JP2018067406A - Dispersant composition for secondary battery slurry and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a dispersant composition for a secondary battery slurry, good in dispersion stability; a secondary battery slurry composition good in coating properties and coat drying properties; a method for producing a secondary battery slurry composition good in coating properties and coat drying properties; and a battery in which the secondary battery slurry composition is used.SOLUTION: A dispersant composition for a secondary battery slurry contains: a polymer composition (A); and a component (B) that is at least one selected from an aldehyde compound composition (B1) represented by the following general formula (1) and a specific ether compound composition (B2).SELECTED DRAWING: None

Description

  The present invention relates to a dispersant composition for secondary battery slurry and use thereof. More specifically, a secondary battery slurry dispersant composition with good slurry dispersion stability, a secondary battery slurry composition with good coatability and coating drying property, and excellent heat resistance and liquid retention. The present invention relates to a coating for a secondary battery and a method for producing the same.

  In recent years, in electronic devices, secondary batteries such as lithium ion secondary batteries, nickel hydride secondary batteries, nickel cadmium secondary batteries and capacitors such as electric double layer capacitors that can be repeatedly used by charging have been used. . Secondary batteries are being rapidly developed as batteries for use in portable electronic devices and hybrid vehicles. For example, a lithium ion secondary battery is mainly composed of a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte solution, and various studies have been made to improve battery characteristics.

For example, a positive electrode is manufactured by applying a positive electrode secondary battery slurry containing a positive electrode active material and a solvent to a current collector and drying it. The negative electrode is produced by applying a negative electrode secondary battery slurry containing a negative electrode active material and a solvent to a current collector and drying it. The separator is a material capable of isolating the positive electrode and the negative electrode and improving the safety of the battery. For example, a polyolefin porous film has excellent characteristics. In addition, a separator whose surface is coated by applying a secondary battery slurry for a separator containing organic particles or inorganic particles to the surface of a separator substrate such as a porous polyolefin film has been developed. However, in a situation where a secondary battery having a larger capacity is demanded, a secondary battery material capable of further improving safety has been demanded.

  As a means for ensuring safety, for example, there is a method of providing a shutdown function for preventing further heat generation by blocking the passage of ions between the positive and negative electrodes by the above-described separator in the event of abnormal heat generation. With the shutdown function, the separator melts and becomes non-porous in the event of abnormal heat generation, blocking the passage of ions and further suppressing heat generation. For example, a separator made of a porous film made of polyolefin suppresses further heat generation by blocking (shutdown) the passage of ions by melting and making non-porous at about 80 to 180 ° C. during abnormal heat generation of the battery. . However, when the heat generation is severe, the separator made of the porous film may cause a short circuit due to direct contact between the positive electrode and the negative electrode due to shrinkage or film breakage. Thus, the separator made of a polyolefin porous film has insufficient shape stability and sometimes cannot suppress abnormal heat generation due to a short circuit.

  For example, Patent Document 1 is formed by laminating a heat-resistant layer containing fine particle filler and a porous film mainly composed of polyolefin as a base material (hereinafter sometimes referred to as “base material porous film”). A separator for a non-aqueous electrolyte secondary battery comprising a laminated porous film; Patent Document 2 discloses a method using a fine particle filler whose surface is modified as a heat-resistant layer of the separator; Patent Document 3 describes a chemical structure of a binder resin. A method of binding a filler is disclosed.

  However, these methods solve the dispersibility of the inorganic particles in the secondary battery slurry, the storage stability of the secondary battery slurry, the film formation property of the secondary battery slurry, the drying property of the coating film, the uniformity and the heat resistance. There is a need for further improvements in performance.

JP 2004-227972 A JP 2007-31151 A JP 2006-331760 A

  An object of the present invention is to provide a dispersion composition for a secondary battery slurry having good dispersion stability, a secondary battery slurry composition having good coatability and film drying characteristics, and good coatability and film drying characteristics. It is providing the manufacturing method of a secondary battery slurry composition, and the battery using this secondary battery slurry composition.

（但し、Ｒ^１は水素原子、アルキル基、アルケニル基、アルカノール基又はアリール基である。）

（但し、Ｒ^２は水素原子、アルキル基、アルケニル基、アルカノール基又はアリール基である。ｎ＝０〜３０である。）
界面活性剤成分（Ｃ）をさらに含むと好ましい。
前記成分（Ａ）に対する前記成分（Ｂ）の重量割合が０重量％超かつ１重量％以下であると好ましい。
ロスマイルス試験法による２５℃における有効濃度０．１重量％の起泡力が、流下直後において５０ｍｍ以下、かつ、流下直後から５分後において２５ｍｍ以下であると好ましい。
前記成分（Ａ）は、下記高分子粒子成分（Ａ１）を必須に含有すると好ましい。
高分子粒子成分（Ａ１）：アルキルエステル基含有単量体単位（ＩＩ）を必須に含み、重合性単量体全体に対するカルボキシル基含有単量体単位（Ｉ）の重量割合が３１重量％未満である
前記成分（Ａ）は、下記高分子成分（Ａ２）を必須に含有すると好ましい。
高分子成分（Ａ２）：重合性単量体全体に対するカルボキシル基含有単量体単位（Ｉ）重量割合が３１重量％以上 As a result of intensive studies, the present inventors have found that the subject of the present application can be solved by a specific aldehyde component or a specific ether compound component, and have reached the present invention.
That is, the dispersant composition for secondary battery slurry of the present invention is represented by the polymer component (A), the aldehyde compound component (B1) represented by the following general formula (1), and the following general formula (2). And at least one component (B) selected from the ether compound components (B2).

(However, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.)

(Wherein, ^{R 2} is a hydrogen atom, an alkyl group, an alkenyl group, an .n = 0 to 30 is an alkanol group or an aryl group.)
It is preferable that the surfactant component (C) is further included.
The weight ratio of the component (B) to the component (A) is preferably more than 0% by weight and 1% by weight or less.
The foaming force with an effective concentration of 0.1% by weight at 25 ° C. according to the Ross Miles test method is preferably 50 mm or less immediately after flowing down, and 25 mm or less immediately after flowing down and 5 minutes later.
The component (A) preferably contains the following polymer particle component (A1) as an essential component.
Polymer particle component (A1): Essentially containing an alkyl ester group-containing monomer unit (II), and the weight ratio of the carboxyl group-containing monomer unit (I) to the whole polymerizable monomer is less than 31% by weight. The component (A) preferably contains the following polymer component (A2) as an essential component.
Polymer component (A2): Carboxyl group-containing monomer unit (I) based on the whole polymerizable monomer The weight ratio is 31% by weight or more

（但し、Ｒ^１は水素原子、アルキル基、アルケニル基、アルカノール基又はアリール基である。）

（但し、Ｒ^２は水素原子、アルキル基、アルケニル基、アルカノール基又はアリール基である。ｎ＝０〜３０である。） The secondary battery slurry composition of the present invention comprises a polymer component (A), an aldehyde compound component (B1) represented by the following general formula (1), and an ether compound component represented by the following general formula (2) ( B2) a secondary battery slurry composition containing at least one component (B) selected from B2) and inorganic particles, each content being 100 parts by weight of the inorganic particles The component (A) is 0.01 to 100 parts by weight and the component (B) is 0.0001 to 1 part by weight.

(However, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.)

(Wherein, ^{R 2} is a hydrogen atom, an alkyl group, an alkenyl group, an .n = 0 to 30 is an alkanol group or an aryl group.)

（但し、Ｒ^１は水素原子、アルキル基、アルケニル基、アルカノール基又はアリール基である。）

（但し、Ｒ^２は水素原子、アルキル基、アルケニル基、アルカノール基又はアリール基である。ｎ＝０〜３０である。） The method for producing a secondary battery material of the present invention comprises a polymer component (A), an aldehyde compound component (B1) represented by the following general formula (1), and an ether compound represented by the following general formula (2). A step (a) of obtaining a dispersant composition by mixing at least one selected from the components (B2), and a step (b) of obtaining a slurry composition by mixing the dispersant composition and inorganic particles. And a step (c) of applying the slurry composition to at least one selected from a positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode, and a separator, and forming a film by drying. Material manufacturing method.

(However, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.)

(Wherein, ^{R 2} is a hydrogen atom, an alkyl group, an alkenyl group, an .n = 0 to 30 is an alkanol group or an aryl group.)

The positive electrode for a secondary battery of the present invention is a positive electrode for a secondary battery having a positive electrode coating on a current collector, and the coating is formed by a nonvolatile component of the secondary battery slurry composition.
The negative electrode for a secondary battery according to the present invention is a negative electrode for a secondary battery having a negative electrode coating on a current collector, and the coating is formed of a non-volatile component of the secondary battery slurry composition.
The separator for a secondary battery of the present invention is a separator having a separator coating, and the coating is formed by a non-volatile component of the secondary battery slurry composition.
The secondary battery of the present invention is a secondary battery including a negative electrode, a positive electrode, a separator, and an electrolyte solution, and at least one of the negative electrode, the positive electrode, and the separator is a non-volatile component of the secondary battery slurry composition. It has the film formed by.

  The slurry containing the dispersant composition for secondary battery slurry of the present invention has good dispersion stability. The secondary battery slurry composition of the present invention is excellent in coating properties and coating drying properties. The coating for secondary batteries produced using the secondary battery slurry composition of the present invention is excellent in heat resistance and liquid retention.

  The dispersant composition for a secondary battery slurry of the present invention includes a component (B) that is at least one selected from the polymer component (A), the aldehyde compound component (B1), and the ether compound component (B2). This will be described in detail below.

[Polymer component (A)]
The polymer component (A) functions as a dispersion aid for inorganic particles and a coatability improver for the secondary battery slurry composition. Moreover, it functions also as a binder of inorganic particles after apply | coating the slurry for secondary batteries to a base material, and drying water. The component (A) contained in the dispersant composition for secondary battery slurry of the present invention is not particularly limited, and the dispersibility or applicability of the secondary battery slurry composition and the inorganic particles after removing water are removed. If it is a compound which does not inhibit a mutual binding, there will be no restriction | limiting in particular.

  The component (A) is not particularly limited, and examples thereof include acrylic polymers; vinyl polymers such as polyvinyl acetate and polyvinyl stearate; styrene-vinyl chloride copolymers, styrene-vinyl acetate copolymers. Styrene polymers such as coalescence; urethane polymers; phenol polymers; olefin polymers such as polyethylene, polypropylene and poly-1-butene; ketone polymers; amide polymers; polyphenylene oxide polymers; Examples thereof include an epoxy polymer, a polyester polymer, a nylon polymer, a natural rubber, a cellulose polymer, a polypeptide, and a protein. Among these, acrylic polymers are preferable because they are excellent in dispersibility in water and the binding property of inorganic particles after removing water.

  The acrylic polymer is not particularly limited, and examples thereof include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and citraconic acid; (meth) acrylonitrile, α-chloroacrylonitrile , Nitrile monomers such as α-ethoxyacrylonitrile and fumaronitrile; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t- (meth) acrylic acid Butyl, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) 2-Ethoxyethyl acrylate, hexyl (meth) acrylate, (meth) acryl Acid nonyl, lauryl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, benzyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, glycidyl (meth) acrylate (Meth) acrylic acid ester-β-methylglycidyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid ester monomer units ; (Meth) acrylamide, N-methylol (meth) acrylamide, acetone acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) ) Acrylamide, N-hexyl (meth) From (meth) acrylamide monomer units such as chloramide, N-cyclohexyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl (meth) acrylamide, and diacetone acrylamide Examples thereof include a polymer composed of at least one selected monomer unit. Among these, since it is excellent in dispersibility and binding properties, it is preferable to contain at least one selected from a carboxyl group-containing monomer, a (meth) acrylic acid ester monomer unit, and a (meth) acrylamide monomer unit as a constituent component. .

  The acrylic polymer may further contain other monomer units other than those described above. Other monomer units are not particularly limited. For example, styrene monomers such as styrene, α-methylstyrene and chlorostyrene; vinyl halide units such as vinyl chloride, vinylidene chloride and vinyl bromide. Monomers and vinylidene halide monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, and neodecanoic acid vinyl ester; N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N-cyclohexylmaleimide, Maleimide monomers such as N-laurylmaleimide; acrolein; unsaturated organic silanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, etc., one or more But you can.

