Electrode composition for secondary batteries, electrodes for secondary batteries, and secondary batteries

Abstract

The present invention provides an electrode composition for secondary batteries that exhibits excellent electrolyte penetration from both the electrode surface and the electrode side, as well as high potential resistance, enabling the manufacture of electrodes that do not experience a decrease in battery performance even after repeated charging and discharging. [Solution] An electrode composition for a secondary battery containing an electrode active material, a binder resin, and an additive, wherein the additive has a weight-average molecular weight of 600 or more and contains compound (A) represented by general formula (1), and the hydroxyl value of the additive is 30 KOH mg / g or less. R 1 -O-(AO) m -R 2 (1)

Description

[Technical Field]

[0001] This invention relates to an electrode composition for secondary batteries, an electrode for secondary batteries, and a secondary battery. [Background technology]

[0002] Rechargeable batteries such as lithium-ion batteries are being put into practical use as batteries for mobile devices including mobile phones and notebook computers, as well as as power sources for hybrid and electric vehicles. To further promote their widespread use, there is a need for higher capacity and higher output lithium-ion batteries, and various technologies are being explored for this purpose.

[0003] One method to improve the capacity of secondary batteries is to increase the electrode density. By densely packing the active material, a larger capacity can be obtained. However, increasing the electrode density makes it more difficult for the electrolyte to penetrate the electrodes, which can result in a lower capacity than the theoretical value being extracted, or a deterioration in output characteristics.

[0004] To address these challenges, Patent Document 1 discloses a technique that improves electrolyte permeability by providing grooves on the electrode surface. Patent Document 2 describes a technique that makes it possible to manufacture electrodes with high electrolyte permeability and a fast electrolyte penetration rate by adding an ethylene oxide adduct of a specific alkyl alcohol to the electrode. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2008-27633 [Patent Document 2] Japanese Patent Publication No. 2024-31763 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the method described in Patent Document 1 has the problem that it requires the introduction of new equipment, as it involves a process of pressing the electrode surface with a roller that has irregularities in order to create grooves. In the battery equipped with an electrode containing an ethylene oxide adduct of an alkyl alcohol as described in Patent Document 2, although the initial Coulomb efficiency is good, there is a problem that side reactions occur during charging and discharging, causing the battery performance to gradually deteriorate (decreasing Coulomb efficiency and capacity).

[0007] The present invention aims to solve the above problems by providing an electrode composition for secondary batteries that has excellent electrolyte penetration from both the electrode surface and the electrode sides, even without grooves on the electrode surface, and that has high potential resistance, and does not degrade in battery performance even after repeated charging and discharging. [Means for solving the problem]

[0008] The inventors of this invention arrived at this present invention after diligent research. The present invention relates to any of the following: An electrode composition for a secondary battery comprising an electrode active material, a binder resin, and an additive, wherein the additive has a weight-average molecular weight of 600 or more and contains compound (A) represented by the following general formula (1), and the hydroxyl value of the additive is 30 KOH mg / g or less. R 1 -O-(AO) m -R 2 (1) [In the formula, AO is an alkylene oxy group having 2 to 4 carbon atoms, and m is a number from 10 to 40 representing the average number of repeats of the alkylene oxy group, (AO) m R is a polyalkylene oxy chain, wherein the polyalkylene oxy chain contains an ethylene oxy group, and the molar ratio of the ethylene oxy group in the polyalkylene oxy chain is 85% or more based on the total number of moles of the alkylene oxy groups. 1 and R 2 Each of these is independently a hydrocarbon group having 3 to 20 carbon atoms, and m is the average value of the total number of moles of ethylene oxy groups in the polyalkylene oxy chain.EO the ratio of the carbon number n of the aforementioned R 1 of the aforementioned R R1 to the carbon number n 2 of the aforementioned R R2 to the sum of [(n R1 +n R2 ) / m EO is 0.15 to 2.1] An electrode for secondary batteries obtained by compression-molding the above electrode composition for secondary batteries. A secondary battery comprising the above electrode for secondary batteries. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an electrode composition for secondary batteries that is capable of producing an electrode which is excellent in both electrolyte permeability from the electrode surface and electrolyte permeability from the electrode side surface, has high potential resistance, and does not cause degradation in battery performance even after repeated charge and discharge cycles.

[0010] Hereinafter, the present invention will be described in detail. The present invention relates to an electrode composition for secondary batteries, an electrode for secondary batteries, and a secondary battery. The electrode composition for secondary batteries of the present invention may be an electrode composition for lithium ion batteries, or may be an electrode composition for sodium ion batteries. In the present specification, the reference to "secondary battery" is a concept that includes lithium ion secondary batteries and sodium ion secondary batteries. In addition, when referring to each corresponding type, they are also described as lithium ion batteries and sodium ion batteries.

[0011] <Electrode Composition> An electrode composition for secondary batteries comprising an electrode active material, a binder resin, and an additive, wherein the additive contains a compound (A) having a weight average molecular weight of 600 or more and represented by the following general formula (1), and the hydroxyl value of the additive is 30 KOHmg / g or less. R 1 -O-(AO) m -R 2 (1) [In the formula, AO is an alkyleneoxy group having 2 to 4 carbon atoms, m is a number of 10 to 40 representing the average number of repetitions of the alkyleneoxy group, and (AO) mR is a polyalkylene oxy chain, wherein the polyalkylene oxy chain contains an ethylene oxy group, and the molar ratio of the ethylene oxy group in the polyalkylene oxy chain is 85% or more based on the total number of moles of the alkylene oxy groups. 1 and R 2 Each of these is independently a hydrocarbon group having 3 to 20 carbon atoms, and m is the average value of the total number of moles of ethylene oxy groups in the polyalkylene oxy chain. EO R 1 Number of carbon atoms n R1 and R 2 Number of carbon atoms n R2 The ratio of the sum of [(n R1 +n R2 ) / m EO [The value is between 0.15 and 2.1]

[0012] The electrode composition of the present invention may be an electrode composition for a positive electrode (also called a positive electrode composition) or an electrode composition for a negative electrode (also called a negative electrode composition). The electrode composition of the present invention itself does not contain an electrolyte. As described later, by incorporating an electrolyte into an electrode made using the electrode composition, it can be used as an electrode layer for a secondary battery.

[0013] (electrode active material) The electrode active material may be either a positive electrode active material or a negative electrode active material.

[0014] The positive electrode active material constituting the electrode composition for lithium-ion batteries includes composite oxides of lithium and transition metals {composite oxides with one transition metal (e.g., LiCoO2, LiNiO2, LiAlMnO4, LiMnO2, and LiMn2O4), and composite oxides with two transition metal elements (e.g., LiFeMnO4, LiNi 1-x Co x O2, LiMn 1-y Co y O2, LiNi1 / 3CO1 / 3Al1 / 3O2, and LiNi 0.8 Co 0.15 Al 0.05 O2) and a composite oxide containing three or more transition metal elements [e.g., LiM a M'b M'' c O2 (M, M', and M'' are each different transition metal elements, and satisfy a+b+c=1. For example, LiNi 0.8 Co 0.1 Mn0.1O2, LiNi 1 / 3 Mn 1 / 3 Co1 / 3O2), etc.], etc.}, lithium-containing transition metal phosphates (e.g., LiFePO4, LiCoPO4, LiMnPO4, and LiNiPO4), transition metal oxides (e.g., MnO2 and V2O5), transition metal sulfides (e.g., MoS2 and TiS2), and conductive polymers (e.g., polyaniline, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polyvinylcarbazole), etc., and two or more types may be used in combination. Note that the lithium-containing transition metal phosphate may have a part of the transition metal site substituted with another transition metal. When the electrode active material is a positive electrode active material, a composite oxide of lithium and a transition metal is preferable as the positive electrode active material.

[0015] The positive electrode active material constituting the electrode composition for sodium-ion batteries is not particularly limited as long as it can be used in sodium-ion batteries, and specific examples include layered active materials, spinel-type active materials, oxoacid salt active materials, and the like, for example, NaFeO2, NaNiO2, NaCoO2, NaCrO2, NaMnO2, NaVO2, Na(Ni X Mn 1-X )O2 (0<X<1), Na(Fe X Mn 1-X )O2 (0<X<1), NaVPO4F, Na2FePO4F, Na3V2(PO4)3, and the like. NaCoO2 and NaCrO2 are preferred.

[0016] The negative electrode active materials constituting the electrode composition for lithium-ion batteries include carbon-based materials [graphite (artificial graphite, natural graphite), non-graphitizable carbon (hard carbon), amorphous carbon, resin calcined bodies (e.g., phenolic resin and furan resin that have been calcined and carbonized), cokes (e.g., pitch coke, needle coke and petroleum coke), and carbon fibers, etc.], silicon-based materials [silicon, silicon oxide (SiO2)], x Examples include silicon-carbon composites (carbon particles coated with silicon and / or silicon carbide, silicon particles or silicon oxide particles coated with carbon and / or silicon carbide, and silicon carbide, etc.) and silicon alloys (silicon-aluminum alloy, silicon-lithium alloy, silicon-nickel alloy, silicon-iron alloy, silicon-titanium alloy, silicon-manganese alloy, silicon-copper alloy, and silicon-tin alloy, etc.), conductive polymers (e.g., polyacetylene and polypyrrole), metals (tin, aluminum, zirconium, and titanium, etc.), metal oxides (titanium oxide and lithium-titanium oxide, etc.) and metal alloys (e.g., lithium-tin alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy, etc.) and mixtures thereof with carbon-based materials, and two or more may be used in combination. When the electrode active material is the negative electrode active material, a carbon-based material is preferred as the negative electrode active material, and artificial graphite or natural graphite is particularly preferred. The shape of the negative electrode active material is not particularly limited when it is graphite, and examples include spheroidal graphite and scaly graphite.

