is a problem that the viscosity of the conductive dispersion increases excessively during the storage process of the manufactured conductive dispersion, and when the conductive dispersion is exposed to a high temperature during the manufacture of the electrode slurry, there is a problem that the viscosity of the electrode slurry increases excessively. In addition, when the viscosity of the conductive dispersion increases, a problem of the electrode slurry remaining inside the pipe may occur during the storage and transport process of the electrode slurry manufactured using the conductive dispersion, and as a result, it becomes difficult to control the discharge of the electrode slurry, which lowers the coating processability.

[0011] Meanwhile, hydrogenated acrylonitrile-butadiene rubber is manufactured through a hydrogenation reaction of nitrile rubber, a polymer manufactured by copolymerizing an ethylenically unsaturated nitrile monomer such as acrylonitrile and a conjugated diene monomer such as 1,3-butadiene. It is a special rubber with excellent heat resistance, ozone resistance, chemical resistance, and oil resistance, and is widely used in various fields such as timing belts, seals, hoses, diaphragms, and rolls.

[0012] The current commercially available hydrogenated acrylonitrile-butadiene rubber (ABR) is manufactured by dissolving nitrile rubber in a solvent, reacting it with gaseous hydrogen under high temperature and pressure conditions in the presence of a precious metal catalyst to hydrogenate the double bonds within the ABR, and then removing the catalyst and solvent. This process is complex, expensive due to the use of a high-pressure reactor and precious metal catalyst, and presents environmental concerns due to the use of solvents, as well as the requirement for using only bulk rubber.

[0013] Another method, which uses diimide to hydrogenate nitrile rubber in the latex state, offers advantages not only in safety but also in economic and environmental aspects compared to the existing process that uses hydrogen, solvents, and expensive precious metal catalysts at high pressure. However, despite these various advantages, commercialization is currently hindered due to gel formation as a side reaction during hydrogenation. Furthermore, crosslinking occurs during and after the hydrogenation reaction and during the drying and storage stages, which negatively affects the properties of the final hydrogenated nitrile rubber latex.

[0014]

[0015] Accordingly, there is a need for a hydrogenated nitrile latex and a method for producing the same that has a low molecular weight and a high degree of hydrogenation, has a low viscosity increase even when stored for a long time or exposed to high temperatures, and can improve the dispersibility of a conductive agent.

[0016] [Prior Art Literature]

[0017] [Patent Document]

[0018] (Patent Document 1) KR 10-2023-0022000 A (February 14, 2023)

[0019]

[0020] The present invention aims to provide a hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer having a controlled oxime content or residual double bond content, a weight average molecular weight, and an oxime content, which can improve the stability and viscosity characteristics of a conductive dispersion while enhancing the conductive dispersion property when applied to the conductive dispersion.

[0021] The purpose of the present invention is to provide a method for producing a hydrogenated nitrile latex comprising the hydrogenated nitrile copolymer.

[0022] In addition, the present invention aims to provide a conductive dispersion comprising the hydrogenated nitrile copolymer.

[0023]

[0024] In order to solve the above problem, the present invention provides a hydrogenated nitrile latex including a hydrogenated nitrile copolymer, a method for producing the same, and a conductive dispersion.

[0025] (1) The present invention provides a hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer having an oxime content of 0.1 wt% or more and 6.5 wt% or less.

[0026] (2) The present invention provides a hydrogenated nitrile-based latex in the above (1), wherein the hydrogenated nitrile-based copolymer has an oxime content of 0.5 wt% or more and 6.0 wt% or less.

[0027] (3) The present invention provides a hydrogenated nitrile-based latex in the above (1) or (2), wherein the hydrogenated nitrile-based copolymer has a residual double bond content of 40 wt% or less.

[0028] (4) The present invention provides a hydrogenated nitrile-based latex in any one of the above (1) to (3), wherein the hydrogenated nitrile-based copolymer has a residual double bond content of 10 wt% or less.

[0029] (5) The present invention provides a hydrogenated nitrile-based latex according to any one of the above (1) to (4), wherein the hydrogenated nitrile-based copolymer has a weight average molecular weight of 200,000 g / mol or less.

[0030] (6) The present invention provides a hydrogenated nitrile-based latex according to any one of the above (1) to (5), wherein the hydrogenated nitrile-based copolymer has a weight average molecular weight of 100,000 g / mol or less.

[0031] (7) The present invention provides a hydrogenated nitrile-based latex according to any one of the above (1) to (6), wherein the hydrogenated nitrile-based copolymer has a weight average molecular weight of 50,000 g / mol or less.

[0032] (8) The present invention provides a hydrogenated nitrile latex according to any one of the above (1) to (7), wherein the hydrogenated nitrile copolymer has a solvent displacement viscosity of 10 cps or more and 200 cps or less, and the solvent displacement viscosity is measured using a Brookfield viscometer (#63 spin, 25°C) for a solution in which the hydrogenated nitrile copolymer is dissolved in an amide dispersion medium at 16 wt%.

[0033] (9) The present invention provides a hydrogenated nitrile-based latex, wherein the hydrogenated nitrile-based copolymer has a residual double bond content of 3 wt% or less, a weight average molecular weight of 5,000 g / mol or more and 30,000 g / mol or less, an oxime content of 0.9 wt% or more and 5.5 wt% or less, and a solvent substitution viscosity of 10 cps or more and 50 cps or less, in any one of the above (1) to (8).

[0034] (10) The present invention provides a hydrogenated nitrile latex, wherein the hydrogenated nitrile copolymer comprises an ethylenically unsaturated nitrile monomer unit and a hydrogenated conjugated diene monomer unit, in any one of the above (1) to (9).

[0035] (11) The present invention provides a hydrogenated nitrile-based latex in the above (10), wherein the hydrogenated nitrile-based copolymer comprises an ethylenically unsaturated nitrile-based monomer unit; and a hydrogenated conjugated diene-based monomer unit in a weight ratio of 28:72 to 39:61.

[0036] (12) The present invention provides a hydrogenated nitrile latex, wherein the hydrogenated nitrile copolymer further includes a conjugated diene monomer unit in (10) or (11).

[0037] (13) The present invention provides a method for producing a hydrogenated nitrile latex according to any one of (1) to (12) above, including a step (S1) of producing a nitrile copolymer by polymerizing a monomer mixture including a conjugated diene monomer and an ethylenically unsaturated nitrile monomer in the presence of an emulsifier; a step (S2) of hydrogenating the nitrile copolymer to produce a hydrogenated nitrile copolymer; and a step (S3) of ozonolysis and oximation of the hydrogenated nitrile copolymer, wherein the step (S3) is performed by bubbling a mixture of air and ozone through the hydrogenated nitrile copolymer and adding dropwise 0.05 mol to 0.40 mol of hydroxyamine, and wherein the mixture of air and ozone includes 0.3 mol to 0.7 mol of ozone.