The acrylic polymer may be a polymer that includes a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds together with the polymerizable monomer.
Although it does not specifically limit as a crosslinking agent, For example, aromatic divinyl compounds, such as divinylbenzene and divinyl naphthalene; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) (Meth) acrylate compounds of acrylate, glycerin di (meth) acrylate, pentaerythritol tetra (meth) acrylate; carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide, polycarbodiimide Compound; polyfunctional epoxy compound; oxazoline compound; polyfunctional hydrazide compound; isocyanate compound; melanin compound; urea compound and the like.

The polymer component (A) preferably contains the following polymer particle component (A1) from the viewpoint of exhibiting the effect of the present application.
The polymer component (A) preferably contains the following polymer component (A2) from the viewpoint of exhibiting the effects of the present application.

[Polymer particle component (A1)]
The polymer particle component (A1) essentially contains an alkyl ester group-containing monomer unit (II), and the carboxyl group-containing monomer unit (I) with respect to the polymerizable monomer is less than 31% by weight.

  In the component (A1), the weight ratio of the carboxyl group-containing monomer unit (I) to the polymerizable monomer is 0 or more and less than 31% by weight, but from the viewpoint of dispersion stability, 0.1 to 30% by weight. Is more preferable, 0.5 to 20% by weight is further preferable, 1 to 10% by weight is particularly preferable, and 2 to 5% by weight is most preferable. If it is 31% by weight or more, the dispersion stability may deteriorate.

  Examples of the alkyl ester group-containing monomer unit (II) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl Acrylic acid alkyl esters such as acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, cetyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl Methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethyl Such as sill methacrylate, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of exerting the effect of the present application, alkyl acrylate is preferable, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate are more preferable, and ethyl acrylate is particularly preferable.

The component (A1) preferably contains a nitrogen-containing monomer unit (III) from the viewpoint of coatability.
Examples of the nitrogen-containing monomer unit (III) include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, acrylamide, methacrylamide, methylenebisacrylamide, N-methylolacrylamide and the like.

When the component (A1) is 100 parts by weight of the monomer unit (II), the monomer unit (I) is preferably 0 to 100 parts by weight from the viewpoint of dispersion stability. 0.1-30 weight part is more preferable, 0.5-20 weight part is further more preferable, 1-10 weight part is especially preferable, and 2-5 weight part is the most preferable. If it exceeds 100 parts by weight, the dispersion stability may be lowered.
When the component (A1) is based on 100 parts by weight of the monomer unit (II), from the viewpoint of dispersion stability, the monomer unit (III) is 0.1 to 200 parts by weight. Preferably, 0.1-100 weight part is more preferable, 0.5-50 weight part is further more preferable, 1-10 weight part is especially preferable, and 2-5 weight part is the most preferable. If it is less than 0.1 part by weight, the coating property may be lowered. If it exceeds 200 parts by weight, the dispersion stability may be lowered.

The solubility of the component (A1) in water is not particularly limited, but it is preferable to exhibit water-insolubility because of excellent coating properties.
The solubility of the component (A1) in water at 25 ° C. is not particularly limited. For example, it is preferably 10 g / 1000 ml or less, more preferably 5 g / 1000 ml or less, still more preferably 1 g / 1000 ml or less, particularly preferably 0.5 g / 1000 ml or less, most preferably 0.1 g / 1000 ml or less. When the solubility of the component (A1) in water is more than 10 g / 1000 ml, the binding property of the secondary battery slurry may not be sufficient. The preferable lower limit of the solubility of the component (A1) in water is 0 g / 1000 ml.

The viscosity of the 20% aqueous dispersion at 25 ° C. of the component (A1) is preferably 0.1 to 1000 mPa · s, more preferably 1 to 500 mPa · s from the viewpoints of dispersion stability and coatability. 2 to 400 mPa · s is more preferable, 3 to 300 mPa · s is particularly preferable, and 4 to 200 mPa · s is most preferable. If it is less than 0.1 mPa · s, the dispersion stability may deteriorate. If it exceeds 1000 mPa · s, the applicability may deteriorate.
The weight reduction at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas and heating from 40 ° C. at a heating rate of 10 ° C./min) is not particularly limited, but preferably 20 % By weight or less, more preferably 15% by weight or less, further preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 3% by weight or less. If the weight loss at 300 ° C. by thermogravimetry of the polymer particles exceeds 20% by weight, the binding property may not be sufficient.

It is preferable that the zeta potential of the component (A1) is in a specific range because the dispersibility is excellent.
The zeta potential of the 5% by weight aqueous dispersion of the component (A1) at 25 ° C. is preferably 0 to −100 mV, more preferably −10 to −90 mV, still more preferably −20 to −80 mV, and particularly preferably − 30 to -70 mV, most preferably -35 to -65 mV. When the zeta potential of the 5% by weight aqueous dispersion of the component (A1) is less than −100 mV, handling properties may not be excellent. On the other hand, if it exceeds 0 mV, the dispersibility of the slurry for the secondary battery may not be sufficient.

  The component (A1) may be in the form of a polymer particle emulsion in which polymer particles are dispersed in water. The concentration of the polymer particles in the case of the polymer particle emulsion is not particularly limited. For example, it is preferably 1 to 80% by weight, more preferably 10 to 70% by weight, still more preferably 15 to 60% by weight, particularly Preferably it is 20-50 weight%, Most preferably, it is 30-50 weight%. If the concentration of the polymer particles in the case of the polymer particle emulsion is less than 1% by weight, the dispersibility may not be excellent. On the other hand, if the concentration of the polymer particles is more than 80% by weight, handling properties may not be excellent.

  The average particle size of the component (A1) is not particularly limited, but is preferably 0.001 to 100 μm, more preferably 0.01 to 10 μm, still more preferably 0.05 to 1 μm, particularly preferably 0.1 to 0.1 μm. 0.8 μm. When the average particle size of the component (A1) is less than 0.001 μm, production may be difficult, which may not be preferable. On the other hand, when the average particle diameter of the component (A1) is more than 100 μm, the dispersion stability may be lowered, which may not be preferable.

Component (A) and component (A1) may contain other monomer units. Other monomer units are not particularly limited, and examples thereof include styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N- Maleimide monomers such as cyclohexylmaleimide and N-laurylmaleimide; acrolein; unsaturated organic silanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane; vinyl chloride, vinylidene chloride, odor Vinyl halide monomers such as vinyl halides and vinylidene halide monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl neodecanoate, etc., and one or more But you can.
As a glass transition point of a component (A1), -100-50 degreeC is preferable, -80-25 degreeC is more preferable, -60-10 degreeC is further more preferable, -40-0 degreeC is especially preferable. If it is less than −100 ° C., the dispersibility may be insufficient, and if it exceeds 50 ° C., the film-forming property may be insufficient.

[Polymer component (A2)]
The polymer component (A2) includes a specific amount or more of the carboxyl group-containing monomer unit (I).
The carboxyl group-containing monomer unit (I) is not particularly limited as long as it is a monomer having one or more unsubstituted (free) carboxyl groups that are not esterified. As such a carboxyl group-containing monomer (I), for example, an α, β-ethylenically unsaturated monocarboxylic acid monomer, an α, β-ethylenically unsaturated polycarboxylic acid monomer, and α , Β-ethylenically unsaturated dicarboxylic acid monoester monomer and the like. The carboxyl group-containing monomer also includes monomers in which the carboxyl group of these monomers forms a carboxylate. Furthermore, an anhydride of α, β-ethylenically unsaturated polyvalent carboxylic acid can also be used as a carboxyl group-containing monomer because it forms a carboxyl group by cleaving the acid anhydride group after copolymerization.

Examples of the α, β-ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, and cinnamic acid.
Examples of the α, β-unsaturated polyvalent carboxylic acid monomer include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, and citraconic acid. Examples of the anhydride of α, β-unsaturated polyvalent carboxylic acid include maleic anhydride and itaconic anhydride.

In the component (A2), from the viewpoint of dispersibility, the weight ratio of the carboxyl group-containing monomer unit (I) to the polymerizable monomer is 31% by weight or more, preferably 40% by weight or more, and preferably 50% by weight or more. Is more preferable, and 60% by weight or more is more preferable.
From the viewpoint of dispersibility, the component (A2) has a preferred upper limit of the weight ratio of the carboxyl group-containing monomer unit (I) to the polymerizable monomer is 100% by weight, preferably 90% by weight, % By weight is more preferred, and 70% by weight is even more preferred.

The component (A2) preferably contains a nitrogen-containing monomer unit (III) from the viewpoint of coatability.
Examples of the nitrogen-containing monomer unit (III) include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, acrylamide, methacrylamide, methylenebisacrylamide, N-methylolacrylamide and the like.

  From the viewpoint of dispersion stability, the component (A2) is preferably 1 to 200 parts by weight of the monomer unit (III) when the monomer unit (I) is 100 parts by weight. 2.5-100 weight part is more preferable, 5-50 weight part is further more preferable, 10-40 weight part is especially preferable, and 20-30 weight part is the most preferable. If it is less than 1 part by weight, the dispersibility may be lowered, and if it exceeds 200 parts by weight, the handleability may be lowered.

The solubility of the component (A2) in water is not particularly limited, but it is preferable to exhibit water solubility because the dispersibility of the inorganic particles is excellent.
The solubility of the component (A2) in water is not particularly limited. For example, it is preferably 1000 g / 1000 ml or more, more preferably 5000 g / 1000 ml or more, still more preferably 9000 g / 1000 ml or more, particularly preferably 20000 g / 1000 ml. As mentioned above, Most preferably, it is 99000 g / 1000 ml or more. When the solubility of the component (A2) in water is less than 1000 g / 1000 ml, the dispersibility of the secondary battery slurry may not be sufficient.
The 20% aqueous solution viscosity at 25 ° C. of the component (A2) is preferably 2000 to 20000 mPa · s, more preferably 5000 to 19000 mPa · s, and more preferably 10,000 to 18000 mPa · s from the viewpoints of dispersion stability and coatability. More preferably, it is s, 11000-17000 mPa * s is especially preferable, and 12000-16000 mPa * s is the most preferable. If it is less than 2000 mPa · s, the dispersion stability may deteriorate. If it exceeds 20000 mPa · s, the applicability may deteriorate.

  The weight loss at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas and heating from 40 ° C. at a heating rate of 10 ° C./min) is not particularly limited, but preferably 0. -50% by weight, more preferably 1-40% by weight, still more preferably 2-30% by weight, particularly preferably 3-20% by weight, and most preferably 5-15% by weight. When the weight loss at 300 ° C. by thermogravimetry of the component (A2) is more than 50% by weight, the heat resistance may not be sufficient.

It is preferable that the zeta potential of the component (A2) is in a specific range because the dispersibility is excellent.
The zeta potential of the 5% by weight aqueous dispersion of the component (A2) at 25 ° C. is preferably 0 to −100 mV, more preferably −10 to −90 mV, still more preferably −20 to −80 mV, and particularly preferably − 30 to -70 mV, most preferably -35 to -65 mV. When the zeta potential of the 5 wt% aqueous dispersion of the component (A) is less than -100 mV, handling properties may not be excellent. On the other hand, when the zeta potential of the 5 wt% aqueous dispersion of the component (A2) is more than 0 mV, the dispersibility of the secondary battery slurry may not be sufficient.

  As glass transition point Tg of a component (A2), 51-250 degreeC is preferable, 80-200 degreeC is more preferable, 100-180 degreeC is further more preferable, and 110-160 degreeC is especially preferable. If it is less than 80 ° C., the dispersibility may be insufficient, and if it exceeds 250 ° C., the film-forming property may be insufficient.

  Component (A), component (A1), and component (A2) may contain other monomer units. Other monomer units are not particularly limited, and examples thereof include styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N- Maleimide monomers such as cyclohexylmaleimide and N-laurylmaleimide; acrolein; unsaturated organic silanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane; vinyl chloride, vinylidene chloride, odor Vinyl halide monomers such as vinyl halides and vinylidene halide monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl neodecanoate, etc., and one or more But you can.