[0017] The negative electrode active materials constituting the electrode composition for sodium-ion batteries include carbon-based materials [hard carbon, resin-fired bodies (e.g., phenolic resin and furan resin that have been fired and carbonized), cokes (e.g., pitch coke, needle coke and petroleum coke), and carbon fibers, etc.], silicon-based materials [silicon, silicon oxide (SiO2)]. xExamples include silicon-carbon composites (carbon particles coated with silicon and / or silicon carbide, silicon particles or silicon oxide particles coated with carbon and / or silicon carbide, and silicon carbide, etc.) and silicon alloys (silicon-aluminum alloy, silicon-sodium alloy, silicon-nickel alloy, silicon-iron alloy, silicon-titanium alloy, silicon-manganese alloy, silicon-copper alloy, and silicon-tin alloy, etc.), conductive polymers (e.g., polyacetylene and polypyrrole), metals (tin, aluminum, zirconium, and titanium, etc.), metal oxides (titanium oxide and sodium-titanium oxide, etc.), metal alloys (e.g., sodium-tin alloy, sodium-aluminum alloy, and sodium-aluminum-manganese alloy, etc.) and mixtures of these with carbon-based materials. Of the negative electrode active material particles mentioned above, those that do not contain sodium or sodium ions may be pre-doped to include sodium or sodium ions in some or all of the negative electrode active material particles. From the viewpoint of increasing electrical capacity, the negative electrode active material is preferably a non-graphitizable carbon or a mixture of non-graphitizable carbon and a silicon-based material.

[0018] The content of electrode active material in the electrode composition is not particularly limited, but from the viewpoint of increasing electrode density and thus battery capacity, a higher content of electrode active material is preferable. It is preferably 78 to 98% by weight, and more preferably 85 to 97% by weight, based on the solid content weight of the electrode composition. The "solid content weight of the electrode composition" refers to the weight of the materials excluding volatile components such as organic solvents (the total weight of the electrode active material, binder resin, conductive additive, and other additives). Specifically, the solid content weight is defined as the weight of the residue after heating the electrode composition at 100°C for 8 hours.

[0019] (Binder resin) The binder resin used in the present invention is not particularly limited and may include natural polymers, synthetic polymers, or derivatives thereof. Examples include starch, cellulose, carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), tetrafluoroethylene resins, (meth)acrylic resins, styrene-butadiene rubber (SBR), styrene-butadiene rubber latex, polyethylene (PE), polypropylene (PP), polyimide, polybutadiene, polyoxyethylene, ethylene-vinyl acetate copolymer, copolymer containing alkali metal neutralized ethylenically unsaturated carboxylic acid and vinyl alcohol, alkyl-modified carboxyl group-containing copolymer, hydroxyalkyl (meth)acrylate, functional group-modified polymer (having carboxyl groups, sulfonic acid groups, epoxy groups, amino groups, etc.), copolymer with styrene or vinyl, crosslinked polymer, water-soluble or water-insoluble polymer, etc. Two or more of these may be used in combination. Furthermore, "(meth)acrylic resin" refers to a polymer mainly composed of acrylic monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, various (meth)acrylic acid esters, hydroxyalkyl (meth)acrylates, and functional group-modified (meth)acrylic monomers (those having carboxyl groups, sulfonic acid groups, epoxy groups, amino groups, etc.), and optionally containing hydrophobic monomers, styrene-based, vinyl-based, and other copolymerizable monomers as copolymer components. Furthermore, binder resins, in a broad sense, include thickeners, such as carboxymethylcellulose (CMC), various cellulose derivatives, polyethylene glycol, polyvinyl alcohol, and natural gum. Preferred binder resins include water-soluble or water-dispersible polymers such as styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), (meth)acrylic resin, various cellulose derivatives, and polyvinylpyrrolidone (PVP). If the electrode composition contains these substances, it shall also contain a binder resin. In this specification, the binder resin is a substance distinct from compound (A).

[0020] The content of the binder resin (including the thickener) is preferably 1 to 20% by weight, and more preferably 1 to 15% by weight, based on the solid content weight of the electrode composition.

[0021] (Additives) The additive in the present invention contains compound (A) represented by the following general formula (1), and has a hydroxyl value of 30 KOH mg / g or less.

[0022] Compound (A) has a weight-average molecular weight of 600 or more and is represented by the following general formula (1). R 1 -O-(AO) m -R 2 (1) [In the formula, AO is an alkylene oxy group having 2 to 4 carbon atoms, and m is a number from 10 to 40 representing the average number of repeating alkylene oxy groups, (AO) m R is a polyalkylene oxy chain, wherein the polyalkylene oxy chain contains an ethylene oxy group, and the molar ratio of the ethylene oxy group in the polyalkylene oxy chain is 85% or more based on the total number of moles of the alkylene oxy groups. 1 and R 2 Each of these is independently a hydrocarbon group having 3 to 20 carbon atoms, and m is the average value of the total number of moles of ethylene oxy groups in the polyalkylene oxy chain. EO R 1 Number of carbon atoms n R1 and R 2 Number of carbon atoms n R2 The ratio of the sum of [(n R1 +n R2 ) / m EO [The value is between 0.15 and 2.1] In this specification, alkylene oxide may be denoted as AO, ethylene oxide as EO, and propylene oxide as PO.

[0023] In general formula (1), AO represents an alkylene oxy group having 2 to 4 carbon atoms. Examples of alkylene oxy groups having 2 to 4 carbon atoms include ethylene oxy groups, propylene oxy groups, and butylene oxy groups. AO may be a single group or two or more groups. Among these, the ethylene oxy group is preferred.

[0024] In general formula (1), m is a number between 10 and 40, representing the average number of repeating alkylene oxy groups. If m is smaller than the above range, the electrolyte permeability of the resulting electrode decreases. If m is larger than the above range, the peel strength (adhesion strength) between the resulting electrode and the current collector decreases. m is preferably a number between 25 and 40. If there are multiple types of alkylene oxy groups, m is the sum of the average number of repeating groups for each alkylene oxy group.

[0025] (AO) m AO is a polyalkylene oxy chain, and the polyalkylene oxy chain contains ethylene oxy groups, with the molar ratio of ethylene oxy groups in the polyalkylene oxy chain being 85% or more of the total number of moles of alkylene oxy groups. When AO is an ethylene oxy group, or when the proportion of ethylene oxy groups in AO is high, the electrolyte permeability is improved. If the molar ratio of ethylene oxy groups in the polyalkylene oxy chain is less than 85% of the total number of alkylene oxy groups, the dispersion stability of the electrode composition slurry and the electrolyte permeability of the resulting electrode will be insufficient. Furthermore, the potential resistance will decrease, the initial Coulomb efficiency will tend to be low, and battery performance will tend to deteriorate after repeated charging and discharging. Preferably, the molar ratio of ethylene oxy groups in the polyalkylene oxy chain is 91% or higher. Furthermore, the alkylene oxy group may consist solely of ethylene oxy groups. That is, the molar ratio of ethylene oxy groups in the alkylene oxy group may be 100% based on the total number of moles of alkylene oxy groups.

[0026] Furthermore, when the alkylene oxy group consists of multiple types of alkylene oxy groups, the addition method may be random addition or block addition.

[0027] In general formula (1), R 1 and R 2 Each of these is independently a hydrocarbon group having 3 to 20 carbon atoms. 1 and R 2 If the number of carbon atoms is 21 or more, the electrolyte permeability of the electrode and the battery performance (Coulomb efficiency and capacity retention rate, etc.) will decrease.

[0028] The hydrocarbon group having 3 to 20 carbon atoms may be linear or branched. It may also be an aromatic hydrocarbon group having an aromatic ring. Examples of linear hydrocarbon groups having 3 to 20 carbon atoms include linear alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and eicosyl groups. Examples of branched hydrocarbon groups having 3 to 20 carbon atoms include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isoundecyl group, isododecyl group, isotridecyl group, 2-ethylhexyl group, 2-ethyldodecyl group, 2-ethyltridecyl group, 2-methyltetradecyl group, isohexadecyl group, 2-octylnonyl group, 2-hexyldecyl group, 2-hexylundecyl group, 2-ethylpentadecyl group, 2-(3-methylhexyl)-7-methylnonyl group, isooctadecyl group, 1-hexyltridecyl group, 2-ethylheptadecyl group, and branched alkyl groups such as isoicosyl group. Aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl groups, 4-butylphenyl groups, 4-hexylphenyl groups, and 4-decylphenyl groups. Note, R 1 and R 2 This may be a hydrocarbon group with a distributed number of carbon atoms (for example, a mixture of groups with 14 and 15 carbon atoms).

[0029] R in the general formula (1) of compound (A) 1 and R2 Preferably, all of them are hydrocarbon groups having 6 to 20 carbon atoms, R 1 and R 2 It is even more preferable that at least one of them is selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms, a branched alkyl group having 6 to 20 carbon atoms, and a linear alkyl group having 11 to 20 carbon atoms, R 1 and R 2 It is more preferable that each of these is selected from the group consisting of aromatic hydrocarbon groups having 6 to 20 carbon atoms, branched alkyl groups having 6 to 20 carbon atoms, and linear alkyl groups having 11 to 20 carbon atoms, for example, A-1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 22, 23, 25, etc., as shown in Table 1 below. 1 and R 2 When the carbon number is between 6 and 20, it is easier to achieve a high level of both electrolyte penetration from the electrode surface and electrolyte penetration from the electrode sides. For the same number of carbon atoms, branched hydrocarbon groups and aromatic hydrocarbon groups with aromatic rings tend to have higher adsorption to the electrode active material than straight-chain hydrocarbon groups, and tend to provide a greater effect in improving electrolyte penetration (especially from the electrode sides).

[0030] m is the average value of the total number of moles of ethylene oxy groups in the polyalkylene oxy chain mentioned above. EO R 1 Number of carbon atoms n R1 and R 2 Number of carbon atoms n R2 The ratio of the sum of [(n R1 +n R2 ) / m EO The ratio is between 0.15 and 2.1. Because it is within this range, an electrode with excellent electrolyte penetration can be obtained while maintaining the peel strength between the electrode and the current collector. If the ratio is less than 0.15, the peel strength (adhesion strength) between the electrode and the current collector deteriorates, and if it is greater than 2.1, sufficient electrolyte penetration cannot be achieved. The ratio is preferably between 0.30 and 1.0. Furthermore, the above m EO This is the average value (numerical mean) of the total number of moles of ethylene oxy groups contained in the polyalkylene oxy chain of each molecule.

[0031] The weight-average molecular weight of compound (A) is 600 or more. If the weight-average molecular weight is less than 600, the applicability of the electrode composition slurry deteriorates. To obtain better dispersion stability and applicability to the electrode when the electrode composition is made into a slurry, the weight-average molecular weight of compound (A) is preferably between 600 and 2400, and more preferably between 1000 and 2400. The weight-average molecular weight of compound (A) can be measured by the following method. <Weight average molecular weight measurement method> Equipment: "Waters Alliance 2695" [manufactured by Waters] Column: "Guardcolumn Super HL" (1 piece), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) linked together" Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 10μl Flow rate: 0.6ml / min Measurement temperature: 40℃ Detection device: Refractive index detector Reference substance: Standard polyethylene glycol

[0032] The larger the weight-average molecular weight of compound (A), the better the dispersion stability of the electrode composition when it is made into a slurry. Furthermore, if the weight-average molecular weight of compound (A) is similar, the main chain length is longer in a straight-chain alkyl structure than in an aromatic hydrocarbon, and the molecular entanglement increases, resulting in better dispersion stability when the electrode composition is made into a slurry.