[0038] (14) The present invention provides a method for producing a hydrogenated nitrile-based latex, wherein in the step (S3), hydroxylamine is added dropwise to the hydrogenated nitrile-based copolymer in an amount of 60 wt% or more of the total amount of hydroxylamine input simultaneously with bubbling of a mixture of air and ozone, and the remaining amount of the total amount input is added dropwise after completion of the bubbling.

[0039] (15) The present invention provides a method for producing a hydrogenated nitrile latex, wherein in the step (S1), the monomer mixture comprises 28 wt% or more and 39 wt% or less of an ethylenically unsaturated nitrile monomer in the above (13) or (14).

[0040] (16) The present invention provides a method for producing a hydrogenated nitrile-based latex, wherein the hydrogenation in step (S2) is performed in the presence of an oxidizing agent and a reducing agent in the nitrile-based copolymer in any one of the above (13) to (15).

[0041] (17) The present invention provides a method for producing a hydrogenated nitrile latex, wherein the step (S3) is performed at a temperature of 0°C to 75°C in any one of the above (13) to (16).

[0042] (18) The present invention provides a conductive dispersion comprising a conductive material, a dispersion medium, and a hydrogenated nitrile copolymer, wherein the hydrogenated nitrile copolymer has an oxime content of 0.1 wt% or more and 6.5 wt% or less.

[0043] (19) The present invention provides a conductive dispersion in (18) above, wherein the hydrogenated nitrile copolymer has a residual double bond content of 40 wt% or less and a weight average molecular weight of 100,000 g / mol or less.

[0044] (20) The present invention provides a conductive dispersion in (18) or (19), wherein the hydrogenated nitrile copolymer has a solvent substitution viscosity of 10 cps or more and 200 cps or less, and the solvent substitution viscosity is measured using a Brookfield viscometer (#63 spin, 25°C) for a solution in which the hydrogenated nitrile copolymer is dissolved in an amide dispersion medium at 16 wt%.

[0045] (21) The present invention provides a conductive dispersion having a viscosity of 1500 Pa.s or more and 2,500 Pa.s or less in any one of the above (18) to (20).

[0046] (22) The present invention relates to a particle size distribution [(D) in any one of the above (18) to (21) 90 -D 10 ) / D 50 ] provides a challenge dispersion having 1 to 2.

[0047] (23) The present invention provides a conductive material dispersion in any one of the above (18) to (22), wherein the conductive material is at least one selected from the group consisting of carbon black, Ketjen black, fullerene, graphene, carbon nanotubes, carbon black, and graphite.

[0048]

[0049] The hydrogenated nitrile latex according to the present invention has an oxime content of 0.1 wt% or more and 6.5 wt% or less, and further includes a hydrogenated nitrile copolymer having a low residual double bond content and molecular weight, thereby having excellent processability, low viscosity, and excellent dispersibility.

[0050] The method for producing a hydrogenated nitrile latex according to the present invention performs an ozonolysis reaction with a controlled ozone content, and introduces an oxime group through an oximation reaction, thereby producing a low molecular weight and low viscosity hydrogenated nitrile latex having excellent processability, low viscosity, and excellent dispersibility.

[0051] The conductive dispersion according to the present invention has excellent stability by including the hydrogenated nitrile copolymer, excellent initial and long-term storage viscosity characteristics, and excellent conductive dispersion properties.

[0052]

[0053] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0054]

[0055] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0056]

[0057] Terminology

[0058] In this specification, the term 'latex' may mean a polymer or copolymer polymerized by polymerization that exists in a dispersed form in water or a solvent, and as a specific example, it means a polymer or copolymer of rubber polymerized by polymerization that exists in a colloidal state dispersed in a solvent, and may also be expressed as an 'emulsion'.

[0059]

[0060] Hydrogenated nitrile latex

[0061] The present invention provides a hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer having a low molecular weight and low viscosity.

[0062] The hydrogenated nitrile latex according to the present invention includes a hydrogenated nitrile copolymer having an oxime content of 0.1 wt% or more and 6.5 wt% or less.

[0063] In addition, the hydrogenated nitrile copolymer may have a residual double bond content of 40 wt% or less and a weight average molecular weight of 200,000 g / mol or less, or a residual double bond content of 40 wt% or less and a weight average molecular weight of 100,000 g / mol or less.

[0064] In addition, the residual double bond content according to the present invention may be 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, or 1 wt% or less. When the residual double bond content of the hydrogenated nitrile copolymer according to the present invention is within the above range, it can be applied to a conductive dispersion to improve the stability of the dispersion, and thus has the effect of alleviating changes in viscosity due to high temperature and light.

[0065] In addition, the hydrogenated nitrile copolymer according to the present invention may have a weight average molecular weight of 200,000 g / mol or less, 100,000 g / mol or less, 80,000 g / mol or less, 50,000 g / mol or less, or 30,000 g / mol or less, and may be 1,000 g / mol or more, 2,000 g / mol or more, 3,000 g / mol or more, 4,000 g / mol or more, or 5,000 g / mol or more. When the weight average molecular weight of the hydrogenated nitrile copolymer according to the present invention is within the above range, it can be applied to a conductive material dispersion to improve the dispersibility of the conductive material.

[0066] In addition, the oxime content according to the present invention may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 1.0 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, 3.0 wt% or more, or 3.5 wt% or more, and may be 6.5 wt% or less, 6.0 wt% or less, or 5.5 wt% or less. When the oxime content of the hydrogenated nitrile-based copolymer according to the present invention is within the above range, the hydrogenated nitrile-based latex containing it can have low molecular weight and low viscosity characteristics while being applied to a conductive material dispersion to improve the conductive material dispersibility.

[0067] In addition, according to the present invention, the hydrogenated nitrile copolymer may have a solvent displacement viscosity of 10 cps or more and 200 cps or less, and the solvent displacement viscosity is measured using a Brookfield viscometer (#63 spin, 25°C) for a solution in which the hydrogenated nitrile copolymer is dissolved in an amide dispersion medium at 16 wt%.