The component (A), the component (A1), and the component (A2) are composed of a polymerizable monomer and a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds. It may be.
Although it does not specifically limit as a crosslinking agent, For example, aromatic divinyl compounds, such as divinylbenzene and divinyl naphthalene; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) (Meth) acrylate compounds of acrylate, glycerin di (meth) acrylate, pentaerythritol tetra (meth) acrylate; carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide, polycarbodiimide Compound; polyfunctional epoxy compound; oxazoline compound; polyfunctional hydrazide compound; isocyanate compound; melanin compound; urea compound and the like.

[Aldehyde compound component (B1)]
The dispersant composition of the present invention essentially contains at least one component (B) selected from an aldehyde compound component (B1) and an ether compound component (B2) described later.
The aldehyde compound component (B1) plays a role of improving the dispersibility of the inorganic particles and the applicability of the secondary battery slurry composition. The factor that the aldehyde compound component (B1) improves the dispersibility of the inorganic particles and the applicability of the secondary battery slurry composition is not clear, but the role of the hydrophilic aldehyde group assists the dispersion of the inorganic particles in water. It is estimated that it bears.
The aldehyde compound component (B1) is represented by the general formula (1).
In general formula (1), R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.

The number of carbon atoms of the alkyl group and alkenyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-5, from the viewpoint of exerting the effect of the present application.
The number of carbon atoms of the alkanol group is preferably 1-20, more preferably 1-10, and even more preferably 1-5, from the viewpoint of exerting the effect of the present application.

  Although it does not specifically limit as an aryl group, For example, a phenyl group, a benzyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned.

  The aldehyde compound component (B1) is a commercially available compound, and a commercially available product can be used. Moreover, as another aspect, when manufacturing a component (A), even if it is contained in raw materials, such as a carboxyl group-containing monomer, a nitrile monomer, and a (meth) acrylamide monomer unit It may be obtained as a by-product.

[Ether compound component (B2)]
The ether compound component (B2) plays a role of improving the dispersibility of the inorganic particles and the applicability of the secondary battery slurry composition. The ether compound component (B2) is not certain for improving the dispersibility of the inorganic particles and the applicability of the secondary battery slurry composition. However, the ether compound used in the present invention has the adsorptivity to the surface of the inorganic particles, and the coverage. It is presumed that it contributes to the improvement of dispersibility and applicability because of its excellent adsorptivity to the surface of the application member.
The ether compound component (B2) is a compound represented by the general formula (2).
In the general formula (2), R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.

The number of carbon atoms of the alkyl group and alkenyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-5, from the viewpoint of exerting the effect of the present application.
The number of carbon atoms of the alkanol group is preferably 1-20, more preferably 1-10, and even more preferably 1-5, from the viewpoint of exerting the effect of the present application.
Said n is 0-30, 1-20 are preferable, 2-10 are more preferable, and 3-5 are more preferable. If it exceeds 30, dispersibility is insufficient.

  Although it does not specifically limit as an aryl group, For example, a phenyl group, a benzyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned.

  The ether compound component (B2) is a commercially available compound, and a commercially available product can be used. Moreover, as another aspect, when manufacturing a component (A), it may be contained in raw materials, such as a carboxyl group-containing monomer and a nitrile monomer, and is obtained as a by-product It may be. When the component (A) is produced, if an acidic substance such as acetic acid, an amine compound, a metal oxide such as activated alumina, a phosphorus compound, an organometallic compound, a metal hydride, a metal carbonyl compound, etc. are present, an ether compound Component (B2) is easily obtained as a by-product.

[Surfactant component (C)]
The dispersant composition of the present invention may further contain a surfactant component (C).
When the surfactant component (C) is contained, it plays a role of improving the dispersion stability and coating property of the slurry.
Examples of the surfactant component (C) include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Examples of the anionic surfactant include fatty acid salts such as sodium oleate, potassium palmitate and triethanolamine; alkyl sulfate esters such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate and sodium cetyl sulfate. Polyoxyalkylene alkyl ether acetates such as sodium polyoxyethylene tridecyl ether acetate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; polyoxyalkylene alkyl ether sulfates; stearoyl methyl taurine Na, lauroyl methyl taurine Na, myristoyl Higher fatty acid amide sulfonates such as methyl taurine Na and palmitoyl methyl taurine Na; N-amino such as lauroyl sarcosine sodium Rusarcosine salts; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether and sodium polyoxyethylene stearyl ether phosphate; di-2-ethylhexyl sulfosuccinate Long-chain sulfosuccinates such as sodium sulfate, sodium dioctylsulfosuccinate, long-chain N-acyl glutamates such as sodium monosodium N-lauroylglutamate, disodium N-stearoyl-L-glutamate; polyacrylic acid, polymethacrylic acid , Polymaleic acid, polymaleic anhydride, copolymer of maleic acid and isobutylene, copolymer of maleic anhydride and isobutylene, copolymer of maleic acid and diisobutylene, Copolymer of maleic acid and diisobutylene, copolymer of acrylic acid and itaconic acid, copolymer of methacrylic acid and itaconic acid, copolymer of maleic acid and styrene, maleic anhydride and styrene Copolymer of acrylic acid and methacrylic acid, copolymer of acrylic acid and methyl acrylate, copolymer of acrylic acid and vinyl acetate, copolymer of acrylic acid and maleic acid Products such as alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts and amine salts of copolymers of acrylic acid and maleic anhydride Polycarboxylate; naphthalene sulfonic acid, alkyl naphthalene sulfonic acid, formalin condensate of naphthalene sulfonic acid, alkyl naphthalene Formalin condensates of phonic acid and their alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), naphthalene sulfonic acids such as ammonium salts and amine salts Salt; melamine sulfonic acid, alkyl melamine sulfonic acid, formalin condensate of melamine sulfonic acid, formalin condensate of alkyl melamine sulfonic acid, and alkali metal salts thereof (lithium salt, sodium salt, potassium salt, etc.), alkaline earth Metal salts (magnesium salts, calcium salts, etc.), melamine sulfonates such as ammonium salts and amine salts, etc .; lignin sulfonic acids, and alkali metal salts thereof (lithium salts, sodium salts, potassium salts, etc.), alkaline earths Metal salt (magnesium salt, calcium Etc.), lignin sulfonic acid salts such as ammonium salts and amine salts and the like, may be alone or in combination of two or more.

  Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkylmethylammonium salts and alkylamine salts. 1 type or 2 types or more may be used in combination.

Examples of the nonionic surfactant include POE (30) lauryl ether, POE (12) lauryl ether, POE (9) myristyl ether, POE (3) lauryl ether, POP (2) POE (8) stearyl ether. Polyoxyalkylene oxide-added alkyl ethers such as POE (50) oleyl ether; polyoxyethylene (24) polyoxyalkylene styrenated phenyl ethers such as styrenated phenyl ether; multivalents such as sorbitan monopalmitate and sorbitan monooleate Ester compound of alcohol and monovalent fatty acid; polyoxyalkylene alkyl phenyl ether such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether; polyoxyethylene monolaur Polyoxyalkylene fatty acid esters such as polyoxyethylene monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerin monostearate and glycerin monopalmitate Glycerin fatty acid esters such as glycerin monolaurate; polyoxyalkylene castor oil; polyoxyalkylene hydrogenated castor oil; polyoxyalkylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkyl glycerin ether; polyoxyalkylene cholesteryl ether; alkyl polyglucoside; Fatty acid ester; polyoxyalkylene alkylamine; polyoxyethylene-polyoxypropylene bromide Kuporima. These may be alone or in combination of two or more.
The POE represents polyoxyethylene, the POP represents polyoxypropylene, and the POE (12) represents 12 mole addition of polyoxyethylene.

  Examples of the amphoteric surfactant include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt. Imidazoline-based amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaines and the like; N -Amino acid type amphoteric surfactants such as laurylglycine, N-lauryl β-alanine, N-stearyl β-alanine and the like may be mentioned, and one or more may be used in combination.

  When the dispersant composition for secondary battery slurry of the present invention contains the component (C), the content of the component (C) is not particularly limited, but the content of the component (A) is 100 wt. Parts, preferably 0.1 to 500 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight, particularly preferably 2 to 25 parts by weight, most preferably 3 to 3 parts by weight. 10 parts by weight. When the content of the component (C) is less than 0.1 parts by weight, dispersibility and coatability may not be sufficient. On the other hand, when the content of the component (C) is more than 500 parts by weight, handling properties may not be excellent.

[Defoaming component (D)]
When the dispersant composition for secondary battery slurry of the present invention contains an antifoam component (D), it is preferable from the viewpoint of improving the handling property and improving the coating property of the secondary battery slurry.
Although there is no limitation in particular as said component (D), For example, fat-type antifoamers, such as castor oil, sesame oil, linseed oil, and animal and vegetable oil; Fatty acid type antifoamers, such as a stearic acid, an oleic acid, and a palmitic acid; Fatty acid ester antifoaming agents such as isoamyl acid, distearyl succinate, ethylene glycol distearate, butyl stearate; polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol, etc. Alcohol-based antifoaming agents; ether-based antifoaming agents such as 3-heptylcellosolve, nonylcellosolve, 3-heptylcarbitol, polyalkylene glycol; phosphate ester-based antifoaming agents such as tributyl phosphate and tris (butoxyethyl) phosphate ; Diamylamine Amine-based antifoaming agents; Amide-based antifoaming agents such as polyalkylene amide and acylate polyamine; Sulfate-based antifoaming agents such as sodium lauryl sulfate; Polysiloxane-based antifoaming agents such as dimethylpolysiloxane; Paraffin-based minerals Examples thereof include mineral oils such as oils, cyclopentene, cyclohexane, phytelite, and naphthenic mineral oils such as oleanane; silica fine powder antifoaming agents and the like, and one or more may be used in combination. Of these, it is preferable that the antifoaming agent is at least one selected from a polysiloxane antifoaming agent and fine silica powder because of excellent antifoaming properties.

  Although there is no limitation in particular as content of the said component (D), when the total content of a component (A) and a component (B) is 100 weight part, Usually 0.0001-10 weight part, Preferably The amount is 0.0005 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, particularly preferably 0.005 to 0.1 part by weight, and most preferably 0.01 to 0.05 part by weight. If the content of the antifoaming agent is less than 0.0001 part by weight, the antifoaming property may not be sufficient. On the other hand, if the content of the antifoaming agent exceeds 10 parts by weight, the coatability may not be excellent.

[Other ingredients]
The dispersant composition for secondary battery slurry of the present invention may contain other components other than the components described above. Although there is no limitation in particular as another component, For example, a dispersion aid, a pH adjuster component, a rheology adjuster etc. are mentioned.
The dispersion aid used in the present invention has an effect of assisting the dispersion of the secondary battery slurry and enhancing the stability of the secondary battery slurry. The dispersing aid is not particularly limited, but examples thereof include ketone compounds such as acetone, acetylacetone, dipivaloylmethane, dehydroacetic acid, diethyl malonate; methanol, ethanol, isopropyl alcohol, butanol, 3-methoxy-3- Alcohol compounds such as methyl-1-butanol; organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, toluenesulfonic acid, citric acid, tartaric acid, ethylenediaminetetraacetic acid; hydrogen chloride, sulfuric acid Inorganic acids such as nitric acid and phosphoric acid, and the like may be used alone or in combination of two or more. Of these, it is preferable that the dispersion aid is at least one selected from inorganic acids and organic acids because of excellent dispersion stability.

  The molecular weight of the dispersion aid is not particularly limited, and is, for example, usually 10 to 2000, preferably 20 to 1000, more preferably 30 to 500, particularly preferably 40 to 300, and most preferably 50 to 200. When the molecular weight of the dispersion aid is less than 10, the dispersion stability may not be sufficient. On the other hand, if the molecular weight of the dispersion aid is more than 2000, dispersibility may not be sufficient.

  The content of the dispersion aid is not particularly limited, but is usually 0.01 to 10 parts by weight, preferably 0. 10 parts by weight when the total content of the components (A) and (B) is 100 parts by weight. 05 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, particularly preferably 0.5 to 3 parts by weight, and most preferably 1 to 2 parts by weight. When the content of the dispersion aid is less than 0.01 parts by weight, the dispersion stability may not be sufficient. On the other hand, if the content of the dispersion aid is more than 10 parts by weight, the coatability may not be excellent.