[0033] The method for producing compound (A) is not particularly limited, but it can be produced, for example, by the following methods (i) and (ii). (i) A method of alkylating the hydroxyl group terminus of an alcohol AO adduct obtained by adding an alkylene oxide (AO) to an alcohol having a hydrocarbon group with 3 to 20 carbon atoms using an alkylating agent such as an alkyl chloride having 3 to 20 carbon atoms, or using an arylating agent such as an aryl chloride having 3 to 20 carbon atoms. (ii) A method of alkylating the two hydroxyl terminals of a polyalkylene glycol with an alkylating agent such as an alkyl chloride having 3 to 20 carbon atoms, and / or arylating the same with an arylating agent such as an aryl chloride having 3 to 20 carbon atoms The aforementioned R 1 has a carbon number n R1 and the aforementioned R 2 has a carbon number n R2 are different, the method (i) is preferred because it allows the target compound to be obtained efficiently and easily. Incidentally, as the polyalkylene glycol in the above method (ii), a commercially available product may be used as it is, or it may be produced by a known method.

[0034] Examples of the aforementioned alkyl alcohol having 3 to 20 carbon atoms, as alkyl alcohols having a linear hydrocarbon group of 3 to 20 carbon atoms, include 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol and 1-icosanol, and alkyl alcohols having a linear hydrocarbon group of 11 to 20 carbon atoms (1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol and 1-icosanol) are preferred. Further, as alkyl alcohols having a branched hydrocarbon of 3 to 20 carbon atoms, 2-propanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol), 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-hexanol, 2-methyl-1-pentanol, 2-ethyl-2-butanol, 2-ethyl-1-hexanol, 2-nonanol, 3,5,5-trimethyl-1-hexanol Examples include hols, isodecanol, 2-undecanol, isotridecanol, and 2-hexyl-1-decanol, with alkyl alcohols having a branched hydrocarbon group with 6 to 20 carbon atoms (such as 2-hexanol, 2-methyl-1-pentanol, 2-ethyl-2-butanol, 2-ethyl-1-hexanol, 2-nonanol, 3,5,5-trimethyl-1-hexanol, isodecanol, 2-undecanol, isotridecanol, and 2-hexyl-1-decanol) being preferred. Furthermore, alcohols having aromatic hydrocarbon groups with 6 to 20 carbon atoms include phenol, 4-methylphenol, 4-butylphenol, and 4-decylphenol.

[0035] Examples of alkyl chlorides having 3 to 20 carbon atoms include propyl chloride, butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, 2-ethylhexyl chloride, nonyl chloride, decyl chloride, undecyl chloride, dodecyl chloride, pentadecyl chloride, 2-hexyldecyl chloride, and eicosil chloride. Preferably, alkyl chlorides having a linear hydrocarbon group with 11 to 20 carbon atoms (undecyl chloride, dodecyl chloride, pentadecyl chloride, etc.) and alkyl chlorides having a branched hydrocarbon group with 6 to 20 carbon atoms (2-hexyldecyl chloride and eicosil chloride, etc.). Examples of aryl chlorides having 6 to 20 carbon atoms include phenyl chloride, 4-butylphenyl chloride, and 4-hexylphenyl chloride.

[0036] Compound (A) may be a single compound or may contain two or more compounds.

[0037] The hydroxyl value of the additive in the present invention is 30 KOHmg / g or less. If the hydroxyl value exceeds 30 KOHmg / g, the potential resistance of the additive decreases, the additive may decompose during charge and discharge of the battery, and further the decomposition product of the additive may adversely affect other components constituting the electrode, leading to deterioration of battery performance (such as Coulombic efficiency and capacity). The hydroxyl value of the additive is more preferably 20 KOHmg / g or less. Incidentally, the hydroxyl value of the additive in the present specification is a value measured by a method conforming to JIS K0070.

[0038] The content of Compound (A) is preferably 0.01 to 2% by weight, more preferably 0.1 to 2% by weight, based on the solid content weight of the electrode composition for secondary batteries. When the content of Compound (A) falls within this range, the quantitative ratio of the additive to the electrode active material becomes appropriate, and the effect resulting from the incorporation of Compound (A) can be suitably exhibited.

[0039] The additive in the present invention may contain a compound other than the above Compound (A), as long as the total hydroxyl value of the additive is 30 KOHmg / g or less. The compounds other than Compound (A) include alcohol AO adducts which are intermediate products when producing Compound (A) by the method (i) above, compounds that have a structure represented by General Formula (1) but do not satisfy one or more of the characteristic features of General Formula (1) (the range of the average repetition number m of alkyleneoxy groups, the molar ratio of ethyleneoxy groups in the alkyleneoxy groups, R 1 the number of carbon atoms n R1 or R 2 the number of carbon atoms n R2 , the above ratio [(n R1 +n R2 ) / m EO range), or polyalkylene glycol (such as PEG). The content of the compound other than Compound (A) in the additive is preferably 62% by weight or less, more preferably 30% by weight or less, and even more preferably 20% by weight or less, based on the weight of the additive. The content of compound (A) and other compounds in the additive can be analyzed by NMR or other methods.

[0040] The electrode composition for secondary batteries of the present invention may also contain a conductive additive in addition to the electrode active material, binder resin, and additives described above.

[0041] (Conductive additive) Examples of conductive additives include metals [aluminum, stainless steel (SUS), silver, gold, copper, and titanium, etc.], carbon [graphite (flaky graphite (UP)), carbon black (acetylene black (AB), Ketjen black, furnace black, channel black, and thermal lamp black, etc.), carbon nanofibers (CNF) and carbon nanotubes (CNT), etc.], and mixtures thereof, and two or more may be used in combination.

[0042] Although carbon-based materials are used as both negative electrode active materials and conductive additives, in this application, materials with a volume-average particle diameter of 10 μm or more are considered negative electrode active materials, and materials with a volume-average particle diameter of less than 10 μm are considered conductive additives.

[0043] In this specification, the value of "volume-average particle diameter (D50) of the negative electrode active material or conductive additive" refers to the 50% diameter value in the volume-based integrated fraction determined by the laser diffraction measurement method.

[0044] <Method for manufacturing electrode compositions for secondary batteries> The electrode composition for secondary batteries of the present invention can be obtained by mixing an electrode active material, a binder resin (including a thickener), and additives, and optionally other components (such as a conductive additive). The method and order of mixing each component are not particularly limited, but when both styrene-butadiene rubber (SBR) and carboxymethylcellulose (CMC) are included, it is preferable not to add and mix SBR and CMC at the same time from the viewpoint of uniformity of the electrode composition. For example, it is preferable to stir the electrode active material and CMC to homogenize them, then add and mix the additive, and then add and mix the SBR. If necessary, a solvent (water or organic solvent) may be added at each mixing stage.

[0045] Compound (A), an essential component in the additive, has a polyalkylene oxy chain of appropriate length containing an ethylene oxy group, and therefore exhibits affinity for the solvent of the electrolyte. Furthermore, compound (A) has alkyl and / or aryl groups bonded to the ends of the polyalkylene oxy chain, and therefore exhibits moderate adsorption to the electrode active material surface. In other words, compound (A) has moderate affinity for both the electrolyte and the electrode active material surface, and is therefore considered to contribute to improving the penetration of the electrolyte into the electrode (electrode active material layer). Furthermore, the additives contained in the electrode composition for secondary batteries of the present invention have a hydroxyl value of 30 KOH mg / g or less and high potential resistance (they do not decompose easily during charging and discharging), so it is considered that problems such as a decrease in battery performance (Coulomb efficiency and capacity, etc.) are less likely to occur even after repeated charging and discharging.

[0046] <Electrode for secondary batteries> The electrode for a secondary battery of the present invention is formed by molding the electrode composition for a secondary battery of the present invention. The electrodes for the secondary battery may be electrodes for lithium-ion batteries or electrodes for sodium-ion batteries. The method for compression molding the electrode composition for secondary batteries is not particularly limited, but methods such as roll pressing and pressing with a press machine can be used. The electrode density of the secondary battery electrode obtained by compression molding the electrode composition for secondary batteries is 1.0 to 2.0 g / cm³ when the electrode is the negative electrode. 3 It is preferable that this be the case. Furthermore, if the electrode is a positive electrode, the concentration for a lithium-ion battery positive electrode is 3.0 to 4.0 g / cm³. 3Preferably, the concentration is 2.5 to 3.5 g / cm³ in the case of a positive electrode for a sodium-ion battery. 3 It is preferable that this be the case. The electrodes for secondary batteries obtained using the electrode composition of the present invention exhibit excellent electrolyte permeability even in cases of high electrode density, where electrolyte permeability tends to deteriorate in general. The electrode density defined herein refers to the density of the electrode composition for secondary batteries before the electrolyte has been permeated into it.

[0047] If the electrode composition is a slurry-like electrode composition containing a solvent, it is preferable to dry it to remove the solvent before compression molding (hereinafter, electrodes manufactured via a slurry-like electrode composition containing a solvent may be referred to as "slurry electrodes").

[0048] <Secondary battery> The secondary battery of the present invention is equipped with electrodes for secondary batteries of the present invention, and because the electrolyte is sufficiently permeated into the electrodes, it has excellent charge-discharge efficiency (Coulomb efficiency).

[0049] Examples of rechargeable batteries include lithium-ion batteries and sodium-ion batteries.

[0050] For components of the secondary battery of the present invention other than the electrodes for the secondary battery, known materials can be used. In other words, known materials can be used for the current collector, electrolyte, separator, and the like. As the electrolyte, it is preferable to use ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), propylene carbonate (PC), or mixtures thereof as a non-aqueous solvent. As the electrolyte contained in the electrolyte, electrolytes used in known electrolytes can be used; for example, lithium salts can be used in lithium-ion batteries, and sodium salts can be used in sodium-ion batteries.

[0051] Examples of lithium salts include lithium salts of inorganic anions such as LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, and LiN(FSO2)2, and lithium salts of organic anions such as LiN(CF3SO2)2, LiN(C2F5SO2)2, and LiC(CF3SO2)3. Of these, LiPF6 (lithium hexafluoride phosphate) and LiFSI (lithium bis(fluorosulfonyl)imide) can be preferably used.