[0068] In addition, the solvent substitution viscosity according to the present invention may be 10 cps or more or 20 cps or more, and may be 200 cps or less, 180 cps or less, 160 cps or less, 140 cps or less, 120 cps or less, 100 cps or less, 80 cps or less, 60 cps or less, or 50 cps or less.

[0069] Here, 1,000 cps is equal to 1 Pa.s.

[0070]

[0071] In addition, the hydrogenated nitrile copolymer may satisfy a molecular weight distribution of 1.0 or more and 4.0 or less, and specifically, the molecular weight distribution may be 1.5 or more and 4.0 or less, 1.5 or more and 3.5 or less, 1.5 or more and 3.0 or less, or 1.5 or more and 2.5 or less.

[0072]

[0073] In addition, according to the present invention, the hydrogenated nitrile copolymer may have a residual double bond content of 3 wt% or less, a weight average molecular weight of 5,000 g / mol or more and 30,000 g / mol or less, an oxime content of 0.9 wt% or more and 5.5 wt% or less, and a solvent substitution viscosity of 10 cps or more and 50 cps or less, and in this case, a hydrogenated nitrile latex containing the same may have low molecular weight and low viscosity characteristics while being applied to a conductive material dispersion to improve dispersion stability and conductive material dispersibility.

[0074]

[0075] In general, hydrogenated nitrile copolymers are manufactured through a hydrogenation reaction of nitrile copolymers. The current commercialized manufacturing process of hydrogenated nitrile copolymers involves dissolving the nitrile copolymer in a solvent, reacting it with gaseous hydrogen under high temperature and high pressure conditions and in the presence of a noble metal catalyst to hydrogenate the double bonds in the nitrile copolymer, and then removing the used catalyst and solvent. If a small amount of the noble metal catalyst is used, the hydrogenation rate is low and the molecular weight of the hydrogenated nitrile copolymer produced is high, which reduces dispersibility and increases viscosity. In addition, if an appropriate amount or a large amount of the noble metal catalyst is used, the amount of metal residue in the hydrogenated nitrile copolymer is large, which increases viscosity due to the residual metal, and requires a high cost to remove the residual metal.

[0076] However, the hydrogenated nitrile latex according to the present invention may be manufactured by a hydrogenation reaction of a nitrile copolymer followed by ozone decomposition and oximation reaction, so that the aldehyde terminal group of the copolymer may be replaced with an oxime group, and thus the oxime content in the molecule may be 0.1 wt% or more and 6.5 wt% or less, and further, the residual double bond content and the weight average molecular weight may satisfy the above conditions, thereby providing low viscosity characteristics and low molecular weight, and thus excellent processability. In addition, since the aldehyde terminal group of the copolymer is replaced with an oxime group, and an oxime group is included at one or both ends of the polymer chain constituting the copolymer, it is included in the conductive material dispersion, and thus debundling of the conductive material (particularly, carbon nanotubes) is facilitated by hydrogen bonding between the rubber and the solvent, thereby improving the stability and dispersibility of the conductive material dispersion.

[0077] In addition, the hydrogenated nitrile copolymer is produced by copolymerizing an ethylenically unsaturated nitrile monomer and a conjugated diene monomer, and is produced by hydrogenating the C=C double bond in the conjugated diene monomer unit of a nitrile rubber including an ethylenically unsaturated nitrile monomer unit and a conjugated diene monomer unit. Accordingly, the hydrogenated nitrile rubber according to the present invention may include an ethylenically unsaturated nitrile monomer unit; and a hydrogenated conjugated diene monomer unit, and may further include a conjugated diene monomer unit.

[0078] Additionally, the weight ratio of the ethylenically unsaturated nitrile monomer unit and the hydrogenated conjugated diene monomer unit may be 28 to 39:61 to 72, or 30 to 38:62 to 70 or 32 to 36:64 to 68.

[0079] The ethylenically unsaturated nitrile monomer forming the above ethylenically unsaturated nitrile monomer unit may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α-chloronitrile, and α-cyano ethyl acrylonitrile. As a specific example, the ethylenically unsaturated nitrile monomer may be acrylonitrile or methacrylonitrile, and more specifically, may be acrylonitrile.

[0080] The above-mentioned hydrogenated conjugated diene monomer unit and the conjugated diene monomer forming the conjugated diene monomer unit may be at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene. As a specific example, the conjugated diene monomer may be 1,3-butadiene.

[0081] In addition, according to the present invention, the hydrogenated nitrile copolymer may further include at least one of an ethylenically unsaturated acid monomer unit and an ethylenically unsaturated monomer unit, as needed.

[0082] The ethylenically unsaturated acid monomer forming the above ethylenically unsaturated acid monomer unit may be an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, or an acid anhydride group. As a specific example, the ethylenically unsaturated acid monomer may include at least one selected from the group consisting of ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; polycarboxylic acid anhydrides such as maleic anhydride and citraconic anhydride; ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid; and ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate. As a more specific example, the ethylenically unsaturated acid monomer may be at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid, and as a more specific example, it may be methacrylic acid. The ethylenically unsaturated acid monomer may also be used in the form of a salt, such as an alkali metal salt or an ammonium salt, during polymerization. The content of the ethylenically unsaturated acid monomer unit may be 1 wt% to 5 wt% based on the total content of the hydrogenated nitrile copolymer.

[0083] In addition, the ethylenically unsaturated monomer forming the ethylenically unsaturated monomer unit is selected from the group consisting of a hydroxyalkyl (meth)acrylate monomer having 1 to 4 carbon atoms; a vinyl aromatic monomer selected from the group consisting of styrene, aryl styrene, and vinyl naphthalene; a fluoroalkyl vinyl ether monomer such as fluoroethyl vinyl ether; an ethylenically unsaturated amide monomer selected from the group consisting of (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylol (meth)acrylamide, N-methoxy methyl (meth)acrylamide, and N-propoxy methyl (meth)acrylamide; a non-conjugated diene monomer such as vinyl pyridine, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, dibutyl maleate, dibutyl fumarate, diethyl maleate, methoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, cyanomethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 1-cyanopropyl (meth)acrylate, 2-ethyl-6-cyanohexyl (meth)acrylate, 3-cyanopropyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, It may include at least one selected from the group consisting of ethylenically unsaturated carboxylic acid ester monomers selected from the group consisting of glycidyl (meth)acrylate, and dimethylamino ethyl (meth)acrylate. The content of the ethylenically unsaturated monomer unit may be 0.5 wt% to 5 wt% based on the total content of the hydrogenated nitrile copolymer.