  The pH adjuster used in the present invention may be included for the purpose of improving dispersion stability. The pH adjuster is not particularly limited. For example, it may be an alkaline (earth) metal such as sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, magnesium hydroxide. Hydroxides; ammonia; carbonates such as sodium carbonate and sodium hydrogen carbonate; metal oxides such as calcium oxide, sodium oxide, potassium oxide, magnesium oxide, barium oxide, silver oxide, chromium oxide, manganese oxide, iron oxide, and bismuth oxide Examples: Amine compounds such as methylamine, dimethylamine, trimethylamine, ethylamine, ethylenediamine, monoethanolamine, spermine, aniline, toluidine, pyrrolidine, morpholine, imidazole, amino acids, etc. Also good. Among these, it is preferable that the pH adjuster is at least one selected from alkali (earth) metal hydroxides because of excellent versatility. Here, the alkali (earth) metal indicates an alkali metal or an alkaline earth metal.

  Although there is no limitation in particular as molecular weight of a pH adjuster, For example, it is 10-2000 normally, Preferably it is 15-1000, More preferably, it is 20-500, Most preferably, it is 25-200, Most preferably, it is 30-100. When the molecular weight of the pH adjuster is less than 10, dispersion stability may not be sufficient. On the other hand, if the molecular weight of the pH adjuster is more than 2000, handling properties may not be sufficient.

  Although there is no limitation in particular as content of a pH adjuster, When the total content of a component (A) and a component (B) is 100 weight part, it is 0.01-10 weight part normally, Preferably it is 0.8. 05 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, particularly preferably 0.5 to 3 parts by weight, and most preferably 1 to 2 parts by weight. When the content of the pH adjuster is less than 0.01 parts by weight, the dispersion stability may not be sufficient. On the other hand, if the content of the pH adjuster is more than 10 parts by weight, the coatability may not be excellent.

  The rheology modifier may be included for the purpose of improving dispersion stability and coating properties. The rheology modifier is appropriately selected and is not particularly limited. For example, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polyethylene glycol, polyethylene oxide, polyoxyethylene / polypropylene block polymer, polyvinyl alcohol, polyvinyl pyrrolidone, and arabic. Water-soluble polymers such as gum, guar gum, xanthan gum, gelatin, corn starch, and polyacrylamide; fiber-based polymers such as cellulose nanofiber, chitin nanofiber, and polyolefin cotton-like fiber; aluminum magnesium silicate, basic magnesium sulfate inorganic fiber, etc. An inorganic type thickener is mentioned.

[Dispersant composition for secondary battery slurry, production method and form thereof]
The manufacturing method of the dispersant composition for secondary battery slurry is not particularly limited, and polymer component (A), component (B), optional surfactant component (C), component (D): antifoaming The method etc. which mix an agent etc. can be mentioned.

The mixing is not particularly limited, and can be performed using an apparatus having a very simple mechanism such as a container and a stirring blade. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned. Moreover, you may use the mixer which can perform a general rocking | swiveling or stirring. Examples of the mixer include a ribbon type mixer and a vertical screw type mixer. A mixer can be mentioned. Super mixer (made by Kawata Co., Ltd.) and high speed mixer (made by Fukae Co., Ltd.), Newgram Machine (made by Seishin Enterprise Co., Ltd.), SV Mixer (manufactured by Shinko Environmental Solution Co., Ltd.), Filmics (Primix Co., Ltd.), Jet Pasta (Nihon Spindle Manufacturing Co., Ltd.), KRC Nida (manufactured by Kurimoto Steel Works), Rotating and Revolving Mixer (Sinky Corporation) , Photochemical Co., Ltd.) or the like. Other examples include jaw crushers, gyratory crushers, cone crushers, roll crushers, impact crushers, hammer crushers, rod mills, ball mills, vibration rod mills, vibration ball mills, disk type mills, jet mills, cyclone mills, etc. It may be used.
Further, an ultrasonic emulsifier, a continuous biaxial kneader, a high-pressure emulsifier, a microreactor, or the like may be used.

  The surface tension at 25 ° C. of the 0.1% by weight aqueous solution of the dispersant composition for secondary battery slurry is not particularly limited, but is preferably 20 to 50 mN / m, more preferably 25 to 45 mN / m. Particularly preferred is 25 to 40 mN / m, most preferred 25 to 35 mN / m. If it is less than 20 mN / m, the drying property may not be excellent. If it exceeds 50 mN / m, the coatability may be poor.

  In the secondary battery slurry dispersant composition, the foaming power is measured by the Ross Miles test method under the measurement conditions of a concentration of 0.1% by weight and a temperature of 25 ° C. described in detail in the following examples. The foaming power immediately after flowing down the slurry dispersant composition is preferably 50 mm or less, more preferably 40 mm or less, still more preferably 30 mm or less, particularly preferably 20 mm or less, and most preferably 10 mm or less. The foaming power 5 minutes after flowing down is preferably 25 mm or less, more preferably 20 mm or less, still more preferably 15 mm or less, particularly preferably 10 mm or less, and most preferably 5 mm or less. When the foaming force immediately after flowing down is more than 50 mm by the Ross Miles test method, the applicability of the secondary battery slurry may not be sufficient. In addition, if the foaming force after 5 minutes immediately after the flow is more than 25 mm, the applicability of the secondary battery slurry may not be sufficient. In any case, the preferred lower limit is 0 mm.

  The zeta potential of the dispersant composition for secondary battery slurry at a measurement temperature of 25 ° C. is not particularly limited, but is preferably −20 to −100 mV, more preferably −25 to −80 mV, and particularly preferably −30 to −. 70 mV, most preferably −35 to −60 mV. If it is less than −100 mV, handling properties may be poor. If it exceeds -20 mV, the dispersibility may not be excellent.

  The effective concentration of the dispersant composition for secondary battery slurry is not particularly limited as the pH in the 20% by weight aqueous dispersion, but is preferably 4.0 to 12.0, more preferably 5.0 to 11.0. Particularly preferred is 6.0 to 10.0, and most preferred is 7.0 to 9.0. If pH is less than 4.0, applicability | paintability may be bad. If it exceeds 12.0, the handleability may be poor.

  The contact angle after 1600 msec from dropping the droplet of the dispersant composition to the polyolefin resin surface of the dispersant composition for secondary battery slurry is not particularly limited, but preferably 10 to 60 °, More preferably, it is 15 to 60 °, particularly preferably 20 to 50 °, and most preferably 30 to 40 °. If it is less than 10 °, the dispersibility may not be excellent. If it exceeds 60 °, applicability may be poor.

  The contact angle after 1600 msec from dropping the droplet of the secondary battery slurry dispersant composition to the surface of the inorganic oxide plate of the secondary battery slurry dispersant composition is not particularly limited, but preferably It is 10 to 60 °, more preferably 15 to 60 °, particularly preferably 20 to 50 °, and most preferably 30 to 40 °. If it is less than 10 °, the dispersibility may not be excellent. If it exceeds 60 °, applicability may be poor.

  The raw material of the inorganic oxide plate used for contact angle measurement is alumina (aluminum oxide). Details are described in the Examples.

  The non-volatile content concentration of the dispersant composition for secondary battery slurry is not particularly limited, but is usually 1 to 90%, preferably 10 to 80%, more preferably 20 to 70%, particularly preferably 30 to, for example. 60%, most preferably 35-55%. If it is less than 1%, the dispersibility may not be excellent. If it exceeds 90%, the stability may be poor.

  The weight ratio of the component (B) to the component (A) is preferably more than 0% by weight and 1% by weight or less, more preferably 1 to 8000 ppm, further preferably 10 to 5000 ppm, from the viewpoint of exerting the effects of the present invention. Preferably, 100 to 3000 ppm is particularly preferable, and 200 to 2000 ppm is most preferable. If it is 0% by weight, the dispersibility and applicability may be insufficient, and if it exceeds 1% by weight, the applicability may be insufficient. In addition, a component (A) and a component (B) here mean a non volatile matter.

  When the component (A) is 100 parts by weight, the component (C) is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50, still more preferably 1 to 30, 20 is particularly preferable, and 3 to 10 is most preferable. If it is less than 0.1 parts by weight, the dispersibility may be insufficient, and if it exceeds 100 parts by weight, the handleability may be insufficient.

When the component (B1) and the component (B2) are contained, it is preferable from the viewpoint of improving dispersibility.
When the component (B1) and the component (B2) are contained, the weight ratio of the component (B2) to the component (B1) is preferably 0.01 to 100% by weight, and 0.05 to 10% by weight. More preferred is 0.1 to 1% by weight.

  The weight ratio of the component (A) in the nonvolatile content of the dispersant composition for secondary battery slurry is preferably 70 to 99.9999%, more preferably 80 to 99%, still more preferably 85 to 97.5%, 90 to 95% is particularly preferable. If it is less than 70%, the binding property may be insufficient, and if it exceeds 99.9999%, the dispersibility and the coating property may be insufficient. In addition, the component (A) here means a non-volatile content. The non-volatile content in the present invention refers to an absolutely dry component when the composition is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.

[Secondary battery slurry composition, production method and use thereof]
The secondary battery slurry composition of the present invention can be obtained by a production method in which inorganic particles are dispersed in a solvent in the presence of the secondary battery slurry dispersant composition described above.
The method for producing the secondary battery slurry composition of the present invention is not particularly limited, and for example, a dispersant adjusting step of mixing the secondary battery slurry dispersant composition and a solvent, and the dispersant adjusting step. The manufacturing method etc. which include the inorganic particle dispersion | distribution process of disperse | distributing an inorganic particle to the liquid mixture obtained by these are mentioned.

The inorganic particles will be described later because they vary depending on the application of the secondary battery slurry composition.
Although there is no limitation in particular as content of the component (A) in a secondary battery slurry composition, 0.01-10 weight part with respect to 100 weight part of inorganic particles, Preferably 0.1-6 weight part, More preferably, it is 0.5-5 weight part, More preferably, it is 1-3 weight part, Most preferably, it is 1.5-2 weight part. If it exceeds 10 parts by weight, the battery performance is not excellent. On the other hand, if it is less than 0.01 parts by weight, the coatability is not sufficient.

  In the secondary battery slurry composition, the foaming force is measured by the Ross Miles test method under the measurement conditions of a concentration of 0.1% by weight and a temperature of 25 ° C. which will be described in detail in the following examples. The foaming force immediately after flowing down is 50 mm or less, preferably 40 mm or less, more preferably 30 mm or less, still more preferably 20 mm or less, and particularly preferably 10 mm or less. The foaming power 5 minutes after flowing down is 25 mm or less, preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, and particularly preferably 5 mm or less. If the foaming force immediately after flowing down is more than 50 mm according to the Ross Miles test method, the coatability is not sufficient. Moreover, applicability | paintability is not enough in the foaming power 5 minutes after immediately after flowing down exceeding 25 mm.

  The specific gravity of the secondary battery slurry composition is not particularly limited. For example, it is usually 1 to 4, preferably 1.1 to 3, more preferably 1.2 to 2.5, and still more preferably 1.3 to 2, particularly preferably 1.4 to 1.9, most preferably 1.5 to 1.8. When the specific gravity of the secondary battery slurry composition is more than 4, the dispersion stability may not be excellent. On the other hand, if the specific gravity of the secondary battery slurry composition is less than 1, the coatability may not be excellent.

  The effective concentration of the secondary battery slurry composition is not particularly limited as the pH in the 20 wt% aqueous dispersion, but is preferably 4.0 to 12.0, more preferably 5.0 to 11.0, and particularly preferably. Is 6.0 to 10.0, most preferably 7.0 to 9.0. If pH is less than 4.0, applicability | paintability may be bad. If it exceeds 12.0, the handleability may be poor.

The solvent for dispersing the inorganic particles is not particularly limited and may be an organic solvent or water, but water is preferred because of its low cost and low risk of harmfulness.
The water contained in the secondary battery slurry composition of the present invention may be any of tap water, ion exchange water, distilled water and the like.