[0052] Examples of sodium salts include inorganic sodium salts such as NaPF6, NaBF4, NaClO4, and NaAsF6; and organic sodium salts such as NaCF3SO3, NaN(CF3SO2)2, NaN(C2F5SO2)2, NaN(FSO2)2, and NaC(CF3SO2)3. Of these, NaPF6 is preferred from the viewpoint of battery output and charge / discharge cycle characteristics.

[0053] The concentration of the electrolyte in the electrolyte solution is not particularly limited, but is preferably 0.3 to 5.0 mol / L, more preferably 0.5 to 2.0 mol / L, and even more preferably 0.8 to 1.5 mol / L.

[0054] The secondary battery of the present invention may have only the positive electrode composed of the secondary battery electrode of the present invention, or only the negative electrode composed of the secondary battery electrode of the present invention, or both the positive electrode and the negative electrode may be composed of the secondary battery electrode of the present invention.

[0055] The secondary battery of the present invention can be used as a secondary battery in mobile phones, personal computers, hybrid vehicles, electric vehicles, stationary power supplies, and the like.

[0056] This specification discloses the following:

[0057] The present disclosure (1) is an electrode composition for a secondary battery comprising an electrode active material, a binder resin, and an additive, wherein the additive has a weight-average molecular weight of 600 or more and contains a compound (A) represented by the following general formula (1), and the hydroxyl value of the additive is 30 KOH mg / g or less. R 1 -O-(AO) m -R 2 (1) [In the formula, AO is an alkylene oxy group having 2 to 4 carbon atoms, m is a number from 10 to 40 representing the average number of repeating alkylene oxy groups, (AO)m is a polyalkylene oxy chain, the polyalkylene oxy chain contains ethylene oxy groups, and the molar ratio of ethylene oxy groups in the polyalkylene oxy chain is 85% or more based on the total number of moles of alkylene oxy groups. R 1 and R 2 Each of these is independently a hydrocarbon group having 3 to 20 carbon atoms, and m is the average value of the total number of moles of ethylene oxy groups in the polyalkylene oxy chain. EO R 1 Number of carbon atoms n R1 and R 2 Number of carbon atoms n R2 The ratio of the sum of [(n R1 +n R2 ) / m EO [The value is between 0.15 and 2.1]

[0058] Disclosure (2) is an electrode composition for a secondary battery according to Disclosure (1), wherein the molar ratio of ethylene oxy groups in the polyalkylene oxy chain is 91% or more based on the total number of moles of alkylene oxy groups.

[0059] This disclosure (3) refers to the R 1 and R 2 The electrode composition for secondary batteries according to disclosure (1) or (2) is wherein all of the hydrocarbon groups have 6 to 20 carbon atoms.

[0060] This disclosure (4) refers to the R 1 and R 2The electrode composition for secondary batteries according to any one of the disclosures (1) to (3) is one selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms, a branched alkyl group having 6 to 20 carbon atoms, and a linear alkyl group having 11 to 20 carbon atoms.

[0061] Disclosure (5) is an electrode composition for a secondary battery according to any of Disclosures (1) to (4), wherein the average number of repeating alkylene oxy groups, m, is 25 to 40.

[0062] Disclosure (6) is an electrode composition for a secondary battery according to any one of Disclosures (1) to (5), wherein the content of compound (A) is 0.01 to 2% by weight based on the weight of the electrode composition.

[0063] Disclosure (7) is a secondary battery electrode obtained by compression molding a secondary battery electrode composition described in any of Disclosures (1) to (6).

[0064] Disclosure (8) is a secondary battery comprising the electrodes for secondary batteries described in Disclosure (7). [Examples]

[0065] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples unless it deviates from the spirit of the invention. Unless otherwise specified, parts refer to parts by weight, and % refers to % by weight.

[0066] (Preparation of additives 1-40) The following additives 1 to 40 were prepared. For each additive, the R of the general formula (1) of the compound (A) it contains was considered. 1 and R 2 And, the average number of repeats of alkylene oxy (AO) groups m, and the polyalkylene oxy chain [(AO) m The average value of the total number of moles of ethylene oxy (EO) groups in ] EO and the molar ratio of ethyleneoxy groups, and m EO R for 1 Number of carbon atoms n R1 and R 2 Number of carbon atoms n R2The ratio of the sum of [( n R1+ n R2) / m EO The weight-average molecular weight of compound (A) measured by the above method, the content of compound (A) in each additive, and the hydroxyl value of the additives are shown in Tables 1 and 2.

[0067] (Manufacturing Example 1: Manufacturing of Additive 1) Ethylene oxide (EO) was added to 1-icosanol to produce a 40-mol EO adduct of 1-icosanol. Then, 2224 parts of the 40-mol EO adduct of 1-icosanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure. 60 parts of 1-icosyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction was complete, 220 parts of deionized water were added to the resulting reaction product and stirred at 20°C for 1 hour to dissolve the excess alkali and generated salt. After standing, the lower layer was discarded using a separatory funnel, and Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added at a ratio of 1% of the weight of the recovered upper layer and stirred. Kyoward 600 was then removed by suction filtration, resulting in the R of general formula (1). 1 is an eicosyl group, R 2 is an icosyl group, m is 40, m EO Additive 1 containing compound (A-1) with a hydroxyl value of 40 was obtained. The content of compound (A-1) in additive 1 was 98.1%. The hydroxyl value of additive 1 was 2.3 KOH mg / g.

[0068] (Manufacturing Example 2: Manufacturing of Additive 2) Ethylene oxide (EO) was added to 2-hexyl-1-decanol to produce a 2-hexyl-1-decanol EO 35 molar adduct. Then, 1876 parts of the 2-hexyl-1-decanol EO 35 molar adduct and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-pentadecyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 2-hexyldecyl group, R 2 is a pentadecyl group, m is 35, m EO Additive 2 was obtained containing compound (A-2) with a hydroxyl value of 35. The content of compound (A-2) in additive 2 was 98.3%. The hydroxyl value of additive 2 was 1.9 KOH mg / g.

[0069] (Manufacturing Example 3: Manufacturing of Additive 3) Ethylene oxide (EO) was added to 4-butylphenol to produce a 35-mol EO adduct of 4-butylphenol. Then, 1693 parts of the 35-mol EO adduct of 4-butylphenol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure. 60 parts of 2-ethyl-1-hexyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 4-butylphenyl group, R 2 is a 2-ethylhexyl group, m is 35, m EO Additive 3 containing compound (A-3) with a hydroxyl value of 35 was obtained. The content of compound (A-3) in additive 3 was 98.2%. The hydroxyl value of additive 3 was 1.6 KOH mg / g.

[0070] (Manufacturing Example 4: Manufacturing of Additive 4) A 40-mol AO adduct of 1-octadecanol (37 moles EO / 2 moles PO / 1 mole BO) was prepared by randomly adding ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) to 1-octadecanol in a molar ratio of EO / PO / BO = 37 / 2 / 1. Next, 2115 parts of the 40-mol AO adduct of 1-octadecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 4-hexylphenyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is an octadecyl group, R 2 is a 4-hexylphenyl group, m is 40, m EO Additive 4 containing compound (A-4) with a hydroxyl value of 37 was obtained. The content of compound (A-4) in additive 4 was 98.6%. The hydroxyl value of additive 4 was 1.9 KOH mg / g.

[0071] (Manufacturing Example 5: Manufacturing of Additive 5) Ethylene oxide (EO) was added to 2-ethyl-1-hexanol to produce a 40-mol EO adduct of 2-ethyl-1-hexanol. Then, 1792 parts of the 40-mol EO adduct of 2-ethyl-1-hexanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of phenyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition of phenyl chloride, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 2-ethylhexyl group, R 2 is a phenyl group, m is 40, m EO Additive 5 containing compound (A-5) with a hydroxyl value of 40 was obtained. The content of compound (A-5) in additive 5 was 98.4%. The hydroxyl value of additive 5 was 1.2KOH mg / g.

[0072] (Manufacturing Example 6: Manufacturing of Additive 6) Ethylene oxide (EO) was added to 1-dodecanol to produce a 25-mol EO adduct of 1-dodecanol. Then, 1293 parts of the 25-mol EO adduct of 1-dodecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure. 60 parts of 4-butylphenyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition of 4-butylphenyl chloride. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a dodecyl group, R 2 is a 4-butylphenyl group, m is 25, m EO Additive 6 containing compound (A-6) with a hydroxyl value of 25 was obtained. The content of compound (A-6) in additive 6 was 98.6%. The hydroxyl value of additive 6 was 1.1 KOH mg / g.

[0073] (Manufacturing Example 7: Manufacturing of Additive 7) Ethylene oxide (EO) was added to 1-dodecanol to produce a 40-mol EO adduct of 1-dodecanol. Then, 1948 parts of the 40-mol EO adduct of 1-dodecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure. 60 parts of 1-dodecyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a dodecyl group, R 2 is a dodecyl group, m is 40, m EO Additive 7 containing compound (A-7) with a hydroxyl value of 40 was obtained. The content of compound (A-7) in additive 7 was 98.1%. The hydroxyl value of additive 7 was 1.2KOH mg / g.

[0074] (Manufacturing example 8: Manufacturing of additive 8) Ethylene oxide (EO) was added to 4-decylphenol to produce a 20-mol EO adduct of 4-decylphenol. Then, 1120 parts of the 20-mol EO adduct of 4-decylphenol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of phenyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition of phenyl chloride, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 4-decylphenyl group, R 2 is a phenyl group, m is 20, m EO Additive 8 containing compound (A-8) with a hydroxyl value of 20 was obtained. The content of compound (A-8) in additive 8 was 98.8%. The hydroxyl value of additive 8 was 1.6 KOH mg / g.

[0075] (Manufacturing Example 9: Manufacturing of Additive 9) Ethylene oxide (EO) was added to 4-butylphenol to produce a 15-mol EO adduct of 4-butylphenol. Then, 773 parts of the 15-mol EO adduct of 4-butylphenol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure. 60 parts of 2-hexyl-1-decyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 4-butylphenyl group, R 2 is a 2-hexyldecyl group, m is 15, m EO Additive 9 containing compound (A-9) with a hydroxyl value of 15 was obtained. The content of compound (A-9) in additive 9 was 99.3%. The hydroxyl value of additive 9 was 1.7KOH mg / g.