[0084]

[0085] Method for producing hydrogenated nitrile latex

[0086] The present invention provides a manufacturing method capable of obtaining a hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer having low viscosity and low molecular weight in the absence of a precious metal catalyst.

[0087] A method for producing a hydrogenated nitrile latex according to the present invention comprises the steps of: (S1) polymerizing a monomer mixture including a conjugated diene monomer and an ethylenically unsaturated nitrile monomer in the presence of an emulsifier to produce a nitrile copolymer; (S2) hydrogenating the nitrile copolymer to produce a hydrogenated nitrile copolymer; and (S3) ozonolyzing and oximating the hydrogenated nitrile copolymer. The step (S3) is performed by bubbling a mixture of air and ozone through the hydrogenated nitrile copolymer and adding dropwise 0.05 mol to 0.40 mol of hydroxyamine, and the mixture of air and ozone may include 0.3 mol to 0.7 mol of ozone.

[0088] In addition, in the step (S3), the hydroxylamine may be added dropwise to the hydrogenated nitrile copolymer in an amount of 60 wt% or more of the total amount of hydroxylamine input simultaneously with bubbling of the mixture of air and ozone, and the remaining amount of the total amount input may be added dropwise after the bubbling is completed.

[0089] Here, the monomers used in the production of the nitrile copolymer are as described above.

[0090]

[0091] Hereinafter, the method for manufacturing the hydrogenated nitrile latex according to the present invention will be described in more detail step by step.

[0092]

[0093] (S1) Step

[0094] The above step (S1) is a step for producing a nitrile copolymer by copolymerizing a conjugated diene monomer and an ethylenically unsaturated nitrile monomer, and can be performed by polymerizing a monomer mixture including the conjugated diene monomer and the ethylenically unsaturated nitrile monomer in the presence of an emulsifier. In addition, the monomer mixture may include the ethylenically unsaturated nitrile monomer in an amount of 28 wt% or more and 39 wt% or less, 30 wt% or more and 38 wt% or less, or 32 wt% or more and 36 wt% or less, in which case the residual double bond content of the hydrogenated nitrile copolymer obtained therefrom may be advantageously controlled within the above-mentioned range.

[0095] Here, the polymerization may be performed through conventional emulsion polymerization, and the emulsifier may be at least one fatty acid salt selected from the group consisting of oleic acid, rosin acid, lauric acid, myristic acid, palmitic acid, stearic acid, naphthalene sulfonic acid, and eicosanoic acid; at least one sulfonate emulsifier selected from the group consisting of sulfosuccinate emulsifiers, disulfonate emulsifiers, and linear alkylbenzene sulfonate emulsifiers, and mixtures thereof.

[0096] In addition, the polymerization can be further carried out using additives such as a polymerization initiator and a molecular weight regulator, and the polymerization initiator is an inorganic peroxide such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; an organic peroxide such as t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutyrate; One or more selected from the group consisting of azobis compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (methyl butyrate) can be used.

[0097] In addition, the molecular weight regulator may be at least one selected from the group consisting of n-octyl mercaptan, n-dodecyl mercaptan, n-decyl mercaptan, t-dodecyl mercaptan, 2,2,4,6,6-pentamethylheptane-4-thiol, and 2,2,4,6,6,8,8-heptamethylnonane-4-thiol.

[0098] In addition, during the polymerization, additives such as activators, chelating agents, dispersants, pH regulators, deoxidizers, particle size regulators, anti-aging agents, and oxygen scavengers may be used within a range that does not deteriorate the physical properties of the rubber, as needed.

[0099] Additionally, the polymerization can be carried out at a temperature range of 10°C to 90°C or a temperature range of 10°C to 75°C.

[0100] In addition, after the polymerization, a polymerization terminator may be added to terminate the polymerization, and the polymerization terminator may be one commonly used in the art, and may include, for example, aromatic hydroxy dithiocarboxylic acids such as hydroxyl amine, N,N-diethyl hydroxylamine, hydroxy amine sulfate, diethyl hydroxy amine, hydroxy amine sulfonic acid and alkali metal ions thereof, sodium dimethyl dithiocarbamate, hydroquinone derivatives, hydroxy diethyl benzene dithiocarboxylic acid, and hydroxy dibutyl benzene dithiocarboxylic acid.

[0101] In addition, after the polymerization, the nitrile-based latex may be obtained in a hydrogenated state, or a conventional post-treatment process may be performed, and a nitrile-based copolymer may be obtained by performing at least one post-treatment process selected from among coagulation, solvent removal or precipitation, and drying.

[0102]

[0103] (S2) Step

[0104] The above step (S2) is a step for producing a hydrogenated nitrile copolymer by hydrogenating the nitrile copolymer produced above, and the hydrogenation can be performed in the presence of an oxidizing agent and a reducing agent.

[0105] The oxidizing agent may be at least one selected from the group consisting of oxygen and peroxide, the peroxide may be hydrogen peroxide, and the content of the oxidizing agent may be 0.8 to 1.2 times mole or 0.9 to 1.1 times mole relative to the mole number of double bonds in the nitrile copolymer.

[0106] In addition, the reducing agent may be at least one selected from the group consisting of hydrazine and hydrazine hydrate, and the content of the reducing agent may be 0.8 to 1.2 times mole or 0.9 to 1.0 times mole relative to the number of moles of double bonds in the nitrile copolymer.

[0107] In addition, when the oxidizing agent and reducing agent are used in amounts within the above range, the production of a hydrogenated nitrile copolymer having a residual double bond content of 40 wt% or less can be more easily achieved.

[0108] In addition, the hydrogenation reaction may be performed at a temperature range of 30°C to 90°C or a temperature range of 30°C to 70°C, and may be performed for 10 to 20 hours or 12 to 20 hours.

[0109]

[0110] (S3) Step

[0111] The above step (S3) is a step for producing an ozonolytically decomposed hydrogenated nitrile copolymer from the hydrogenated nitrile copolymer produced above, and introducing an oxime group through a terminal oximation reaction simultaneously or sequentially, which can be performed by subjecting the hydrogenated nitrile copolymer to ozonolysis and oximation reactions.