  Although there is no limitation in particular as content of the solvent in a secondary battery slurry composition, For example, 1-10000 weight part with respect to 100 weight part of inorganic particles, Preferably it is 10-1000 weight part, More preferably, 50- 500 parts by weight, more preferably 60 to 300 parts by weight, particularly preferably 80 to 200 parts by weight, and most preferably 100 to 150 parts by weight. When the content of the solvent in the secondary battery slurry composition is more than 10,000 parts by weight with respect to 100 parts by weight of the inorganic particles, battery performance may not be excellent. On the other hand, when the content of the solvent in the secondary battery slurry composition is less than 1 part by weight with respect to 100 parts by weight of the inorganic particles, applicability may not be sufficient.

In addition to the components described above, the secondary battery slurry composition of the present invention includes a hydrotrope agent, protective colloid agent, antibacterial agent, antifungal agent, colorant, antioxidant, deodorant, cross-linking agent, catalyst. Further, an emulsion stabilizer, a chelating agent and the like may be further contained.
In order to obtain the secondary battery slurry composition of the present invention, there is no particular limitation on the method of mixing each component such as the dispersant composition for secondary battery slurry, inorganic particles, water, etc. It can be performed using an apparatus having a simple mechanism. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned. Moreover, you may use the mixer which can perform a general rocking | swiveling or stirring. Examples of the mixer include a mixer that can perform rocking stirring or stirring such as a ribbon type mixer and a vertical screw type mixer. Super mixer (made by Kawata Co., Ltd.) and high speed mixer (made by Fukae Co., Ltd.), Newgram Machine (made by Seishin Enterprise Co., Ltd.), SV A mixer (manufactured by Shinko Environmental Solution Co., Ltd.), Filmics (Primix Co., Ltd.), Jet Pasta (Nihon Spindle Manufacturing Co., Ltd.), KRC Kneader (manufactured by Kurimoto Steel Works Co., Ltd.) or the like may be used. Other examples include jaw crushers, gyratory crushers, cone crushers, roll crushers, impact crushers, hammer crushers, rod mills, ball mills, vibration rod mills, vibration ball mills, disk type mills, jet mills, cyclone mills, etc. It may be used. Further, an ultrasonic emulsifier, a continuous biaxial kneader, a high-pressure emulsifier, a microreactor, or the like may be used.

Moreover, the manufacturing method of the secondary battery slurry composition of this invention may include the process of disperse | distributing each component which comprises the dispersing agent composition for secondary battery slurries to a solvent separately. In addition, the quantity of each component at the time of making it disperse | distribute separately to a solvent follows each component content of an above-described secondary battery slurry composition.
The step of separately dispersing the components constituting the dispersant composition for secondary battery slurry in a solvent is not particularly limited. For example, the step of mixing the component (A) and a solvent to obtain a mixture ( a), a step (b) of obtaining a dispersant composition by mixing the mixed solution and the component (B), and a step of obtaining a slurry composition by mixing the dispersant composition and inorganic particles (c) ). In the case of using at least one selected from component (C), component (D) and other components, the step of mixing at least one selected from component (C), component (D) and other components, Any of the step (a), the step (b), and the step (c) may be used, but mixing in the step (a) is preferable because the effect of the present application can be easily obtained because the dispersant composition becomes uniform.
Although there is no limitation in particular as a use of the secondary battery slurry composition of this invention, Surface coating uses, such as a positive electrode use, a negative electrode use, a positive electrode, a negative electrode, a separator, etc. are mentioned.
Hereinafter, various uses will be described in detail.

(Secondary battery positive electrode use)
The secondary battery slurry composition of the present invention can be used as a secondary battery positive electrode application. Examples of the inorganic particles of the slurry composition for a secondary battery positive electrode when the secondary battery slurry composition is used for a secondary battery positive electrode include a positive electrode active material and a conductive auxiliary agent. A secondary battery slurry composition for use in a secondary battery positive electrode can be applied to a current collector sheet, dried, and thinned to be used as a positive electrode for a secondary battery.

As the positive electrode active material is not particularly limited, for example, lithium iron phosphate (LiFePO _4), lithium manganese phosphate (LiMnPO _4), lithium cobalt phosphate (LiCoPO _4), iron pyrophosphate _(Li 2 _FeP 2 O ₇ ), lithium cobaltate composite oxide (LiCoO ₂ ), spinel type lithium manganate lithium cobaltate composite oxide (LiMn ₂ O ₄ ), lithium manganate composite oxide (LiMnO ₂ ), lithium nickelate composite oxide ( LiNiO _2), lithium niobate composite oxide (LiNbO _2), ferrate lithium composite oxide (LiFeO _2), lithium magnesium acid complex oxide (LiMgO _2), calcium lithium composite oxide (LiCaO _2), cuprate lithium composite oxide (LiCuO _2), zinc Lithium composite oxide (LiZnO _2), molybdate lithium composite oxide (LiMoO _2), lithium tantalate complex oxide (LiTaO _2), tungstic acid lithium composite oxide (LiWO _2), lithium - nickel - cobalt - aluminum complex Oxide (LiNi _0.8 Co _0.15 Al _0.05 O ₂ ), lithium-nickel-cobalt-manganese composite oxide (LiNi _0.33 Co _0.33 Mn _0.33 O ₂ , LiNi _0.8 Co _0.1 Mn _0.1 O ₂ ), manganese nickel oxide (LiNi _0.5 Mn _1.5 O ₄ ), manganese oxide (MnO ₂ ), lithium-rich nickel-cobalt-manganese composite oxide, nickel hydroxide ( Ni (OH) ₂ ), vanadium oxide, sulfur oxide, silicate oxide, etc. 1 type or 2 types or more may be sufficient.

  The conductive auxiliary agent is not particularly limited. For example, carbon black such as furnace black, acetylene black, and ketjen black; graphene; carbon nanotube such as carbon nanofiber, single-walled carbon nanotube, and multi-walled carbon nanotube; silver, copper Metal fine particles such as tin, zinc, zinc oxide, nickel and manganese; composite metal fine particles such as indium tin oxide and the like.

  The current collector of the positive electrode is not particularly limited as long as it is a material that has electronic conductivity and can pass through the positive electrode material. For example, C, Ti, Cr, Mo, Ru, Rh, Ta, W, Conductive substances such as Os, Ir, Pt, Au, Al, and Ni, and alloys containing two or more of these conductive substances (for example, stainless steel) can be used. The current collector is preferably C, Al, Ni, stainless steel or the like from the viewpoint of high electrical conductivity and good stability in the electrolytic solution and oxidation resistance, and more preferably Al or the like from the viewpoint of material cost. The shape of the current collector is not particularly limited, and for example, a foil-like substrate, a three-dimensional substrate, or the like can be used. A primer layer may be formed on the current collector surface in advance, and the primer layer may contain a conductive additive.

The method for applying the positive electrode slurry composition to the positive electrode current collector is not particularly limited as long as it can be uniformly wet-coated, and examples thereof include a capillary coating method, a spin coating method, and a slit. A die coating method, a spray coating method, a dip coating method, a roll coating method, a screen printing method, a flexographic printing method, a bar coater method, a gravure coater method, a die coater method and the like can be employed.
The method for removing the solvent from the coating film is generally a method by drying. The drying temperature of the solvent is not particularly limited, but is usually 10 to 200 ° C, preferably 30 to 190 ° C, more preferably 50 to 180 ° C, particularly preferably 80 to 170 ° C, and most preferably 90 to 160 ° C. is there. When the drying temperature of the solvent is higher than 200 ° C., the function of the positive electrode may be deteriorated, which is not preferable.

The surface coat film formed by applying and drying the slurry composition for a secondary battery positive electrode of the present invention on the surface of the current collector may be formed on one side of the current collector, or may be formed on both sides.
The film thickness of the positive electrode coating for one side formed by applying and drying the slurry composition for secondary battery positive electrode of the present invention on the surface of the current collector is not particularly limited, but for example, usually 1 to 500 μm, preferably Is 10 to 400 μm, more preferably 20 to 300 μm, particularly preferably 30 to 200 μm, and most preferably 50 to 150 μm. When the film thickness of the positive electrode film for one side is less than 1 μm, the battery performance may be deteriorated, which is not preferable. When the film thickness of the surface coat film for one side is more than 500 μm, the handling property may be lowered, which is not preferable.

(Use for secondary battery negative electrode)
The secondary battery slurry composition of the present invention can be used for secondary battery negative electrode applications. Examples of the inorganic particles of the secondary battery negative electrode slurry composition when the secondary battery slurry composition is used as a secondary battery negative electrode application include a negative electrode active material and a conductive auxiliary agent. The secondary battery slurry composition for secondary battery negative electrode is usually applied to a current collector sheet, dried and thinned to be used as a secondary battery negative electrode.

As the negative electrode active material is not particularly limited, for example, natural graphite, artificial graphite, expanded graphite, activated carbon, carbon fiber, coke, soft carbon, carbon materials such as hard carbon, silicon, SiO, SnO, _SnO 2, Metal oxides such as CuO, Li ₄ Ti ₅ O ₁₂ ; Si—Al, Al—Zn, Si—Mg, Al—Ge, Si—Ge, Si—Ag, Zn—Sn, Ge—Ag, Ge—Sn , Ge—Sb, Ag—Sn, Ag—Ge, Sn—Sb and other alloys; tin phosphate glass type and the like may be mentioned, and one or more may be used.

  The conductive auxiliary agent is not particularly limited. For example, carbon black such as furnace black, acetylene black, and ketjen black; graphene; carbon nanotube such as carbon nanofiber, single-walled carbon nanotube, and multi-walled carbon nanotube; silver, copper Metal fine particles such as tin, zinc, zinc oxide, nickel and manganese; composite metal fine particles such as indium tin oxide and the like.

  The negative electrode current collector is not particularly limited as long as it has electronic conductivity and can pass through the negative electrode material. For example, Cu, Ni, C, Ti, Cr, Mo, Ru, Rh, Conductive substances such as Ta, W, Os, Ir, Pt, Au, and Al, and alloys containing two or more of these conductive substances (for example, stainless steel) can be used. The current collector is preferably Cu, C, Al, stainless steel or the like from the viewpoint of high electrical conductivity and good stability in the electrolyte and oxidation resistance, and Cu or the like is more preferable from the viewpoint of material cost. The shape of the current collector is not particularly limited, and for example, a foil-like base material, a three-dimensional base material, and the like can be used. Specifically, a rolled copper foil, an electrolytic copper foil, and the like are preferable. A primer layer may be formed on the current collector surface in advance, and the primer layer may contain a conductive additive.

  The method for applying the slurry composition for secondary battery negative electrode to the current collector of the negative electrode is not particularly limited as long as it can be uniformly wet-coated, and examples thereof include a capillary coating method, a spin coating method, and a slit. A die coating method, a spray coating method, a dip coating method, a roll coating method, a screen printing method, a flexographic printing method, a bar coater method, a gravure coater method, a die coater method and the like can be employed.

The method for removing the solvent from the coating film is generally a method by drying. The drying temperature of the solvent is not particularly limited, but is usually 10 to 200 ° C, preferably 30 to 190 ° C, more preferably 50 to 180 ° C, particularly preferably 80 to 170 ° C, and most preferably 90 to 160 ° C. is there. When the drying temperature of the solvent is higher than 200 ° C., the function of the negative electrode may be deteriorated, which is not preferable.
The surface coat film formed by applying and drying the slurry composition for secondary battery negative electrode of the present invention on the surface of the current collector may be formed on one side of the current collector, or may be formed on both sides.
The film thickness of the negative electrode film for one side formed by applying and drying the slurry composition for secondary battery negative electrode of the present invention on the surface of the current collector is not particularly limited, but for example, usually 1 to 500 μm, preferably Is 10 to 400 μm, more preferably 20 to 300 μm, particularly preferably 30 to 200 μm, and most preferably 50 to 150 μm. When the film thickness of the negative electrode film for one side is less than 1 μm, the battery performance may be deteriorated, which is not preferable. When the film thickness of the surface coat film for one side is more than 500 μm, the handling property may be lowered, which is not preferable.