[0076] (Manufacturing Example 10: Manufacturing of Additive 10) Ethylene oxide (EO) was added to 4-decylphenol to produce a 15-mol EO adduct of 4-decylphenol. Then, 1039 parts of the 15-mol EO adduct of 4-decylphenol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-pentadecyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 4-decylphenyl group, R 2 is a pentadecyl group, m is 15, m EO An additive 10 containing compound (A-10) with a hydroxyl value of 15 was obtained. The content of compound (A-10) in additive 10 was 98.9%. The hydroxyl value of additive 10 was 2.0 KOH mg / g.

[0077] (Manufacturing Example 11: Manufacturing of Additive 11) A 40-mol EO adduct of 1-hexanol was prepared by adding ethylene oxide (EO) to 1-hexanol. Then, 1735 parts of the 40-mol EO adduct of 1-hexanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was purged with nitrogen at 30°C, and then the pressure inside the vessel was reduced, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was allowed to continue for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a hexyl group, R 2 is a propyl group, m is 40, m EO An additive 11 containing compound (A-11) with a hydroxyl value of 40 was obtained. The content of compound (A-11) in additive 11 was 98.3%. The hydroxyl value of additive 11 was 1.2KOH mg / g.

[0078] (Manufacturing Example 12: Manufacturing of Additive 12) A 30-mol EO adduct of 1-pentadecanol was prepared by adding ethylene oxide (EO) to 1-pentadecanol. Then, 1433 parts of the 30-mol EO adduct of 1-pentadecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a pentadecyl group, R 2 is a propyl group, m is 30, m EO An additive 12 containing compound (A-12) with a hydroxyl value of 30 was obtained. The content of compound (A-12) in additive 12 was 98.4%. The hydroxyl value of additive 12 was 1.3KOH mg / g.

[0079] (Manufacturing Example 13: Manufacturing of Additive 13) A 35-mol AO adduct of 1-octadecanol (32 moles EO / 3 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 1-octadecanol in a molar ratio of EO / PO = 32 / 3. Next, 1842 parts of the 35-mol AO adduct of 1-octadecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-hexyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is an octadecyl group, R 2 is a hexyl group, m is 35, m EO An additive 13 containing compound (A-13) with a hydroxyl value of 32 was obtained. The content of compound (A-13) in additive 13 was 98.3%. The hydroxyl value of additive 13 was 1.5KOH mg / g.

[0080] (Manufacturing Example 14: Manufacturing of Additive 14) Ethylene oxide (EO) was added to 1-propanol to produce a 40-mol EO adduct of 1-propanol. Then, 1697 parts of the 40-mol EO adduct of 1-propanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a propyl group, R 2 is a propyl group, m is 40, m EO An additive 14 containing compound (A-14) with a hydroxyl value of 40 was obtained. The content of compound (A-14) in additive 14 was 98.6%. The hydroxyl value of additive 14 was 1.2KOH mg / g.

[0081] (Manufacturing Example 15: Manufacturing of Additive 15) Ethylene oxide (EO) was added to 1-icosanol to produce a 25-mol EO adduct of 1-icosanol. Then, 1327 parts of the 25-mol EO adduct of 1-icosanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is an eicosyl group, R 2 is a propyl group, m is 25, m EO An additive 15 containing compound (A-15) with a hydroxyl value of 25 was obtained. The content of compound (A-15) in additive 15 was 98.7%. The hydroxyl value of additive 15 was 1.2KOH mg / g.

[0082] (Manufacturing Example 16: Manufacturing of Additive 16) Ethylene oxide (EO) was added to 1-decanol to produce a 20-mol EO adduct of 1-decanol. Then, 1097 parts of the 20-mol EO adduct of 1-decanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-decyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a decyl group, R 2 is a decyl group, m is 20, m EO An additive 16 containing compound (A-16) with a hydroxyl value of 20 was obtained. The content of compound (A-16) in additive 16 was 98.9%. The hydroxyl value of additive 16 was 1.9 KOH mg / g.

[0083] (Manufacturing Example 17: Manufacturing of Additive 17) A 30-mol AO adduct of 1-pentadecanol (28 moles EO / 2 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 1-pentadecanol in a molar ratio of EO / PO = 28 / 2. Next, 1615 parts of the 30-mol AO adduct of 1-pentadecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-decyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a pentadecyl group, R 2 is a decyl group, m is 30, m EO An additive 17 containing compound (A-17) with a hydroxyl value of 28 was obtained. The content of compound (A-17) in additive 17 was 98.4%. The hydroxyl value of additive 17 was 1.7KOH mg / g.

[0084] (Manufacturing Example 18: Manufacturing of Additive 18) A 25-mol AO adduct of 1-dodecanol (23 moles EO / 2 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 1-dodecanol in a molar ratio of EO / PO = 23 / 2. Next, 1274 parts of the 25-mol AO adduct of 1-dodecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-hexyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a dodecyl group, R 2 is a hexyl group, m is 25, m EO An additive 18 containing compound (A-18) with a hydroxyl value of 23 was obtained. The content of compound (A-18) in additive 18 was 98.7%. The hydroxyl value of additive 18 was 1.3KOH mg / g.

[0085] (Manufacturing Example 19: Manufacturing of Additive 19) Ethylene oxide (EO) was added to 1-hexanol to produce a 15-mol EO adduct of 1-hexanol. Then, 762 parts of the 15-mol EO adduct of 1-hexanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-hexyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a hexyl group, R 2 is a hexyl group, m is 15, m EO An additive 19 containing compound (A-19) with a hydroxyl value of 15 was obtained. The content of compound (A-19) in additive 19 was 99.1%. The hydroxyl value of additive 19 was 1.3KOH mg / g.

[0086] (Manufacturing example 20: Manufacturing of additive 20) A 25-mol AO adduct of 2-hexyl-1-decanol was prepared by randomly adding ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) to 2-hexyl-1-decanol in a molar ratio of EO / PO / BO = 22 / 2 / 1. Then, 1380 parts of the 25-mol AO adduct of 2-hexyl-1-decanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was purged with nitrogen at 30°C, and then the pressure inside the vessel was reduced, and 60 parts of 1-hexyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the dropwise addition, the reaction was allowed to continue for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 2-hexyldecyl group, R 2 is a hexyl group, m is 25, m EO An additive 20 containing compound (A-20) with a hydroxyl value of 22 was obtained. The content of compound (A-20) in additive 20 was 98.6%. The hydroxyl value of additive 20 was 1.4 KOH mg / g.

[0087] (Manufacturing Example 21: Manufacturing of Additive 21) A 20-mol AO adduct of 4-butylphenol (17 moles EO / 3 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 4-butylphenol in a molar ratio of EO / PO = 17 / 3. Next, 1064 parts of the 20-mol AO adduct of 4-butylphenol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-propyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition of 1-propyl chloride. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 4-butylphenyl group, R 2 is a propyl group, m is 20, m EOAn additive 21 containing compound (A-21) with a hydroxyl value of 17 was obtained. The content of compound (A-21) in additive 21 was 98.9%. The hydroxyl value of additive 21 was 1.1 KOH mg / g.

[0088] (Manufacturing Example 22: Manufacturing of Additive 22) A 10-mol AO adduct of 2-ethyl-1-hexanol (9 moles EO / 1 mole PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 2-ethyl-1-hexanol in a molar ratio of EO / PO = 9 / 1. Next, 588 parts of the 10-mol AO adduct of 2-ethyl-1-hexanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of phenyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition of phenyl chloride. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 2-ethylhexyl group, R 2 is a phenyl group, m is 10, m EO An additive 22 containing compound (A-22) with a hydroxyl value of 9 was obtained. The content of compound (A-22) in additive 22 was 99.2%. The hydroxyl value of additive 22 was 1.2KOH mg / g.

[0089] (Manufacturing Example 23: Manufacturing of Additive 23) By performing the same procedure as in Production Example 22, except that the amount of 2-ethyl-1-hexanol AO10 molar adduct is changed from 588 parts to 582 parts and the amount of phenyl chloride is changed from 60 parts to 46 parts, the R in general formula (1) can be obtained. 1 is a 2-ethylhexyl group, R 2 is a phenyl group, m is 10, m EO An additive 23 containing compound (A-22) with a hydroxyl value of 9 was obtained. The content of compound (A-22) in additive 23 was 76.5%. The hydroxyl value of additive 23 was 23.1 KOH mg / g. Additives 22, 23, 37, and 39 contain the same compound (A-22), but they differ in the amount of compound (A-22) they contain, and therefore their hydroxyl values ​​also differ.

[0090] (Manufacturing Example 24: Manufacturing of Additive 24) A 20-mol AO adduct of 2-hexyl-1-decanol (18 moles EO / 2 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 2-hexyl-1-decanol in a molar ratio of EO / PO = 18 / 2. Next, 1268 parts of the 20-mol AO adduct of 2-hexyl-1-decanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-pentadecyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a 2-hexyldecyl group, R 2 is a pentadecyl group, m is 20, m EO An additive 24 containing compound (A-23) with a hydroxyl value of 18 was obtained. The content of compound (A-23) in additive 24 was 98.7%. The hydroxyl value of additive 24 was 2.0 KOH mg / g.

[0091] (Manufacturing Example 25: Manufacturing of Additive 25) A 20-mol AO adduct of 1-hexanol (17 moles EO / 3 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 1-hexanol in a molar ratio of EO / PO = 17 / 3. Next, 1024 parts of the 20-mol AO adduct of 1-hexanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of phenyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition of phenyl chloride. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a hexyl group, R 2 is a phenyl group, m is 20, m EO An additive 25 containing compound (A-24) with a hydroxyl value of 17 was obtained. The content of compound (A-24) in additive 25 was 98.9%. The hydroxyl value of additive 25 was 1.4 KOH mg / g.

[0092] (Manufacturing Example 26: Manufacturing of Additive 26) A 20-mol AO adduct of 1-icosanol (18 moles EO / 2 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 1-icosanol in a molar ratio of EO / PO = 18 / 2. Next, 1252 parts of the 20-mol AO adduct of 1-icosanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The reaction was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-dodecyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is an eicosyl group, R 2 is a dodecyl group, m is 20, m EO An additive 26 containing compound (A-25) with a hydroxyl value of 18 was obtained. The content of compound (A-25) in additive 26 was 98.6%. The hydroxyl value of additive 26 was 1.8 KOH mg / g.