[0112] Specifically, the ozonolysis reaction is to remove the remaining reducing agent and split the polymer chain to generate an aldehyde group at the polymer chain terminal and lower the molecular weight, and a hydrogenated nitrile copolymer having a controlled amount of aldehyde terminal groups can be obtained by appropriately controlling the conditions during the ozonolysis reaction. In addition, the oximation reaction can replace the aldehyde terminal groups generated by the ozonolysis reaction with oxime groups and simultaneously suppress the reversible reaction, thereby producing an oximated hydrogenated nitrile copolymer having a controlled amount of oxime terminal groups. Therefore, the production method according to the present invention can obtain a hydrogenated nitrile copolymer having an aldehyde terminal group through the step (S3), and subject it to an oximation reaction to replace the aldehyde terminal groups with oxime groups, thereby producing a hydrogenated nitrile copolymer having an oxime group introduced into the polymer chain. That is, in order to produce a hydrogenated nitrile copolymer having a desired oxime content, the ozonolysis reaction and the oximation reaction need to be appropriately controlled simultaneously.

[0113] In the manufacturing method according to the present invention, the step (S3) may be performed by bubbling a mixture of air and ozone into the hydrogenated nitrile copolymer and adding 0.05 mol to 0.40 mol of hydroxyamine dropwise, wherein the hydroxyamine may be added dropwise to the hydrogenated nitrile copolymer in an amount of 60 wt% or more of the total amount of hydroxyamine input simultaneously with the bubbling of the mixture of air and ozone, and the remaining amount of the total amount input may be added dropwise after the bubbling is completed, and the mixture of air and ozone may include 0.3 mol to 0.7 mol of ozone.

[0114]

[0115] The above step (S3) may be performed at a temperature of 0°C to 75°C.

[0116]

[0117] Dispersion of challenge agent

[0118] The present invention provides a conductive dispersion having excellent dispersibility.

[0119] The conductive dispersion according to the present invention comprises a conductive material, a dispersion medium, and a hydrogenated nitrile copolymer, and the hydrogenated nitrile copolymer may have an oxime content of 0.1 wt% or more and 6.5 wt% or less.

[0120] In addition, the hydrogenated nitrile copolymer may have a residual double bond content of 40 wt% or less and a weight average molecular weight of 100,000 g / mol or less.

[0121] In addition, the hydrogenated nitrile copolymer may have a solvent displacement viscosity of 10 cps or more and 200 cps or less, and the solvent displacement viscosity may be measured using a Brookfield viscometer (#63 spin, 25°C) for a solution in which the hydrogenated nitrile copolymer is dissolved in an amide dispersion medium at 16 wt%.

[0122] In addition, the conductive dispersion according to the present invention may have a viscosity of 1,500 Pa.s or more and 2,500 Pa.s or less, and thus may have excellent dispersibility.

[0123] In addition, the conductive dispersion according to the present invention has a particle size distribution [(D 90 -D 10 ) / D 50 ] may be 1 to 2 or 1.0 or more and 1.5 or less. The conductive dispersion according to the present invention comprises the above-described hydrogenated nitrile-based latex as a dispersant, and the dispersant is physically or chemically bonded to the surface of the conductive material to form conductive material-dispersant complex particles and is dispersed in the dispersion, and satisfaction of the narrow particle size distribution means that the conductive dispersion according to the present invention has excellent uniform dispersibility.

[0124] D in the above particle size distribution 10 , D 50 and D 90means the particle size at 10%, 50% and 90% of the particle size distribution, respectively, and D of the conductive dispersion according to the present invention 10 is 1 to 3 ㎛, 1 to 2 ㎛ or 1.1 to 1.7 ㎛, and D 50 is 2 to 5 μm, 2.5 to 4.0 μm or 2.7 to 3.0 μm, and D 90 may be 3 to 10 μm, 4 to 8 μm or 4.5 to 5.5 μm.

[0125]

[0126] Additionally, the conductive material according to the present invention may be carbon black, Ketjen black, fullerene, graphene, carbon nanotube, or carbon black.

[0127]

[0128] In addition, the hydrogenated nitrile latex according to the present invention can be used in various fields such as timing belts, seals, hoses, diaphragms, rolls, dispersants, and electrode active material slurry compositions.

[0129]

[0130] Example

[0131] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0132]

[0133] Example 1

[0134] (1) Production of nitrile copolymer latex

[0135] An activated solution was prepared by dissolving 706.8 g of ion-exchanged water, 0.19 g of ferrosulfate (FES), 25.75 g of sodium formaldehyde sulfoxylate (SFS), and 3.50 g of disodium ethylenediaminetetraacetate (EDTA).

[0136] In a nitrogen-substituted polymerization reactor, 100 parts by weight of a monomer consisting of 66 wt% of 1,3-butadiene and 34 wt% of acrylonitrile, and alkyldiphenyloxide disulfonate (DOWFAX) were added. TM 2A1, DOW) 0.5 parts by weight, ammonium polyoxyalkylene alkenyl ether sulfate (LATEMUL PD-104, KAO Chemicals Global) 1.0 parts by weight, diisopropylbenzene hydroperoxide (DIPHP, 54 wt% solution) 0.05 parts by weight, pentamethylheptanethiol (TIB-TDM, Chevron Phillips, containing 65 mol% or more of 2,2,4,4,6-pentamethylheptane-4-thiol, including the remaining isomers) 0.5 parts by weight, and ion-exchanged water 200 parts by weight were mixed, and when the temperature of the mixture reached 10°C, 5 parts by weight of the above-described activation solution was added to initiate emulsion polymerization. When the polymerization conversion reached 85%, the polymerization was stopped to obtain a nitrile-based copolymer latex.

[0137]

[0138] (2) Production of hydrogenated nitrile latex

[0139] In a 5-liter three-necked round-bottom flask equipped with a mechanical paddle stirrer, a thermometer, a reflux condenser, and an inlet tube for supplying hydrogen peroxide solution, 322.58 g (solids content 31%, copolymer 100 g, double bond content 1.2 mol) of the nitrile copolymer latex prepared above was added, and 119.8 g (1.2 mol) of 64% aqueous hydrazine was added while stirring at room temperature. After heating to 45°C in a constant temperature bath, 141.53 g (1.29 mol) of 31% aqueous hydrogen peroxide was added dropwise using a pump over 16 hours to carry out the hydrogenation reaction.

[0140] Afterwards, an air / ozone mixture containing 0.3 mol of ozone was passed through a glass tube at 45°C to bubble gas into the bottom of the hydrogenated nitrile copolymer latex to carry out an ozone decomposition reaction. Simultaneously with the bubbling, 0.03 mol of hydroxylamine was added dropwise to the hydrogenated nitrile copolymer latex, and after the bubbling was completed, 0.02 mol of hydroxylamine was added dropwise, stirred for 2 hours, and reacted to produce a hydrogenated nitrile latex containing a hydrogenated nitrile copolymer.