(For surface coating)
The secondary battery slurry composition of the present invention can be used as a separator for surface coating or as a positive electrode or negative electrode surface coating as described above. Non-conductive particles etc. are mentioned as an inorganic particle of a secondary battery slurry composition in case a secondary battery slurry composition is used as a surface coat use. The non-conductive particles are not particularly limited. For example, silica (silicon oxide), α-alumina, β-alumina, γ-alumina, θ-alumina and other alumina (aluminum oxide), titania (titanium oxide), Magnesia (magnesium oxide), zirconia (zirconium oxide), calcium oxide, barium oxide, tin oxide, strontium oxide, niobium oxide, cerium oxide, tungsten oxide, indium oxide, gallium oxide, yttrium oxide, iron oxide, antimony oxide, white carbon Inorganic oxide particles such as aluminum nitride and silicon nitride; ion crystal particles such as calcium fluoride, barium fluoride, barium sulfide and calcium sulfide; covalently bonded crystal particles such as silicon and diamond; mica , Talc, vent Ito, kaolin, aluminum silicate, silicates such as sericite; calcium carbonate, magnesium carbonate, carbonates such as barium carbonate and the like, may be one or more. Of these, α-alumina is preferred because of its particularly high thermal and chemical stability.

  The average particle size of the non-conductive particles is not particularly limited, but is usually 0.001 to 100 μm, preferably 0.01 to 10 μm, more preferably 0.1 to 1 μm, and particularly preferably 0.1 to 0.8 μm. Most preferably, the thickness is 0.2 to 0.7 μm. If the average particle size of the non-conductive particles is less than 0.001 μm, the production may be difficult, which may not be preferable. On the other hand, when the average particle diameter of the non-conductive particles is more than 100 μm, the dispersibility is lowered, which is not preferable.

The BET specific surface area of the non-conductive particles is not particularly limited, but is usually 0.1 to 30 m ² / g, preferably 1 to 18 m ² / g, more preferably 4 to 14 m ² / g, particularly preferably. Is 5-10 m ² / g, most preferably 8-10 m ² / g. When the BET specific surface area of the non-conductive particles is less than 0.1 m ² / g, the film-forming property is lowered, which is not preferable. On the other hand, when the BET specific surface area of the non-conductive particles is more than 30 m ² / g, the handling property is lowered, which may not be preferable.

The electric conductivity of the non-conductive particles is not particularly limited. For example, it is preferably 100 μS / cm or less, more preferably 80 μS / cm or less, particularly preferably 40 μS / cm or less, and most preferably 20 μS / cm or less. is there. When the electric conductivity of the non-conductive particles is more than 100 μS / cm, the battery performance is deteriorated, which may not be preferable.
The nonconductive particles may contain a free metal (or metal ion). Although there is no limitation in particular as a free metal, For example, iron, a silica, magnesium, sodium, copper etc. are mentioned.

The content of the free metal is not particularly limited, but is usually 10,000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or less, particularly preferably 10 ppm or less, and most preferably 1 ppm or less. When the content of free metal exceeds 10,000 ppm, battery performance may be deteriorated, which is not preferable.
The zeta potential of the secondary battery slurry composition for surface coating is not particularly limited, but the zeta potential of a 5 wt% aqueous dispersion at a measurement temperature of 25 ° C. is preferably −10 to −100 mV, more preferably It is −10 to −90 mV, more preferably −20 to −80 mV, particularly preferably −30 to −70 mV, and most preferably −35 to −65 mV. When the zeta potential of the secondary battery slurry composition for surface coating having a concentration of 5% by weight is less than -100 mV, handling properties may not be excellent. On the other hand, if the zeta potential of the secondary battery slurry composition for surface coating having a concentration of 5% by weight exceeds -10 mV, the dispersibility may not be sufficient.
Here, the case where the secondary battery slurry composition of the present invention is used as a surface coating for a secondary battery separator will be described in detail.

In secondary batteries, a separator is usually used to prevent a short circuit between the positive electrode and the negative electrode. For example, in the case of a lithium ion battery, when a short circuit occurs inside the battery, the separator has a shutdown function that blocks the hole of the separator, making it impossible for lithium ions to move in the shorted part. By losing the function, it plays a role of maintaining the safety of the lithium ion secondary battery. However, when the battery temperature exceeds, for example, 150 ° C. due to instantaneous heat generation, the separator may contract rapidly and the short-circuited portion between the positive electrode and the negative electrode may expand. In this case, the battery temperature may reach a state where it is abnormally heated to several hundred degrees C or more, which is a problem in terms of safety. Therefore, as means for solving the above problems, an inorganic oxide porous film containing an inorganic oxide filler having insulating properties is formed on the surface of the positive electrode, the negative electrode or the separator constituting the lithium ion secondary battery.
The method for applying the slurry composition for coating a secondary battery separator to the separator is not particularly limited as long as it is a method that enables uniform wet coating, and examples thereof include a capillary coating method, a spin coating method, a slit die coating method, Spray coating, dip coating, roll coating, screen printing, flexographic printing, bar coater, gravure coater, die coater, etc. can be employed.

  The method for removing the solvent from the coating film is generally a method by drying. The drying temperature of the solvent is preferably a temperature not higher than the softening point of the separator, and is usually 10 to 200 ° C, preferably 30 to 150 ° C, more preferably 40 to 120 ° C, particularly preferably 50 to 100 ° C, and most preferably 60. ~ 90 ° C. When the drying temperature of the solvent is higher than 200 ° C., the function of the separator may be deteriorated, which is not preferable.

The resin constituting the composition of the separator is not particularly limited. For example, polyolefin resins such as polyethylene, polypropylene, and polybutylene; polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyamide resins such as nylon; polyamideimide resins; polyacetal resins; polystyrene resins; methacrylic resins; polyvinyl chloride resins; polycarbonate resins; polyphenylene sulfide resins, cellulose resins, and the like.
There is no limitation in particular as a shape of a separator, For example, a microporous film, a nonwoven fabric, etc. are mentioned.
The surface of the separator may be coated with a polyvinylidene fluoride resin, a polyaramid resin, or the like before applying the slurry composition for coating a secondary battery separator.
The separator may be subjected to a hydrophilization treatment before the slurry composition for coating a secondary battery separator is applied. Examples of the hydrophilization treatment include chemical treatment with acid or alkali, corona treatment, and plasma treatment.
The surface coat film formed by applying and drying the slurry composition for coating a secondary battery separator of the present invention on the separator surface may be formed on one side of the separator or on both sides.

The film thickness of the surface coat film for one surface formed by applying and drying the slurry composition for coating a secondary battery separator of the present invention on the separator surface is not particularly limited, but is usually 0.1 to 30 μm, for example. The thickness is preferably 0.3 to 10 μm, more preferably 0.5 to 5 μm, particularly preferably 1 to 4 μm, and most preferably 1 to 3 μm. When the film thickness of the surface coat film for one side is less than 0.1 μm, the heat resistance may deteriorate, which may be undesirable. When the film thickness of the surface coat film for one side is more than 30 μm, the function of the separator may be deteriorated, which is not preferable.
The thickness of the separator coated with the slurry for coating a secondary battery separator of the present invention and dried and surface-coated is not particularly limited. For example, it is usually 1 to 100 μm, preferably 5 to 50 μm, more preferably. Is 10 to 30 μm, particularly preferably 15 to 25 μm, and most preferably 20 to 25 μm. When the film thickness of the surface-coated separator is less than 1 μm, the heat resistance may deteriorate, which may not be preferable. When the film thickness of the surface coat film for one side is more than 100 μm, the function of the separator may be deteriorated, which is not preferable.

It is preferable that the contact angle of the solvent with respect to the separator whose surface is coated by applying the slurry composition for coating a secondary battery separator of the present invention is in a specific range because battery performance is excellent.
The contact angle of water with respect to the separator whose surface is coated by applying and drying the slurry composition for coating a secondary battery separator of the present invention is not particularly limited. For example, it is normal when 1600 msec elapses after water is dropped. It is 60 ° or less, preferably 50 ° or less, more preferably 40 ° or less, further preferably 30 ° or less, and particularly preferably 20 ° or less. If the contact angle of water with the surface-coated separator exceeds 60 °, battery performance may not be excellent.

The contact angle of the electrolytic solution with respect to the separator whose surface is coated by applying the slurry composition for coating a secondary battery separator of the present invention is not particularly limited. For example, when 1600 msec has elapsed since the electrolytic solution was dropped. Is usually 80 ° or less, preferably 70 ° or less, more preferably 60 ° or less, still more preferably 55 ° or less, and particularly preferably 50 ° or less. When the contact angle of the electrolytic solution with respect to the surface-coated separator is more than 80 °, battery performance may not be excellent.
The electrolytic solution used for the measurement of the contact angle of the present invention is propylene carbonate.

[Material for secondary battery and manufacturing method thereof]
Examples of the secondary battery material of the present invention include the positive electrode, the negative electrode, and the separator described above for each use of the secondary battery slurry composition. That is, the positive electrode of the present invention is a positive electrode for a secondary battery having a positive electrode coating on a current collector, and the coating is formed by a nonvolatile component of the secondary battery slurry composition. The negative electrode of the present invention is a negative electrode for a secondary battery having a negative electrode coating film on a current collector, and the coating film is formed by a nonvolatile component of the secondary battery slurry composition. The separator of this invention is a separator which has a coating film for separators, Comprising: The said coating film is formed by the non volatile matter of the secondary battery slurry composition of Claim 5 or 6.

The method for producing the secondary battery material of the present invention is not particularly limited. For example, the step (a) of mixing the component (A), the component (B), and a solvent to obtain a dispersant composition; Step (b) of obtaining a slurry composition by mixing a dispersant composition and inorganic particles, and at least one selected from a positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode, and a separator. The manufacturing method including the process (c) of apply | coating an object and drying and forming a film is mentioned. The step of mixing at least one selected from the component (C), the component (D), and the other components may be any of the step (a), the step (b), and the step (c). Mixing in (a) is preferable because the effect of the present application can be easily obtained by making the dispersant composition uniform.
In addition, about the application | coating method and the drying method, the method already described by each use of the said secondary battery slurry composition is employable.

[Secondary battery]
The secondary battery of this invention can be produced using the positive electrode, negative electrode, and separator which were produced using the dispersing agent composition for secondary battery slurries of this invention, and the manufacturing method is not specifically limited. For example, the above-described negative electrode and positive electrode are overlapped with a separator and wound, folded, or laminated according to the shape of the battery to produce an electrode body, put in the battery container, and inject the electrolyte into the battery container to seal it. May be.
The battery shape is not particularly limited, and examples thereof include a coin type, a cylindrical type, a square type, and a sheet type.
The battery packaging method is not particularly limited, and examples thereof include a metal case, a mold resin, and an aluminum laminate film.

The type of secondary battery is not particularly limited, and lithium ion secondary batteries such as lithium ion batteries and lithium ion polymer batteries; alkaline secondary batteries such as nickel metal hydride batteries and nickel cadmium batteries; sodium sulfur batteries; redox flow batteries An air battery or the like.
Although there is no limitation in particular as electrolyte solution, in the case of a lithium ion battery, what melt | dissolved lithium salt as a supporting electrolyte in a non-aqueous solvent can be used, for example. Examples of the lithium salt include LiPF ₆ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlCl ₄ , LiClO ₄ , CF ₃ SO ₃ Li, C ₄ H ₉ SO ₃ Li, CF ₃ COOLi, (CF ₃ CO) ₂ NLi , (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) ₂ NLi, and the like, and one or more of them may be used. The solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, alkyl carbonate compounds such as dimethyl carbonate, ethylene carbonate, diethyl carbonate, propylene carbonate, butylene carbonate, and methyl ethyl carbonate; γ -Ester compounds such as butyrolactone and methyl formate; ether compounds such as 1,2 dimethoxyethane and tetrahydrofuran; and sulfur-containing compounds such as sulfolane and dimethyl sulfoxide. Other additives may be mixed in the electrolytic solution, and examples thereof include vinylene carbonate.
The electrolytic solution when the secondary battery is a nickel metal hydride battery is not particularly limited and may be an alkaline aqueous solution. Examples thereof include an aqueous solution containing potassium hydroxide or sodium hydroxide.