[0093] (Manufacturing Example 27: Manufacturing of Additive 27) A 30-mol AO adduct of 1-decanol (26 moles EO / 3 moles PO / 1 mole BO) was prepared by randomly adding ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) to 1-decanol in a molar ratio of EO / PO / BO = 26 / 3 / 1. Next, 1572 parts of the 30-mol AO adduct of 1-decanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-decyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a decyl group, R 2 is a decyl group, m is 30, m EO An additive 27 containing compound (A-26), where the hydroxyl value is 26, was obtained. The content of compound (A-26) in additive 27 was 98.5%. The hydroxyl value of additive 27 was 1.8 KOH mg / g.

[0094] (Manufacturing example 28: Manufacturing of additive 28) By performing the same procedure as in Production Example 27, except that the amount of 1-decanol AO30 molar adduct is changed from 1572 parts to 1555 parts and the amount of 1-decyl chloride is changed from 60 parts to 25 parts, the R in general formula (1) can be obtained. 1 is a decyl group, R 2 is a decyl group, m is 30, m EO An additive 28 containing compound (A-26), where the hydroxyl value is 26, was obtained. The content of compound (A-26) in additive 28 was 38.1%. The hydroxyl value of additive 28 was 22.4 KOH mg / g. Additives 27, 28, 38, and 40 contain the same compound (A-26), but they differ in the amount of compound (A-26) they contain, and therefore their hydroxyl values ​​also differ.

[0095] (Manufacturing example 29: Manufacturing of additive 29) Ethylene oxide (EO) was added to 1-icosanol to produce a 10-mol EO adduct of 1-icosanol. Then, 800 parts of the 10-mol EO adduct of 1-icosanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-octyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is an eicosyl group, R 2 is an octyl group, m is 10, m EO An additive 29 was obtained containing a comparative compound (ratio A-1) in which the ratio was 10. The comparative compound (ratio A-1) is the above ratio [(n R1 +n R2 ) / m EO ] is a compound outside the scope of claim 1.

[0096] (Manufacturing example 30: Manufacturing of additive 30) A 15-mol AO adduct of 1-pentadecanol (13 moles EO / 2 moles PO) was prepared by randomly adding ethylene oxide (EO) and propylene oxide (PO) to 1-pentadecanol in a molar ratio of EO / PO = 13 / 2. Next, 1026 parts of the 15-mol AO adduct of 1-pentadecanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-pentadecinyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a pentadecyl group, R 2 is a pentadecyl group, m is 15, m EO An additive 30 was obtained containing a comparative compound (ratio A-2) in which the ratio was 13. The comparative compound (ratio A-2) is the above ratio [(n R1 +n R2 ) / m EO] is a compound outside the scope of claim 1.

[0097] (Manufacturing example 31: Manufacturing of additive 31) A 30-mol AO adduct of 1-propanol (25 moles EO / 3 moles PO / 2 moles BO) was prepared by randomly adding ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) to 1-propanol in a molar ratio of EO / PO / BO = 25 / 3 / 2. Next, 1370 parts of the 30-mol AO adduct of 1-propanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. The mixture was then purged with nitrogen at 30°C, and the inside of the vessel was reduced in pressure. 60 parts of 1-propyl chloride were then added dropwise while maintaining a temperature not exceeding 50°C. The reaction was continued for a further 8 hours after the addition. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a propyl group, R 2 is a propyl group, m is 30, m EO An additive 31 was obtained containing a comparative compound (ratio A-3) in which the ratio was 25. The comparative compound (ratio A-3) is a compound in which the molar ratio of ethylene oxy groups in the polyalkylene oxy chain is outside the range of claim 1.

[0098] (Manufacturing example 32: Manufacturing of additive 32) Ethylene oxide (EO) was added to 1-propanol to produce a 10-mol EO adduct of 1-propanol. Then, 505 parts of the 10-mol EO adduct of 1-propanol and 40 parts of sodium hydroxide were placed in a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a propyl group, R 2 is a propyl group, m is 10, m EOAn additive 32 was obtained containing a comparative compound (ratio A-4) in which the ratio was 10. The comparative compound (ratio A-4) is a compound whose weight-average molecular weight is outside the range of claim 1.

[0099] (Manufacturing example 33: Manufacturing of additive 33) Ethylene oxide (EO) was added to 1-propanol to produce an 8-mol EO adduct of 1-propanol. Then, 427 parts of the 8-mol EO adduct of 1-propanol and 40 parts of sodium hydroxide were placed in a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a propyl group, R 2 is a propyl group, m is 8, m EO An additive 33 was obtained containing a comparative compound (ratio A-5) in which m is 8. The comparative compound (ratio A-5) is a compound whose m and weight-average molecular weight are outside the range of claim 1.

[0100] (Manufacturing example 34: Manufacturing of additive 34) Ethylene oxide (EO) was added to 1-propanol to produce a 10-mol EO adduct of 1-propanol. Then, 489 parts of the 10-mol EO adduct of 1-propanol and 40 parts of sodium hydroxide were placed in a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of methyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition of methyl chloride, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a propyl group, R 2 is a methyl group, m is 10, m EO Additive 34 was obtained containing a comparative compound (ratio A-6) in which the ratio was 10. The comparative compound (ratio A-6) is the same as above R 2 Number of carbon atoms n R2and the compound has a weight-average molecular weight outside the range of claim 1.

[0101] (Manufacturing example 35: Manufacturing of additive 35) Ethylene oxide (EO) was added to 1-pentacosanol to produce a 10-mol EO adduct of 1-pentacosanol. Then, 809 parts of the 10-mol EO adduct of 1-pentacosanol and 40 parts of sodium hydroxide were placed in a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition of 1-propyl chloride, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a pentacosyl group, R 2 is a propyl group, m is 10, m EO Additive 35 was obtained containing a comparative compound (ratio A-7) in which the ratio was 10. The comparative compound (ratio A-7) is the same as above R 1 Number of carbon atoms n R1 and the above ratio [(n R1 +n R2 ) / m EO ] is a compound outside the scope of claim 1.

[0102] (Manufacturing Example 36: Manufacturing of Additive 36) Ethylene oxide (EO) was added to 1-propanol to produce a 45-mol EO adduct of 1-propanol. Then, 1960 parts of the 45-mol EO adduct of 1-propanol and 40 parts of sodium hydroxide were added to a pressure-resistant reaction vessel equipped with a thermometer, stirrer, heating / cooling device, and dropping cylinder. Nitrogen purging was performed at 30°C, and then the inside of the vessel was reduced in pressure, and 60 parts of 1-propyl chloride were added dropwise while maintaining a temperature not exceeding 50°C. After the addition, the reaction was continued for a further 8 hours. After the reaction is complete, the same procedure as in Production Example 1 is performed to obtain R in general formula (1). 1 is a propyl group, R 2 is a propyl group, m is 45, m EOAn additive 36 was obtained containing a comparative compound (ratio A-8) in which the ratio was 45. The comparative compound (ratio A-8) is the above m and the above ratio [(n R1 +n R2 ) / m EO ] is a compound outside the scope of claim 1.

[0103] (Manufacturing example 37: Manufacturing of additive 37) By performing the same procedure as in Production Example 22, except that the amount of 2-ethyl-1-hexanol AO10 molar adduct is changed from 588 parts to 590 parts and the amount of phenyl chloride is changed from 60 parts to 49 parts, the R in general formula (1) can be obtained. 1 is a 2-ethylhexyl group, R 2 is a phenyl group, m is 10, m EO An additive 37 containing compound (A-22) with a hydroxyl value of 9 was obtained. The content of compound (A-22) in additive 37 was 80.8%. The hydroxyl value of additive 37 was 18.9 KOH mg / g. Additives 22 and 23, and manufacturing examples 37 and 39 all contain the same compound (A-22), but they differ in the amount of compound (A-22) they contain, and therefore their hydroxyl values ​​also differ.

[0104] (Manufacturing example 38: Manufacturing of additive 38) By performing the same procedure as in Production Example 27, except that the amount of 1-decanol AO30 molar adduct is changed from 1572 parts to 1561 parts and the amount of 1-decyl chloride is changed from 60 parts to 30 parts, the R in general formula (1) can be obtained. 1 is a decyl group, R 2 is a decyl group, m is 30, m EO An additive 38 containing compound (A-26) with a hydroxyl value of 26 was obtained. The content of compound (A-26) in additive 38 was 46.9%. The hydroxyl value of additive 38 was 19.2 KOH mg / g. Additives 27, 28, 38, and 40 contain the same compound (A-26), but they differ in the amount of compound (A-26) they contain, and therefore their hydroxyl values ​​also differ.

[0105] (Manufacturing example 39: Manufacturing of additive 39) By performing the same procedure as in Production Example 22, except that the amount of 2-ethyl-1-hexanol AO10 molar adduct is changed from 588 parts to 587 parts and the amount of phenyl chloride is changed from 60 parts to 41 parts, the R in general formula (1) can be obtained. 1 is a 2-ethylhexyl group, R 2 is a phenyl group, m is 10, m EO An additive 39 containing compound (A-22) with a hydroxyl value of 9 was obtained. The content of compound (A-22) in additive 39 was 68.3%. The hydroxyl value of additive 39 was 31.2 KOH mg / g. Additives 22 and 23, and manufacturing examples 37 and 39 all contain the same compound (A-22), but differ in the amount of compound (A-22) they contain, and therefore also differ in their hydroxyl values. Additive 39, used for comparison, is an additive whose hydroxyl value falls outside the range of claim 1.

[0106] (Manufacturing example 40: Manufacturing of additive 40) By performing the same procedure as in Production Example 27, except that the amount of 1-decanol AO30 molar adduct is changed from 1572 parts to 1567 parts and the amount of 1-decyl chloride is changed from 60 parts to 11 parts, the R in general formula (1) can be obtained. 1 is a decyl group, R 2 is a decyl group, m is 30, m EO An additive 40 containing compound (A-26), whose hydroxyl value is 26, was obtained. The content of compound (A-26) in additive 40 was 11.6%. The hydroxyl value of additive 40 was 32.0 KOH mg / g. Additives 27, 28, 38, and 40 contain the same compound (A-26), but differ in the amount of compound (A-26) they contain, and therefore also differ in their hydroxyl values. Additive 40, used for comparison, is an additive whose hydroxyl value falls outside the range of claim 1.