[0141]

[0142] Example 2

[0143] In the above Example 1, a hydrogenated nitrile latex was manufactured in the same manner as in Example 1, except that 0.067 mol of hydroxylamine was added dropwise simultaneously with bubbling, and 0.033 mol of hydroxylamine was added dropwise after bubbling was completed.

[0144]

[0145] Example 3

[0146] In the above Example 1, a hydrogenated nitrile latex was manufactured in the same manner as in Example 1, except that 0.13 mol of hydroxylamine was added dropwise simultaneously with bubbling, and 0.07 mol of hydroxylamine was added dropwise after bubbling was completed.

[0147]

[0148] Example 4

[0149] In Example 3, a hydrogenated nitrile latex was manufactured in the same manner as in Example 3, except that bubbling was performed using an air / ozone mixture containing 0.7 mol of ozone.

[0150]

[0151] Example 5

[0152] In the above Example 4, a hydrogenated nitrile latex was manufactured in the same manner as Example 1, except that 0.27 mol of hydroxylamine was added dropwise simultaneously with bubbling, and 0.13 mol of hydroxylamine was added dropwise after bubbling was completed.

[0153]

[0154] Example 6

[0155] In the above Example 2, a hydrogenated nitrile-based latex was produced in the same manner as in Example 2, except that 100 parts by weight of a monomer composed of 65 wt% of 1,3-butadiene and 35 wt% of acrylonitrile was used when producing the nitrile-based copolymer latex.

[0156]

[0157] Example 7

[0158] In the above Example 6, a hydrogenated nitrile latex was manufactured in the same manner as in Example 6, except that bubbling was performed using an air / ozone mixture containing 0.5 mol of ozone, 0.13 mol of hydroxylamine was added dropwise simultaneously with the bubbling, and 0.07 mol of hydroxylamine was added dropwise after the bubbling was completed.

[0159]

[0160] Example 8

[0161] In the above Example 1, a hydrogenated nitrile-based latex was produced in the same manner as in Example 1, except that 100 parts by weight of a monomer consisting of 59 wt% of 1,3-butadiene and 41 wt% of acrylonitrile was used when producing the nitrile-based copolymer latex.

[0162]

[0163] Example 9

[0164] In the above Example 1, a hydrogenated nitrile latex was manufactured in the same manner as in Example 1, except that 0.05 mol of hydroxylamine was added dropwise only after bubbling was completed and the reaction was stirred for 2 hours.

[0165]

[0166] Comparative Example 1

[0167] In the above Example 1, a hydrogenated nitrile latex was manufactured in the same manner as in Experimental Example 1, except that bubbling was performed using an air / ozone mixture containing 0.1 mol of ozone, 0.01 mol of hydroxylamine was added dropwise only after the completion of bubbling, and the reaction was stirred for 2 hours.

[0168]

[0169] Comparative Example 2

[0170] In the above Example 1, a hydrogenated nitrile latex was manufactured in the same manner as in Example 1, except that bubbling was performed using an air / ozone mixture containing 0.8 mol of ozone and hydroxylamine was not added.

[0171]

[0172] Comparative Example 3

[0173] In the above Example 1, a hydrogenated nitrile latex was manufactured in the same manner as in Example 1, except that bubbling was performed using an air / ozone mixture containing 0.8 mol of ozone, 0.2 mol of hydroxyamine was added dropwise simultaneously with the bubbling, and 0.2 mol of hydroxyamine was added dropwise after the bubbling was completed.

[0174]

[0175] Comparative Example 4

[0176] In the same manner as in Example 1, a nitrile copolymer latex was prepared, coagulated, and obtained as rubber. After dissolving it in monochlorobenzene (mCB), 1 kg of the nitrile rubber (based on solid content) was pressurized into a 2 L autoclave reactor under 1 bar of argon gas. After the pressurization of the nitrile rubber was completed, the inside of the reactor was replaced with a hydrogen gas atmosphere of 10 bar, and then the temperature was raised to 70°C, and a metathesis hydrogenation composition in which a catalyst and a cocatalyst were dissolved in 10 g of monochlorobenzene was introduced into the reactor. At this time, the metathesis hydrogenation composition contained 0.8 parts by weight of Wilkinson's catalyst (Sigma-Aldrich) as a rhodium-based catalyst based on 100 parts by weight of the nitrile-based rubber, and 2 equivalents of triphenylphosphine (Sigma-Aldrich) as a cocatalyst based on 1 equivalent of the rhodium-based catalyst. Thereafter, the hydrogen gas pressure inside the reactor was increased to 40 bar, and the reaction was performed for 6 hours. After completion of the reaction, 0.2 parts by weight of Irganox 1076 (BASF) was added to the reactor based on 100 parts by weight of the nitrile-based rubber, and the hydrogenated nitrile-based rubber was precipitated and recovered using methanol.

[0177]

[0178] Experimental Example 1

[0179] The residual double bond content, weight average molecular weight, oxime content, and solvent displacement viscosity of the hydrogenated nitrile copolymers manufactured in the above examples and comparative examples were measured, and the results are shown in Table 1 below.

[0180] (1) Residual double bond content (weight%)

[0181] First, nitrogen elements in each hydrogenated nitrile latex containing a hydrogenated nitrile copolymer were analyzed using an elemental analyzer (ICP-OES device, RF power 1300 W, plasma gas flow 15 l / min), and the weight % (a) was calculated from the results. At this time, the sample for ICP-OES measurement was prepared by diluting 0.1 g of hydrogenated nitrile copolymer in 15 ml of hydrofluoric acid, heat-treating by heating from room temperature (23±5℃) to 250℃ for 90 minutes, and then maintaining it for 60 minutes.

[0182] since, 1 The NMR peak was obtained by measuring with H-NMR, and the nitrile group hydrogen (N≡CCH) integral at 2.5 ppm, the acetaldoxime group hydrogen (N=CH) integral at 6.9 ppm and 7.5 ppm, and the 1,4-butadiene hydrogen (HC=CH) integral at 5.6 ppm / 2 were used as molar ratios using the MestReC program, and the nitrile group content (weight %) was calculated using the following mathematical formula 1. Here, 1 H-NMR was measured at room temperature (23±5°C) using a Bruker Avance Neo 500MHz NMR instrument. The sample was prepared by dissolving 0.1 g of hydrogenated nitrile copolymer in 1 ml of TCE (trichloroethylene).