The secondary battery of the present invention can be used as a power source for various electric devices (including vehicles that use electricity).
Examples of electrical equipment include air conditioners, washing machines, televisions, refrigerators, freezers, air conditioners, laptop computers, tablets, smartphones, computer keyboards, computer displays, desktop computers, CRT monitors, computer racks, printers, and integrated computers. , Mouse, hard disk, computer peripherals, iron, clothes dryer, window fan, walkie-talkie, blower, ventilation fan, music recorder, music player, oven, range, toilet seat with washing function, hot air heater, car component, car navigation, flashlight, Humidifier, portable karaoke machine, ventilation fan, dryer, dry cell, air purifier, mobile phone, emergency light, game machine, blood pressure monitor, coffee mill, coffee maker, kotatsu, copy machine, disc changer, radio, shaver Juicer, shredder, water purifier, lighting equipment, dehumidifier, dish dryer, rice cooker, stereo, stove, speaker, trouser press, vacuum cleaner, body fat scale, weight scale, health meter, movie player, electric carpet, electric kettle , Rice cooker, electric razor, table lamp, electric pot, electronic game machine, portable game machine, electronic dictionary, electronic notebook, microwave oven, electromagnetic cooker, calculator, electric cart, electric wheelchair, electric tool, electric toothbrush, red bean , Haircut equipment, telephones, watches, intercoms, air circulators, lightning insecticide, copiers, hot plates, toasters, dryers, electric drills, water heaters, panel heaters, crushers, soldering irons, video cameras, video decks, facsimiles , Fan heater, food processor, futon dryer, headphone , Electric kettle, hot carpet, microphone, massage machine, bean bulb, mixer, sewing machine, mochi machine, floor heating panel, lantern, remote control, cold storage, water cooler, refrigeration stocker, cold air blower, word processor, bubbler, electronic Musical instruments, motorcycles, toys, lawn mowers, walkers, bicycles, automobiles, hybrid cars, plug-in hybrid cars, electric cars, railways, ships, airplanes, emergency storage batteries, etc.

[Measurement of viscosity]
A 20% concentration aqueous dispersion of component (A) was prepared and measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd .: BL type) in an atmosphere at 25 ° C.

[Foaming power]
The measurement was performed under a measurement condition at a temperature of 25 ° C. by the Ross Miles test method based on the method of JIS K3362. An aqueous solution having an effective concentration of 0.1% by weight of the composition was used as a test solution, 50 ml of the test solution was poured along the tube wall of the Ross Miles measuring device, and 200 ml of the test solution was also placed in the upper falling pipette. Set the pipette so that the drop of the test solution falls in the center of the cylinder of the Ross Miles measuring device, let the test solution flow down from the height of 90 cm, and the height of the foam immediately after the flow ends (immediately after the flow) and immediately after the flow The height of the foam after 5 minutes was measured. The effective concentration in the present specification refers to the weight ratio of the absolutely dry component when the composition is heat-treated at 105 ° C. to remove the solvent and reach a constant weight with respect to the weight of the composition. .

〔surface tension〕
An aqueous solution having an effective concentration of 0.1% by weight was used as a test solution, and an automatic surface tension meter (manufactured by KRUSS, product number Tensiometer K100) was used, and measurement was performed at a temperature of 25 ° C. by the Wilhelmy method.

[Contact angle]
The measurement was performed using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number DM-901) using an aqueous solution of 5% by weight effective concentration of the dispersant composition for secondary battery slurry as a test solution. As the alumina plate, a dense alumina plate (50 × 50 × 2 mm, sold by ASONE) was used.
[Measurement of glass transition point]
It measured using the dynamic-viscoelasticity measuring apparatus (The TI instrument company make, product number Q800).
[Measurement of thermogravimetry (TGA)]
Using a differential thermal balance (manufactured by Rigaku Corporation, product number Thermo plus EVO), the measurement was performed under the measurement conditions of a setting start temperature of 20 ° C., a setting final temperature of 300 ° C., and a heating rate of 10 ° C. per minute.
[Measurement of average particle size and zeta potential]
Measurement was performed using a particle size / zeta potential measurement system (ELSZ-1000, manufactured by Otsuka Electronics Co., Ltd.).

The method for detecting the component (B) of the present invention is as follows.
A dispersion composition for secondary battery slurry 100 mg, 2, 4 dinitrophenylhydrazine hydrochloride 2 mg, acetonitrile 2 ml, 0.01 mol / l hydrochloric acid 1 ml were mixed to prepare a measurement sample, and then a high-speed liquid was measured under the following measurement conditions. The component (B) of the present invention can be detected by measuring chromatography (HPLC).
(Measurement condition)
Instrument name: General-purpose HPLC Prominence, manufactured by Shimadzu Corporation
Column: manufactured by GL Science, ODS 5C18-200A (4.6 mmφ × 200 mm)
Eluent: Water / acetonitrile (50/50, gradient 20/80)
Flow rate: 1 ml / min Column temperature: 40 ° C
Detector: UVD254nm
Injection volume: 20 μl

[Polymer component (A)]
About the high molecular component (A) used by the Example and the comparative example, those specific manufacturing methods and physical property are shown to the following manufacture examples A-1 to A-19 of Tables 1-3.

[Component (B)]
The component (B) used in the examples and comparative examples is shown below.
[Aldehyde compound component (B1)]
Aldehyde compound B1-1: Compound represented by general formula (1) wherein R is a methyl group. Aldehyde compound B1-2: Compound represented by general formula (1) and R is an ethyl group. Compound aldehyde compound B1-3: General formula (1) ), Wherein R is a butyl group. Aldehyde compound B1-4: a compound in which R is a phenyl group in the general formula (1)

[Aldehyde compound component (B2)]
Ether compound B2-1: a compound (mixture) in which R is a methyl group and the value of n is 0 to 5 in the general formula (2)
Ether compound B2-2: a compound (mixture) in which R is an ethyl group and the value of n is 0 to 5 in the general formula (2)
Ether compound B2-3: compound (mixture) in which the general formula (2), R is a butyl group, and the value of n is 0 to 5
Ether compound B2-4: Compound (mixture) in the general formula (2), wherein R is a phenyl group and the value of n is 0 to 5

[Defoaming component (D)]
The antifoaming agents used in Examples and Comparative Examples are shown below.
Polysiloxane antifoaming agent 1: dimethylpolysiloxane, viscosity 100 mPa · s
Polysiloxane antifoaming agent 2: dimethylpolysiloxane, viscosity 1000 mPa · s
Silica fine powder defoaming agent: Silica fine powder mineral oil defoaming agent hydrophobized with trimethylethoxysilane: Paraffin mineral oil

[Inorganic particles]
Inorganic particles used in Examples and Comparative Examples are shown below.
α-alumina 1: primary particle size 0.3 μm, BET specific surface area 8.4 m ² / g
α-alumina 2: primary particle size 0.8 μm, BET specific surface area 4.9 m ² / g
γ-alumina: primary particle size 0.3 μm, BET specific surface area 4.7 m ² / g
θ alumina: primary particle size 0.3 μm, BET specific surface area 5.3 m ² / g
Silica: primary particle size 0.3 μm, BET specific surface area 5.4 m ² / g
Lithium cobaltate; primary particle size 7.3 μm, BET specific surface area 0.4 m ² / g
Lithium-nickel-cobalt-manganese composite oxide (LiNi _0.33 Co _0.33 Mn _0.33 O ₂ ; primary particle diameter 11.5 μm, BET specific surface area 0.3 m ² / g
Lithium manganate composite oxide (LiMnO ₂ ); primary particle size 10.1 μm, BET specific surface area 0.3 m ² / g
Lithium iron phosphate (LiFeO ₄ ); primary particle size 12.1 μm, BET specific surface area 0.3 m ² / g
Graphite; primary particle size 11.1 μm, BET specific surface area 0.4 m ² / g
Hard carbon; primary particle size 13.3 μm, BET specific surface area 0.2 m ² / g
Acetylene black; average particle diameter 70.1 nm, BET specific surface area 68 m ² / g
Carbon nanofiber: fiber diameter 150.0 nm, BET specific surface area 13 m ² / g

[Production Example A-1]
First, 10 g of acrylic acid and 90 g of acrylamide were prepared as polymerizable monomers, and 0.1 g of ammonium persulfate was prepared as a catalyst.
The polymerizable monomer and catalyst prepared above and 400 g of ion exchange water were mixed and stirred with a homogenizer, and reacted in a 1000 ml separable flask at 80 ° C. for 3 hours in a nitrogen stream. Finally, 5 g of sodium hydroxide was added and mixed to obtain an acrylic polymer component A-1. This acrylic polymer component A-1 is water-soluble and has a nonvolatile content concentration of 20.3% by weight, a viscosity of 20000 mPa · s, a zeta potential of −20 mV, a thermogravimetric measurement of 3.3%, and a glass transition point of 155 ° C. there were.

[Production Examples A-2 to A-19]
In Production Examples A-2 to A-19, each of the polymer components was obtained in the same manner as in Production Example A-1, except that the raw materials were changed as shown in Tables 1 to 3 in Production Example A-1. Physical properties and the like were evaluated in the same manner as in Production Example A-1.

[Production Example 1]
Dispersion for secondary battery slurry by uniformly mixing 500 g of an acrylic polymer aqueous solution containing 100 g of polymer component A-1 as component (A) and 1 g of aldehyde component B-1 as component (B) An agent composition was obtained. The amount of ion-exchanged water was 400 g of ion-exchanged water contained in the polymer component A-1. The dispersant composition for secondary battery slurry has a non-volatile concentration of 20.5%, a viscosity of 20000 mPa · s, a pH of 6.6, a surface tension of 36.8 mN / m, a zeta potential of −25 mV, and a foaming power of 80 mm immediately after. The value after 5 minutes was 20 mm, the contact angle to the alumina plate as an inorganic oxide plate was 45 ° when 1600 msec had elapsed, and the contact angle to the polyolefin resin was 20 ° when 1600 msec had elapsed.

[Production Examples 2 to 21]
In Production Examples 2 to 21, a secondary battery slurry dispersant composition was obtained in the same manner as in Production Example 1 except that the raw materials were changed as shown in Tables 4 to 6, and physical properties and the like were also as in Production Example 1. Evaluation was performed in the same manner. The results are shown in Tables 4-6.

[Example 1]
A secondary battery slurry composition was obtained by uniformly mixing 100 g of α-alumina 1 as inorganic particles, 30 g of the dispersant composition 9 for secondary battery slurry as a dispersant, and 100 g of ion-exchanged water.
The obtained secondary battery slurry composition had a non-volatile content concentration of 46.8% by weight, a viscosity of 60 mPa · s, an average particle size of 340 nm, a zeta potential of −50 mV, and a foaming force of 20 mm immediately after, and a value after 5 minutes. Was 5 mm.
When the dispersion stability of the secondary battery slurry dispersant composition was evaluated using this secondary battery slurry composition, the weight of the sediment was less than 5% by weight, and the dispersion stability was excellent.
The secondary battery slurry composition obtained above was applied to a polyolefin resin separator having a thickness of 20 μm and dried in an oven at 80 ° C. After drying, the coated area of the separator surface was 95% or more, and the coating property was excellent. The surface coat film thickness was 5 μm. A surface-coated separator having a surface-coated separator surface has a shrinkage rate of 95% or more and excellent heat resistance.

[Examples 2 to 8]
In Examples 2 to 8, secondary battery slurry compositions were obtained in the same manner as in Example 1 except that the raw materials were changed as shown in Table 7 in Example 1. Evaluation was performed in the same manner. The results are shown in Table 7.

Example 9
95 g of lithium cobaltate as inorganic particles, 5 g of acetylene black and 30 g of the dispersant composition 9 for secondary battery slurry as a dispersant and 50 g of ion-exchanged water are uniformly mixed to obtain a secondary battery slurry composition. It was. The resulting secondary battery slurry composition had a non-volatile content of 69.3% by weight, a viscosity of 6000 mPa · s, an average particle size of 11.1 μm, a pH of 8.3, a zeta potential of −45 mV, and a foaming power of 20 mm immediately after. The value after 5 minutes was 5 mm.
When the dispersion stability of the secondary battery slurry dispersant composition was evaluated using this secondary battery slurry composition, the weight of the sediment was less than 5% by weight, and the dispersion stability was excellent.
The secondary battery slurry composition obtained above was applied to an aluminum foil having a thickness of 20 μm and dried in an oven at 150 ° C. to obtain a positive electrode film for a secondary battery. The coated area of the current collector after drying was 95% or more, and the coating property was excellent without cracking on the surface. The drying property was also within 300 seconds, and the drying property was excellent. The film thickness of the positive electrode coating for secondary batteries was 50 μm. When an equivalent mixed solution of ethylene carbonate and dimethyl carbonate was dropped on the surface of the positive electrode coating for a secondary battery and the contact angle at 1600 msec elapsed was measured, the contact angle was less than 20 °, and the liquid retention of the electrolyte was excellent. It was.