[0107] [Table 1]

[0108] [Table 2]

[0109] (Preparation of negative electrode active material) The following negative electrode active materials were prepared. Electrode for lithium ion batteries Graphite: Artificial graphite (FSN-1, manufactured by Shanghai Sugisugi Technology Co., Ltd., D50 particle size: 15.3μm) Sodium-ion battery electrode hard carbon (Carbotron® PS(F), manufactured by Kureha Battery Materials Japan Co., Ltd., D50 particle size: 20 μm)

[0110] (Preparation of binder resin and thickener) The following binder resins and thickeners were prepared. SBR: Styrene-butadiene rubber (BM451B, manufactured by Nippon Zeon Co., Ltd.) CMC: Carboxymethylcellulose (CMC2260, manufactured by Daicel Corporation)

[0111] (Preparation of conductive additive) The following conductive additives were prepared. AB: Acetylene black ("Denka Black Li100", manufactured by Denka Co., Ltd., primary particle D50 particle size: 35nm)

[0112] (Examples 1-33, Comparative Examples 1-11: Preparation of electrode compositions (negative electrode compositions) and electrodes (negative electrodes) for lithium-ion batteries) 1.5 parts of CMC as a thickening agent and 40.0 parts of ion-exchanged water were stirred at 2000 rpm for 5 minutes using a planetary stirring type mixing and kneading device {Awatori Rentaro [manufactured by Shinky Co., Ltd.]}. Next, 2.5 parts of SBR as a binder resin were added, and the mixture was stirred at 2000 rpm for 5 minutes using an Awatori Rentaro. To the resulting dispersion, graphite in the amounts shown in Tables 3 and 4, 1.0 part of each additive (however, 0.1 part of the additive in Example 29, 0.5 part in Example 30, 2.0 part in Example 31, and no additive in Comparative Example 9), and 60.0 parts of ion-exchanged water were added as the negative electrode active material, and the mixture was stirred at 2000 rpm for 5 minutes using an Awatori Rentaro to prepare the electrode composition (negative electrode composition). Each of the obtained electrode compositions was applied to one side of a current collector (copper foil) using a wire bar in the atmosphere, and pre-dried overnight in a fume hood to form an electrode layer on the current collector. (Hereafter, the current collector and electrode layer together will be referred to as the electrode sheet.) The center of the obtained electrode sheet was punched out to a diameter of 16 mm, and then dried under reduced pressure (1.3 kPa) at 100°C for 2 hours. Finally, it was pressed using a roll press (manufactured by Tester Industries Co., Ltd.) to the target electrode density (electrode thickness). Specifically, the target electrode density was 1.6 g / cm³. 3 An electrode (negative electrode) for evaluating electrolyte penetration time was fabricated by pressing, with a target electrode density of 1.5 g / cm³. 3 We used a press to fabricate electrodes (negative electrodes) for charge-discharge testing. Furthermore, the electrode sheet is cut with a cutter to a length of 8.0 cm x width of 2.5 cm, dried in a vacuum dryer at 80°C for 3 hours, and then pressed in a roll press to achieve a target electrode density of 1.5 g / cm³. 3 The electrode (negative electrode) for the peel test was fabricated by pressing. Furthermore, the electrode sheet is cut with a cutter to a length of 7 cm x width of 2 cm, dried in a vacuum dryer at 80°C for 3 hours, and then pressed in a roll press to achieve a target electrode density of 1.6 g / cm³. 3 An electrode (negative electrode) for evaluating the weight of electrolyte absorption was fabricated by pressing.

[0113] (Examples 34-37, Comparative Examples 12-15: Electrode compositions (negative electrode compositions) and electrode (negative electrode) for sodium-ion batteries) 1.5 parts of AB as a conductive additive, 1.5 parts of CMC as a thickening agent, and 40.0 parts of ion-exchanged water were stirred at 2000 rpm for 5 minutes using a planetary stirring type mixing and kneading device {Awatori Rentaro [manufactured by Shinky Co., Ltd.]}. Next, 1.5 parts of SBR as a binder resin was added and the mixture was stirred at 2000 rpm for 5 minutes using an Awatori Rentaro. To the resulting dispersion, the amounts of hard carbon shown in Table 4, 0.5 parts of each additive (however, no additives were used in Comparative Example 15), and 60.0 parts of ion-exchanged water were added as negative electrode active material, and the mixture was stirred at 2000 rpm for 5 minutes using an Awatori Rentaro to prepare the electrode composition (negative electrode composition). Each of the obtained electrode compositions was subjected to the same procedure as in Examples 1-33 and Comparative Examples 1-11, with an electrode density of 1.2 g / cm³. 3 We fabricated electrodes for evaluating electrolyte penetration time (negative electrode), charge / discharge testing (negative electrode), peeling testing (negative electrode), and electrolyte absorption weight evaluation (negative electrode).

[0114] <Viscosity> The slurry of the electrode composition obtained above was stored at room temperature in a sealed container, and its viscosity was measured using a rotary viscometer both after slurry preparation and 24 hours after slurry preparation. The slurry viscosity retention rate was calculated from the measured viscosity. The results are shown in Tables 3 to 5.

[0115] <Calculation of electrode density> For the electrodes used to evaluate electrolyte penetration time and the electrodes used to evaluate electrolyte absorption weight, which were pressed to the target electrode density (electrode thickness) using a roll press machine (manufactured by Tester Industries Co., Ltd.), the electrode weight, the weight and thickness of the current collector (copper foil) were measured and calculated using the following formula. Electrode density (g / cm 3 ) = (Electrode weight (g) - Current collector weight (mg) × 10 -3 ) / (electrode area (cm 2 ) × ((Electrode thickness for electrolyte permeability evaluation (μm) - Current collector thickness (μm)) × 10 -4 )) Tables 3-5 show the calculated electrode densities for the electrodes used to evaluate electrolyte penetration time and electrolyte absorption weight. Furthermore, for the electrodes used in charge / discharge testing and peeling testing, the target electrode density is 1.5 g / cm³. 3 against Electrode density 1.45~1.55g / cm 3 We confirmed that it could be produced with ±0.05 g / cm³.3 Errors within this range will not affect the results of the charge / discharge test and the peel test.

[0116] <Electrode peel test (evaluation of adhesive strength between the electrode (electrode layer) and the current collector)> The electrode composition surface of the peel test electrode prepared as described above was covered with double-sided tape (Nichiban Nicetack: model number NW-K15), and the electrode composition surface was bonded to a SUS plate (thickness 1.2 mm) so that it faced the SUS plate to create the test specimen. A metal foil (copper foil) from one end of the test specimen was peeled off the SUS plate. A peel test (interfacial fracture test) was then performed on a benchtop precision universal testing machine (Autograph AGS-X, manufactured by Shimadzu Corporation). The SUS plate was gripped with the chuck on the lower test fixture, and the metal foil was gripped with the chuck on the upper fixture, to peel the electrode composition from the current collector. A 20N test fixture was used, and the tensile speed was 150 mm / min. The obtained measurement results were read in accordance with JIS K 6854-2:1999, and the average peeling force (N) was determined. The average peeling force was divided by the width of the test specimen (0.025 m) to obtain the interfacial fracture force (N / m), which is recorded in Tables 3 to 5. For each example and comparative example, the interfacial fracture force (N / m) was measured and calculated using three test pieces, and the arithmetic mean was used as the analytical value. A higher interfacial fracture force (N / m) is preferable because it indicates higher adhesion strength between the electrode (electrode layer) and the current collector.

[0117] <Evaluation of electrolyte penetration time (electrolyte penetration from electrode surface)> Electrolyte 1 was dropped into the electrode (negative electrode) prepared above for evaluating electrolyte penetration time, and the time (minutes) it took for the electrolyte to penetrate the electrode was measured. The electrolyte penetration time (minutes) is shown in Tables 3-5. A shorter penetration time indicates better penetration in the thickness direction from the electrode surface. When electrolyte solution is dropped onto the electrode, the color of the area where the solution was dropped darkens. The color returns to normal once the electrolyte solution soaks into the electrode, so the time it took for the electrode color to return to normal was measured. The following was used as electrolyte solution 1. Electrolyte 1 (EC / DEC = 1 / 1 (volume ratio), LiPF61M) EC stands for ethylene carbonate, and DEC stands for diethyl carbonate. LiPF6 stands for lithium hexafluoride phosphate. For each example and comparative example, the measurement and electrolyte immersion time (minutes) was measured using three evaluation electrodes, and the arithmetic mean was used as the analytical value. Furthermore, the results of evaluating (grading) the electrolyte penetration time (minutes) according to the following criteria are shown in Tables 3-5. (Evaluation Criteria) The electrolyte penetration time evaluation score, calculated using the formula below, was graded according to the following criteria. A higher grade number indicates superior electrolyte penetration from the electrode surface. (Evaluation score for electrolyte penetration time) = 100 ÷ (Electrolyte penetration time [minutes]) Grade 10: Electrolyte immersion time evaluation score of 9 or higher Grade 9: Electrolyte immersion time evaluation score is 8 or higher but less than 9. Grade 8: Electrolyte immersion time evaluation score is 7 or higher but less than 8. Grade 7: Electrolyte immersion time evaluation score is 6 or higher but less than 7. Grade 6: Electrolyte immersion time evaluation score is 5 or higher but less than 6. Grade 5: Electrolyte immersion time evaluation score is 4 or higher but less than 5. Grade 4: Electrolyte immersion time evaluation score is 3 or higher but less than 4. Grade 3: Electrolyte immersion time evaluation score is 2 or higher but less than 3. Grade 2: Electrolyte immersion time evaluation score is 1 or more but less than 2. Grade 1: Electrolyte immersion time evaluation score is less than 1.