[0183] [Mathematical Formula 1]

[0184] Nitrile group content (weight %) = [Nitrogen element weight % (a) × (Nitrile group molar ratio / (Nitrile group molar ratio + Acetaldoxime group molar ratio))] × [Nitrile group molecular weight / Nitrogen atomic weight]

[0185] Afterwards, the integral value (peak area) of the nitrile group peak at 2.5 ppm and the double bond peak at 5.5 ppm in the above NMR peak was calculated to obtain the weight ratio of the nitrile group and the double bond, and the residual double bond content (weight %) was calculated using the following mathematical formula 2.

[0186] Nitrile group weight ratio (b) = [nitrile group molar ratio (NMR) × nitrile group molecular weight]

[0187] Double bond weight ratio (c) = [double bond molar ratio (NMR) × butadiene molecular weight]

[0188] [Equation 2]

[0189] Residual double bond content (weight %) = [Nitrile group content (weight %) / (Nitrile group weight ratio (b) / Total weight ratio (Nitrile group weight ratio (b) + Double bond weight ratio (c))] × [Double bond weight ratio (c) / Total weight ratio (Nitrile group weight ratio (b) + Double bond weight ratio (c)]

[0190]

[0191] (2) Weight average molecular weight (g / mol) and molecular weight distribution (PDI)

[0192] The weight average molecular weight and number average molecular weight were measured by gel permeation chromatography, and the molecular weight distribution (Mw / Mn) was calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn).

[0193] Gel permeation chromatography (Waters PL-GPC220) was measured using a Polymer Lavoratories PLgel MIX-B 300 mm column under the following conditions.

[0194] Measurement temperature: 38℃

[0195] Flow rate: 1 ml / min

[0196] Injection volume: 200 μl

[0197] Standard specimen: polystyrene

[0198]

[0199] (3) Oxime content (weight%)

[0200] The oxime content was determined from the content of acetaldoxime groups in the copolymer molecule.

[0201] The acetaldoxime content was measured by H-NMR to obtain the NMR peak, and the α-hydrogen peak of the nitrile group was confirmed at 2.5 ppm from the results, and the hydrogen peaks of syn- and anti-aldoxime were confirmed at 6.9 ppm and 7.5 ppm, and the integral value (peak area) was calculated to obtain the nitrile group weight ratio (b) and the acetaldoxime group weight ratio (d), and the acetaldoxime content (weight %) was calculated using the following mathematical formula 3. Here, 1 H-NMR was measured at room temperature (23±5°C) using a Bruker Avance Neo 500MHz NMR instrument. The sample was prepared by dissolving 0.1 g of hydrogenated nitrile copolymer in 1 ml of TCE (trichloroethylene).

[0202] In addition, each peak integral was calculated using the MestReC program using the hydrogen (N≡CCH) integral of the nitrile group at 2.5 ppm, the hydrogen (N=CH) integral of the acetoaldoxime group at 6.9 ppm and 7.5 ppm, and the hydrogen (HC=CH) integral of 1,4-butadiene at 5.6 ppm / 2 as a molar ratio.

[0203] Nitrile group weight ratio (b) = [nitrile group molar ratio (NMR) × nitrile group molecular weight]

[0204] Acetaldoxime group weight ratio (d) = [acetaldoxime group molar ratio (NMR) × acetaldoxime group molecular weight]

[0205] [Equation 3]

[0206] Acetaldoxime content (weight %) = [Nitrile group content (weight %) / {Nitrile group weight ratio (b) / Total weight ratio (nitrile group weight ratio (b) + acetaldoxime group weight ratio (d))}] × [Acetaldoxime group weight ratio (d) / Total weight ratio (nitrile group weight ratio (b) + acetaldoxime group weight ratio (d))]

[0207]

[0208] (4) Viscosity

[0209] Each hydrogenated nitrile latex (100 g rubber, 17 wt% solids) was added dropwise to a 5-liter sealed flask equipped with a mechanical paddle stirrer, a reflux condenser, an inlet tube for supplying N-methyl-2-pyrrolidone (NMP), and a vacuum pump while stirring. 525 L of N-methyl-2-pyrrolidone (NMP) was then added dropwise using a pump over 1 hour. Upon completion of the addition, the temperature of the sealed flask was increased to 90°C and the vacuum pump was operated to reduce the pressure to 10 torr. The pressure was reduced for 2 hours to sufficiently remove water, and a 16 wt% solvent replacement solution was prepared, which was measured using a Brookfield viscometer (#63 spin, 25°C).

[0210]

[0211] As confirmed in Table 1 above, the hydrogenated nitrile copolymers of Examples 1 to 9 had an oxime content of 0.1 wt% or more and 6.5 wt% or less, more specifically 0.9 wt% or more and 5.5 wt% or less, a residual double bond content of less than 1 wt%, a weight average molecular weight of 5,000 g / mol or more and 30,000 g / mol or less, and a solvent displacement viscosity of 10 cps or more and 50 cps or less.

[0212]

[0213] Experimental Example 2

[0214] A conductive dispersion liquid containing the hydrogenated nitrile latex prepared in the above examples and comparative examples was prepared, and its viscosity and dispersed particle size (particle diameter) were measured. The results are shown in Table 2 below.

[0215] (1) Preparation of a pre-dispersed solution for the challenge agent

[0216] In a 5-liter sealed flask equipped with a mechanical paddle stirrer, a reflux condenser, an inlet tube for supplying N-methyl-2-pyrrolidone (NMP), and a vacuum pump, 600 g of each hydrogenated nitrile latex (100 g of rubber, 17 wt% solids) was stirred while adding 525 L of N-methyl-2-pyrrolidone (NMP) dropwise using a pump over 1 hour. Upon completion of the addition, the temperature of the sealed flask was increased to 90°C and the pressure was reduced to 10 torr by operating the vacuum pump. The pressure was reduced for 2 hours to sufficiently remove water, and a solvent-substituted solution was prepared in which the hydrogenated nitrile copolymer was dissolved in the N-methyl-2-pyrrolidone at 16 wt%.

[0217] The conductive dispersion has a unit diameter of 13 nm and a BET of 165-205 m 2 / g bundled carbon nanotubes (3.3 g), a dispersion medium (96.04 g) of N-methylpyrrolidone (NMP), and each of the above solvent substitution solutions (0.66 g based on hydrogenated nitrile copolymer) were mixed using a beads bill to produce the product.

[0218]

[0219] (2) Viscosity

[0220] The above-mentioned conductive dispersion liquid was measured using a viscometer (Viscometer TV-22, TOKI) at 25°C and 1 rpm.