[Examples 10 to 16]
In Examples 10 to 16, secondary battery slurry compositions were obtained in the same manner as in Example 9 except that the raw materials were changed as shown in Table 8 in Example 9. Evaluation was performed in the same manner. The results are shown in Table 8.

Example 17
A secondary battery slurry composition was obtained by uniformly mixing 95 g of graphite as inorganic particles, 5 g of acetylene black, and 30 g of dispersant composition 1 for secondary battery slurry as a dispersant and 50 g of ion-exchanged water. The obtained secondary battery slurry composition had a non-volatile content concentration of 67.2% by weight, a viscosity of 5500 mPa · s, an average particle size of 15.2 μm, a pH of 7.4, a zeta potential of −48 mV, and a foaming power of 15 mm immediately after. The value after 5 minutes was 5 mm.
When the dispersion stability of the secondary battery slurry dispersant composition was evaluated using this secondary battery slurry composition, the weight of the sediment was less than 5% by weight, and the dispersion stability was excellent.
The secondary battery slurry composition obtained above was applied to a copper foil having a film thickness of 18 μm and dried in an oven at 150 ° C. to obtain a negative electrode film for a secondary battery. The coated area of the current collector after drying was 95% or more, and the coating property was excellent without cracking on the surface. The drying property was also within 300 seconds, and the drying property was excellent. The film thickness of the negative electrode film for secondary batteries was 70 μm. When an equivalent mixed solution of ethylene carbonate and dimethyl carbonate was dropped onto the surface of the negative electrode film for a secondary battery and the contact angle after 1600 msec was measured, the contact angle was less than 20 °, and the liquid retention of the electrolyte was excellent. It was.

[Examples 18 to 23]
In Examples 18 to 23, secondary battery slurry compositions were obtained in the same manner as in Example 17 except that the raw materials were changed as shown in Table 9 in Example 17. Evaluation was performed in the same manner. The results are shown in Table 9.

[Comparative Example 1]
A secondary battery slurry composition was obtained by uniformly mixing 100 g of α-alumina 1 as inorganic particles, 30 g of the dispersant composition 9 for secondary battery slurry as a dispersant, and 100 g of ion-exchanged water.
The obtained secondary battery slurry composition had a non-volatile content of 46.5% by weight, a viscosity of 50 mPa · s, an average particle size of 650 nm, a zeta potential of −10 mV, and a foaming power of 10 mm immediately after, and a value after 5 minutes. Was 5 mm.
When the dispersion stability of the secondary battery slurry dispersant composition was evaluated using this secondary battery slurry composition, the weight of the sediment was 10% by weight or more and less than 30% by weight, and the dispersion stability was poor. .
The secondary battery slurry composition obtained above was applied to a polyolefin resin separator having a thickness of 20 μm and dried in an oven at 80 ° C. The area of the coated surface of the separator after drying is less than 80%, which is inferior in applicability. The surface coat film thickness was 2 μm. The secondary battery film having the separator surface coated thereon has a shrinkage rate of less than 80% and is inferior in heat resistance.

[Comparative Examples 2 to 10]
In Comparative Examples 2 to 10, secondary battery slurry compositions were obtained in the same manner as in Comparative Example 1 except that the raw materials were changed as shown in Table 10 and Table 11 in Comparative Example 1, and the physical properties and the like were also compared. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 10 and Table 11.

As can be seen from Tables 7 to 9, the slurry compositions for secondary batteries of Examples 1 to 23 were the polymer component (A), the aldehyde compound component (B1) represented by the general formula (1), and the general Since it contains at least one component (B) selected from the ether compound component (B2) represented by the formula (2), the problem of the present application can be solved.
On the other hand, as can be seen from Tables 10 and 11, when there is no component (B) (Comparative Examples 1 to 10), any of the problems of the present application cannot be solved.

[Evaluation of dispersion stability]
The prepared secondary battery slurry composition was stored in a 100 ml centrifuge tube at room temperature for 24 hours, and the weight of the sediment was measured. The evaluation criteria for dispersion stability are as follows.
(Double-circle): The weight of a sediment is less than 5 weight%, and is excellent in dispersion stability.
A: The weight of the sediment is 5% by weight or more and less than 10% by weight, and the dispersion stability is excellent.
(Triangle | delta): The weight of a sediment is 10 weight% or more and less than 30 weight%, and is inferior to dispersion stability.
X: The weight of a sediment is 30 weight% or more, and it is inferior to dispersion stability.

[Evaluation of coating properties]
(In case of separator)
The secondary battery slurry composition was applied to the surface of the polyolefin-based separator at 15 g / m ² , heated to a temperature of 80 ° C. and dried. The area covered with the separator surface was measured. The evaluation criteria for applicability are as follows.
A: The coated area is 95% or more, and the coating property is excellent.
A: The covering area is 90% or more and less than 95%, and the coating property is excellent.
(Triangle | delta): A coating area is 80% or more and less than 90%, and is inferior to applicability | paintability.
X: The coating area is less than 80%, and the applicability is poor.
(For positive electrode and negative electrode)
The secondary battery slurry composition was applied to the surface of the current collector at 10 mg / cm ² , heated to a temperature of 150 ° C. and dried. The area covered with the surface of the current collector was measured. The evaluation criteria for applicability are as follows.
○: The coated area is 95% or more, and the coating surface is not cracked during drying, and the coating property is excellent.
X: Cracks occurred on the coated surface at the time of drying, and the coated area was less than 95%, and the coating property was inferior.

[Evaluation of dryness]
(In case of separator)
The secondary battery slurry composition is applied to the surface of the polyolefin-based separator at 15 g / m ^2, and the time until the coated surface is dried at a temperature of 80 ° C. is visually measured. The dryness evaluation criteria are as follows.
○: If the drying time is 30 seconds or less, the waiting time is small and the drying property is good.
X: If the drying time exceeds 30 seconds, the waiting time is long and the workability is hindered, so the drying property is not good.
(For positive electrode and negative electrode)
The secondary battery slurry composition is applied to the current collector surface at 10 mg / cm ^2, and the time until the coated surface dries at a temperature of 150 ° C. is measured visually. The dryness evaluation criteria are as follows.
○: If the drying time is 300 seconds or less, the waiting time is small and the drying property is good.
X: If the drying time exceeds 300 seconds, the waiting time is long and the workability is hindered, so the drying property is not good.

[Evaluation of heat resistance]
A sample of 10 cm long × 10 cm wide of the produced surface-coated separator was stored in a constant temperature bath at 120 ° C. for 8 hours and heated, and then the length of each sample was measured to calculate the shrinkage. The evaluation criteria for heat resistance are as follows. The heat resistance of the surface-coated separator was evaluated based on the smaller shrinkage ratio, either vertical or horizontal.
Shrinkage rate (%) = (length or width of surface coat separator after heating for 8 hours / 10) × 100
A: Shrinkage is 95% or more and excellent in heat resistance.
A: The shrinkage rate is 90% or more and less than 95%, and the heat resistance is excellent.
(Triangle | delta): Shrinkage is 80% or more and less than 90%, and is inferior to heat resistance.
X: Shrinkage is less than 80%, and heat resistance is poor.

[Evaluation of water retention properties]
Using a contact angle meter (product number DM-901, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle when 1600 msec had elapsed after dropping water on the surface coat separator was evaluated.
(Double-circle): A contact angle is less than 20 degrees and is excellent in the liquid retention of water.
◯: The contact angle is 20 ° or more and less than 30 °, and the liquid retainability is excellent.
(Triangle | delta): A contact angle is 30 degrees or more and less than 40 degrees, and is inferior to the liquid retention of water.
X: A contact angle is 40 degrees or more, and it is inferior to the liquid retention of water.

[Evaluation of electrolyte retention]
Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number DM-901), an equivalent mixed solution of ethylene carbonate and dimethyl carbonate was dropped onto any one of the surface coat separator, the positive electrode, and the negative electrode, and contact was made after 1600 msec. The angle was measured and evaluated.
(Double-circle): A contact angle is less than 20 degrees, and it is excellent in the liquid retention property of electrolyte solution.
◯: The contact angle is 20 ° or more and less than 30 °, and the electrolyte retainability is excellent.
(Triangle | delta): A contact angle is 30 degrees or more and less than 40 degrees, and is inferior to the liquid holding property of electrolyte solution.
X: A contact angle is 40 degrees or more, and it is inferior to the liquid retention property of electrolyte solution.

Claims (12)

A component that is at least one selected from a polymer component (A), an aldehyde compound component (B1) represented by the following general formula (1), and an ether compound component (B2) represented by the following general formula (2) A dispersant composition for a secondary battery slurry, comprising (B).

(However, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.)

(Wherein, ^{R 2} is a hydrogen atom, an alkyl group, an alkenyl group, an .n = 0 to 30 is an alkanol group or an aryl group.)   The dispersant composition for secondary battery slurry according to claim 1, further comprising a surfactant component (C).   The dispersant composition for secondary battery slurry according to claim 1 or 2, wherein a weight ratio of the component (B) to the component (A) is more than 0 wt% and 1 wt% or less.   The foaming force with an effective concentration of 0.1% by weight at 25 ° C. according to the Ross Miles test method is 50 mm or less immediately after flowing down and 25 mm or less immediately after flowing down and 5 minutes after flowing. The dispersing agent composition for secondary battery slurry as described. The said component (A) is a dispersing agent composition for secondary battery slurries in any one of Claims 1-4 which contains the following polymer particle component (A1) essential.
Polymer particle component (A1): Essentially containing an alkyl ester group-containing monomer unit (II), and the weight ratio of the carboxyl group-containing monomer unit (I) to the whole polymerizable monomer is less than 31% by weight. is there The said component (A) is a dispersing agent composition for secondary battery slurries in any one of Claims 1-5 which contains the following polymer component (A2) essential.
Polymer component (A2): Carboxyl group-containing monomer unit (I) based on the whole polymerizable monomer The weight ratio is 31% by weight or more A component that is at least one selected from a polymer component (A), an aldehyde compound component (B1) represented by the following general formula (1), and an ether compound component (B2) represented by the following general formula (2) A secondary battery slurry composition containing (B) and inorganic particles,
When the content of the inorganic particles is 100 parts by weight, the respective contents are 0.01 to 100 parts by weight for the component (A) and 0.0001 to 1 part by weight for the component (B). Secondary battery slurry composition.

(However, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.)

(Wherein, ^{R 2} is a hydrogen atom, an alkyl group, an alkenyl group, an .n = 0 to 30 is an alkanol group or an aryl group.) A polymer component (A) is mixed with at least one selected from an aldehyde compound component (B1) represented by the following general formula (1) and an ether compound component (B2) represented by the following general formula (2) Step (a) to obtain a dispersant composition, step (b) to obtain a slurry composition by mixing the dispersant composition and inorganic particles, a positive electrode current collector, a negative electrode current collector, The manufacturing method of the material for secondary batteries including the process (c) which apply | coats the said slurry composition to at least 1 sort (s) chosen from a positive electrode, a negative electrode, and a separator, and forms a film by drying.

(However, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkanol group or an aryl group.)

(Wherein, ^{R 2} is a hydrogen atom, an alkyl group, an alkenyl group, an .n = 0 to 30 is an alkanol group or an aryl group.)   A positive electrode for a secondary battery, which is a positive electrode for a secondary battery having a positive electrode coating film on a current collector, wherein the coating film is formed of a nonvolatile content of the secondary battery slurry composition according to claim 7.   A negative electrode for a secondary battery having a negative electrode coating film on a current collector, wherein the coating film is formed of a non-volatile component of the secondary battery slurry composition according to claim 7.   The separator for secondary batteries which is a separator which has a coating film for separators, Comprising: The said film is formed with the non volatile matter of the secondary battery slurry composition of Claim 7.   A secondary battery including a negative electrode, a positive electrode, a separator, and an electrolyte solution, wherein at least one of the negative electrode, the positive electrode, and the separator is formed of a non-volatile component of the secondary battery slurry composition according to claim 7. A secondary battery having a coating.