[0118] <Evaluation of electrolyte absorption weight (electrolyte permeability from the electrode side)> The pre-test weight (mg) of the electrode prepared above for evaluating electrolyte absorption weight was measured. 1 mL of electrolyte was taken into a screw-cap tube (Maruemu Co., Ltd., No. 7), and the electrode for the electrolyte absorption weight test was placed upright inside the screw-cap tube with its short side facing downwards, ensuring it did not touch the side wall of the tube. The lid was then closed, and after standing for 2 hours, the electrode for evaluating electrolyte absorption weight was removed. The electrolyte adhering to the surface of the immersion part was wiped off, and the post-test weight (mg) was measured. The increase compared to the pre-test weight (mg) was defined as the electrolyte absorption weight (mg). A larger electrolyte absorption weight (mg) indicates superior electrolyte penetration from the side of the electrode (parallel to the current collector). The measurement results are shown in Tables 3-5. The electrolyte solution used was the electrolyte solution 1 described above. For each example and comparative example, the weight of the measured electrolyte absorbed (mg) was measured using three evaluation electrodes, and the arithmetic mean was used as the analytical value. Furthermore, the results of evaluating (grading) the electrolyte absorption weight (mg) according to the following criteria are shown in Tables 3-5. (Evaluation Criteria) The electrolyte absorption weight evaluation score, calculated using the formula below, was graded according to the following criteria. A higher grade number indicates superior electrolyte penetration from the electrode side. (Evaluation score based on electrolyte absorption weight) = (Electrolyte absorption weight [mg] ÷ 2) Grade 10: Electrolyte absorption weight evaluation score of 9 or higher Grade 9: Electrolyte absorption weight evaluation score is 8 or higher but less than 9. Grade 8: Electrolyte absorption weight evaluation score is 7 or higher but less than 8. Grade 7: Electrolyte absorption weight evaluation score is 6 or higher but less than 7. Grade 6: Electrolyte absorption weight evaluation score is 5 or higher but less than 6. Grade 5: Electrolyte absorption weight evaluation score is 4 or higher but less than 5. Grade 4: Electrolyte absorption weight evaluation score is 3 or higher but less than 4. Grade 3: Electrolyte absorption weight evaluation score is 2 or higher but less than 3. Grade 2: Electrolyte absorption weight evaluation score is 1 or more but less than 2. Grade 1: Electrolyte absorption weight evaluation score is less than 1.

[0119] <Comprehensive evaluation (grading) of electrolyte permeability> Based on the electrolyte penetration time evaluation score and electrolyte absorption weight evaluation score calculated above, the results of the overall evaluation (grading) of electrolyte permeability according to the following criteria are shown in Tables 3 to 5. Furthermore, the evaluation criteria emphasized the electrolyte absorption weight, which represents the electrolyte permeability from the electrode side, a particularly important factor in the production of secondary batteries such as lithium-ion batteries. (Evaluation Criteria) The overall electrolyte penetration score, calculated using the formula below, was graded according to the following criteria. A higher grade number indicates superior overall electrolyte penetration. (Comprehensive evaluation score for electrolyte permeability) = {Electrolyte permeation time evaluation score + (Electrolyte absorption weight evaluation score × 1.5)} ÷ 2.5 Grade 10: The comprehensive evaluation score for electrolyte permeability is 9 or higher Grade 9: The comprehensive evaluation score for electrolyte permeability is 8 or higher and less than 9 Grade 8: The comprehensive evaluation score for electrolyte permeability is 7 or higher and less than 8 Grade 7: The comprehensive evaluation score for electrolyte permeability is 6 or higher and less than 7 Grade 6: The comprehensive evaluation score for electrolyte permeability is 5 or higher and less than 6 Grade 5: The comprehensive evaluation score for electrolyte permeability is 4 or higher and less than 5 Grade 4: The comprehensive evaluation score for electrolyte permeability is 3 or higher and less than 4 Grade 3: The comprehensive evaluation score for electrolyte permeability is 2 or higher and less than 3 Grade 2: The comprehensive evaluation score for electrolyte permeability is 1 or higher and less than 2 Grade 1: The comprehensive evaluation score for electrolyte permeability is less than 1

[0120] (Preparation of lithium-ion battery for charge-discharge test (negative electrode half-cell)) From the positive electrode side, a lithium metal foil (manufactured by Honjo Metal Co., Ltd.), a separator (trade name "#3501", manufactured by Celgard LLC), and the electrodes for charge-discharge test (negative electrodes) prepared in Examples 1 to 33 and Comparative Examples 1 to 11 were stacked in this order, Electrolyte solution 1 was injected, and a lithium-ion battery for charge-discharge test (2032-type coin cell) was fabricated.

[0121] (Preparation of sodium-ion battery for charge-discharge test (negative electrode half-cell)) From the positive electrode side, a sodium metal foil (manufactured by Kanto Chemical Co., Ltd.), a separator (trade name "#3501", manufactured by Celgard LLC), and the electrodes for charge-discharge test (negative electrodes) prepared in Examples 34 to 37 and Comparative Examples 12 to 15 were stacked in this order, Electrolyte solution 2 was injected, and a sodium-ion battery for charge-discharge test (2032-type coin cell) was fabricated. The following was used as Electrolyte solution 2. Electrolyte solution 2 (EC / DEC = 1 / 1 (volume ratio), 1M NaPF₆) EC refers to ethylene carbonate, and DEC refers to diethyl carbonate. NaPF₆ refers to sodium hexafluorophosphate.

[0122] <Charge / Discharge Test: Measurement of Initial Coulomb Efficiency> At 25°C, the initial Coulomb efficiency of the charge-discharge test battery was evaluated using the charge-discharge measurement device "HJ-SD8" [manufactured by Hokuto Denko Co., Ltd.] by the following method: The battery was charged to 0.0V with a current of 0.05C using a constant current charging method (CC mode), and after a 10-minute rest, it was discharged to 1.5V with a current of 0.05C. The capacity charged at this time was defined as the [initial charge capacity (mAh)], and the capacity discharged was defined as the [initial discharge capacity (mAh)]. The initial Coulomb efficiency was calculated using the following formula, and the results are shown in Tables 3-5. For each example and comparative example, the initial Coulomb efficiency (%) was measured and calculated using three batteries, and the arithmetic mean was used as the analytical value. [Initial Coulomb Efficiency (%)] = [Initial Discharge Capacity] ÷ [Initial Charge Capacity] × 100

[0123] <Charge / Discharge Test: Measurement of Capacity Retention Rate After Severe Testing> At 25°C, the capacity retention rate of the battery used for charge-discharge testing was evaluated using the charge-discharge measurement device "HJ-SD8" [manufactured by Hokuto Denko Co., Ltd.] by the following method. The battery was charged to 0V using a constant current charging method (also known as CC mode) with a current of 0.05C, then discharged to 1.5V with a current of 0.05C after a 10-minute pause. The discharged capacity at this time was defined as the [1-Cycle Discharge Capacity (mAh)]. The same charging and discharging process was repeated, and the discharged capacity at this time was defined as [2-Cycle Discharge Capacity (mAh)]. Next, the battery was charged to 0V with a current of 0.1C, and after a 10-minute rest, it was discharged to 1.5V with a current of 0.1C. The discharged capacity at this time was defined as [3-Cycle Discharge Capacity (mAh)]. Furthermore, the battery was charged to 0V with a current of 0.5C, and after a 10-minute rest, it was discharged to 1.5V with a current of 0.1C. The discharged capacity at this time was defined as [4-Cycle Discharge Capacity (mAh)]. Finally, the battery was charged to 0V with a current of 1.0C, then left to rest for 10 minutes, and finally discharged to 1.5V with a current of 0.1C. The discharged capacity at this time was defined as [5-Cycle Discharge Capacity (mAh)]. The capacity retention rate (%) after harsh testing was calculated using the following formula, and the results are shown in Tables 3-5. For each example and comparative example, the test capacity retention rate (%) was calculated using three batteries, and the arithmetic mean was used as the analytical value. Capacity retention rate after harsh testing (%) = [5-cycle discharge capacity (mAh)] / [2-cycle discharge capacity (mAh)]

[0124] [Table 3]

[0125] [Table 4]

[0126] [Table 5]

[0127] From the evaluation results shown in Tables 3, 4, and 5, it can be seen that the electrodes of each example have superior electrolyte permeability (especially electrolyte permeability from the side of the electrode) compared to the electrodes of each comparative example. Furthermore, since the batteries equipped with the electrodes of each example exhibit battery performance (capacity retention rate) comparable to the batteries equipped with the electrodes of Comparative Examples 9 and 15, which do not contain additives, it can be seen that the additive containing compound (A) has high potential resistance and does not easily degrade battery performance (capacity retention rate) even after repeated charging and discharging. Furthermore, the electrode peel strength of the electrodes in each example is comparable to that of electrodes without additives, and it can be seen that there is almost no decrease in the adhesive strength between the current collector and the electrode (electrode layer) due to the addition of the additive containing compound (A). [Industrial applicability]

[0128] The secondary battery obtained from the electrode composition for secondary batteries of the present invention is particularly useful as a secondary battery for use in mobile phones, personal computers, hybrid vehicles, and electric vehicles.

Claims

1. An electrode composition for a secondary battery comprising an electrode active material, a binder resin, and an additive, wherein the additive has a weight-average molecular weight of 600 or more and contains compound (A) represented by the following general formula (1), and the hydroxyl value of the additive is 30 KOH mg / g or less. R １ -O-(AO) ｍ -R ２ (1) [In the formula, AO is an alkyleneoxy group having 2 to 4 carbon atoms, m is a number of 10 to 40 representing the average number of repetitions of the alkyleneoxy group, and (AO) ｍ is a polyalkyleneoxy chain, the polyalkyleneoxy chain contains ethyleneoxy groups, and the molar ratio of ethyleneoxy groups in the polyalkyleneoxy chain is 85% or more based on the total number of moles of the alkyleneoxy groups. R １ and R ２ are each independently a hydrocarbon group having 3 to 20 carbon atoms, and the ratio of the sum of the carbon number n, which is the average value of the total number of moles of ethyleneoxy groups in the polyalkyleneoxy chain, to m ＥＯ of the aforementioned R １ the carbon number n Ｒ１ and the aforementioned R ２ the carbon number n Ｒ２ the ratio of the sum of [(n Ｒ１ + n Ｒ２ ) / m ＥＯ is 0.15 to 2.1]

2. The electrode composition for a secondary battery according to claim 1, wherein the molar ratio of ethylene oxy groups in the polyalkylene oxy chain is 91% or more based on the total number of moles of alkylene oxy groups.

3. The aforementioned R １ and R ２ The electrode composition for a secondary battery according to claim 1, wherein all of them are hydrocarbon groups having 6 to 20 carbon atoms.

4. The aforementioned R １ and R ２ The electrode composition for a secondary battery according to claim 1, wherein each of them is selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms, a branched alkyl group having 6 to 20 carbon atoms, and a linear alkyl group having 11 to 20 carbon atoms.

5. The electrode composition for a secondary battery according to claim 1, wherein the average number of repeating alkylene oxy groups, m, is 25 to 40.

6. The electrode composition for a secondary battery according to claim 1, wherein the content of compound (A) is 0.01 to 2% by weight based on the solid content weight of the electrode composition.

7. An electrode for a secondary battery, formed by molding the electrode composition for a secondary battery according to any one of claims 1 to 6.

8. A secondary battery comprising electrodes for a secondary battery as described in claim 7.

Images