[0221]

[0222] (3) Particle size analysis

[0223] After dispersing each conductive dispersion liquid in NMP, it was introduced into a laser diffraction particle size measuring device (Malvern, Mastersizer 3000) and the particle size distribution was calculated by measuring the difference in diffraction pattern according to particle size when the particles passed through the laser beam, and 10% (D) of the volume cumulative distribution according to particle size (particle diameter) 10 ), 50%(D 50 ) and 90%(D 90) was measured. In addition, the particle size distribution ([(D)) was obtained from the measured particle size results. 90 -D 10 ) / D 50 ]) was calculated.

[0224]

[0225] As confirmed in Table 2 above, Examples 1 to 9 have a reduced viscosity compared to the comparative example, and at the same time, it can be confirmed that they have uniform particle characteristics with a narrow particle size distribution of 1.0 to 1.5. In addition, Examples 1 to 7 showed viscosity characteristics that were further improved compared to Examples 8 and 9 with a viscosity of less than 2500 cps, and at this time, Examples 1 to 7 are conductive dispersion liquids obtained using a hydrogenated nitrile-based latex including a hydrogenated nitrile-based copolymer having an oxime content of 0.9 wt% or more.

Claims

1. A hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer having an oxime content of 0.1 wt% or more and 6.5 wt% or less.

2. In paragraph 1, The above hydrogenated nitrile copolymer is a hydrogenated nitrile latex having an oxime content of 0.5 wt% or more and 6.0 wt% or less.

3. In paragraph 1, The above hydrogenated nitrile copolymer is a hydrogenated nitrile latex having a residual double bond content of 40 wt% or less.

4. In paragraph 1, The above hydrogenated nitrile copolymer is a hydrogenated nitrile latex having a residual double bond content of 10 wt% or less.

5. In paragraph 1, The above hydrogenated nitrile copolymer is a hydrogenated nitrile latex having a weight average molecular weight of 200,000 g / mol or less.

6. In paragraph 1, The above hydrogenated nitrile copolymer is a hydrogenated nitrile latex having a weight average molecular weight of 100,000 g / mol or less.

7. In paragraph 1, The above hydrogenated nitrile copolymer is a hydrogenated nitrile latex having a weight average molecular weight of 50,000 g / mol or less.

8. In paragraph 1, The above hydrogenated nitrile copolymer has a solvent displacement viscosity of 10 cps or more and 200 cps or less, and the solvent displacement viscosity is measured using a Brookfield viscometer (#63 spin, 25°C) for a solution in which the hydrogenated nitrile copolymer is dissolved at 16 wt% in an amide dispersion medium.

9. In paragraph 1, The hydrogenated nitrile-based copolymer is a hydrogenated nitrile-based latex having a residual double bond content of 3 wt% or less, a weight average molecular weight of 5,000 g / mol or more and 30,000 g / mol or less, an oxime content of 0.9 wt% or more and 5.5 wt% or less, and a solvent substitution viscosity of 10 cps or more and 50 cps or less.

10. In paragraph 1, The hydrogenated nitrile copolymer comprises an ethylenically unsaturated nitrile monomer unit; and a hydrogenated conjugated diene monomer unit. A hydrogenated nitrile latex.

11. In paragraph 10, A hydrogenated nitrile latex, wherein the weight ratio of the ethylenically unsaturated nitrile monomer unit and the hydrogenated conjugated diene monomer unit is 28:72 to 39:

61.

12. In paragraph 10, The hydrogenated nitrile-based copolymer is a hydrogenated nitrile-based latex that further includes a conjugated diene-based monomer unit.

13. A step (S1) of producing a nitrile copolymer by polymerizing a monomer mixture including a conjugated diene monomer and an ethylenically unsaturated nitrile monomer in the presence of an emulsifier; A step (S2) of hydrogenating the above nitrile copolymer to produce a hydrogenated nitrile copolymer; It includes a step (S3) of ozonolysis and oximation of the above hydrogenated nitrile copolymer, The above step (S3) is performed by bubbling a mixture of air and ozone through the hydrogenated nitrile copolymer and adding 0.05 mol to 0.40 mol of hydroxylamine dropwise. A method for producing a hydrogenated nitrile latex comprising a hydrogenated nitrile copolymer, wherein the air and ozone mixture contains 0.3 mol to 0.7 mol of ozone.

14. In paragraph 13, A method for producing a hydrogenated nitrile-based latex, wherein in the step (S3), hydroxylamine is added dropwise to the hydrogenated nitrile-based copolymer simultaneously with bubbling of a mixture of air and ozone in an amount of 60 wt% or more of the total amount of hydroxylamine, and the remaining amount of the total amount is added dropwise after the bubbling is completed.

15. In paragraph 13, A method for producing a hydrogenated nitrile latex, wherein in the step (S1), the monomer mixture contains 28 wt% or more and 39 wt% or less of an ethylenically unsaturated nitrile monomer.

16. In paragraph 13, A method for producing a hydrogenated nitrile latex, wherein the hydrogenation in the above step (S2) is performed in the presence of an oxidizing agent and a reducing agent.

17. In paragraph 13, A method for producing a hydrogenated nitrile latex, wherein the above step (S3) is performed at a temperature of 0°C to 75°C.

18. Containing a challenge agent, a dispersion medium and a hydrogenated nitrile copolymer, The above hydrogenated nitrile copolymer is a conductive dispersion having an oxime content of 0.1 wt% or more and 6.5 wt% or less.

19. In paragraph 18, The above hydrogenated nitrile copolymer is a conductive dispersion having a residual double bond content of 40 wt% or less and a weight average molecular weight of 100,000 g / mol or less.

20. In paragraph 18, The above hydrogenated nitrile copolymer has a solvent displacement viscosity of 10 cps or more and 200 cps or less, and the solvent displacement viscosity is a conductive dispersion solution measured using a Brookfield viscometer (#63 spin, 25°C) for a solution in which the hydrogenated nitrile copolymer is dissolved at 16 wt% in an amide dispersion medium.

21. In paragraph 18, A conductive dispersion having a viscosity of 1500 Pa.s or more and 2,500 Pa.s or less.

22. In paragraph 18, Particle size distribution [(D 90 -D 10 ) / D 50 ] is a dispersion of a challenge agent having 1 to 2.

23. In paragraph 18, A conductive material dispersion liquid wherein the conductive material is at least one selected from the group consisting of carbon black, Ketjen black, fullerene, graphene, carbon nanotubes, carbon black, and graphite.