JP2020015816A - Polymer, coating agent, ink composition, electricity storage device electrode, and electricity storage device - Google Patents

Abstract

To provide a polymer capable of providing an electricity storage device excellent in adhesiveness with an inorganic material such as a powder collection body or an active material, and having excellent charge and discharge cycle property, a coating agent, an ink composition, and an electrode for electricity storage device using the polymer, and an electricity storage device using the electrode.SOLUTION: There is provided a polymer which is a polymer of a monomer mixture containing a monomer (A) represented by the formula (1) of 2 to 50 wt.%, and a (meth)acrylamide-based monomer (B) of 50 to 98 wt.% based on 100 wt.% of the monomer mixture. Ar-CH=CH-COOH (1), wherein Ar is a phenyl group having Rto R, each being independently a hydrogen atom, a hydroxyl group, or a methoxy group, and at least one of Rto Ris the hydroxyl group.SELECTED DRAWING: None

Description

  The present invention relates to a polymer, a coating agent, an ink composition, an electrode for a power storage device, and a power storage device.

In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. In these electronic devices, it is always required to minimize the volume and reduce the weight, and it is also required to realize a small-sized, light-weight, and large-capacity battery. Also in large secondary batteries for automobiles, etc., it is desired to realize large secondary batteries in place of conventional lead-acid batteries, and further longer life is required in various environments where batteries are used. Have been. Furthermore, capacitors such as an electric double layer capacitor and a lithium ion capacitor have attracted attention as power storage devices with high output and high energy density.

In order to meet such demands, there is increasing interest in the development of secondary batteries such as lithium ion secondary batteries and alkaline secondary batteries, and the storage devices such as capacitors, for example, the development of binders for electrode plates.

The electrode of the power storage device requires a binder for binding the electrode active material to the current collector in addition to the electrode active material. Among the electricity storage devices, in particular, fluorine resins such as polyvinylidene fluoride and polytetrafluoroethylene have been often used for both the positive electrode and the negative electrode as binder resins for secondary batteries (Non-Patent Documents 1 and 2).
However, in a secondary battery, since the positive electrode or the negative electrode repeatedly expands and contracts in volume during charge and discharge, the charge / discharge cycle life may be shortened due to dropout of the active material and the conductive agent. Therefore, the electrode binder is required to have a cushioning property capable of withstanding swelling and shrinking of the electrode. However, the fluororesin has insufficient cushioning properties to follow the electrodes. Further, adhesion to a current collector and an active material is poor, and unless a large amount of a binder resin is used, no effect is exhibited as a binder. For this reason, the active material density in the electrode cannot be increased, which has been an obstacle to producing a high-capacity battery electrode. In addition, the fluororesin has a feature that it is soluble only in a specific solvent such as N-methylpyrrolidone, and has a problem of adverse effects on human bodies and the environment, such as an unpleasant odor during electrode production.

To solve these problems, development of an aqueous resin as a binder for an electrode has been advanced. Patent Literature 1 reports a resin in which an acidic functional group, a nitrile group, and a crosslinking group are incorporated, and discloses that the resin has excellent cycle characteristics and electrode plate adhesion. Patent Document 2 reports a water-soluble resin having a carboxyl group and a sulfo group, and discloses that the active material can be prevented from peeling due to a volume change during charge and discharge.
Although the development of aqueous resins as binders for electrodes has been promoted in this way, the demand for smaller, higher capacity, and safer energy storage devices continues to increase every day. There is a demand for improved charge / discharge cycle characteristics and higher performance.

"Battery Handbook" published by Denki Shoin 1980 "Industrial Materials" September 2008 Issue (Vol. 56, No. 9)

International Patent Publication WO2011 / 002057 JP 2013-033692

An object of the present invention is to provide a polymer which has excellent adhesion to an inorganic material such as a current collector or an active material and can provide an electric storage device having excellent charge / discharge cycle characteristics. Furthermore, it is another object of the present invention to provide a coating agent, an ink composition, an electrode for a power storage device using the polymer, and a power storage device using the electrode.

The present invention provides a monomer containing 2 to 50% by weight of a monomer (A) represented by the following general formula (1) and 50 to 98% by weight of a (meth) acrylamide-based monomer (B) based on 100% by weight of a monomer mixture. The present invention relates to a polymer (P), which is a polymer of a mixture.
General formula (1)
(R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, or a methoxy group, and at least one of R _{1 to} R ₄ is a hydroxyl group.)

The present invention also relates to the polymer (P), wherein at least two of R _{1 to} R ₄ are a hydroxyl group.

  Further, the present invention relates to the polymer (P), which has a glass transition temperature of 60 to 200 ° C.

  The present invention also relates to the polymer (P), wherein the number average molecular weight is 3,000 or more.

  The present invention also relates to a coating agent comprising the polymer (P).

  Further, the present invention relates to a coating substrate having an inorganic substrate and a film made of the coating agent.

  The present invention also relates to an ink composition (R) comprising the polymer (P) and a pigment (Q).

  Further, the present invention relates to a power storage device electrode (S) having a current collector and an ink film formed from the ink composition.

    The present invention also relates to a power storage device including a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the power storage device electrode (S).

The resin composition of the present invention has excellent adhesion to a current collector and an active material, and by using this polymer, it is possible to provide an electrode having excellent adhesion to a current collector, and thus to provide an excellent charge. An electricity storage device having discharge cycle characteristics can be provided.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example (representative example) of the embodiment of the present description, and the present invention is not limited to these contents unless it exceeds the gist.

<Polymer (P)>
The polymer (P) used in the present invention is a polymer of a monomer mixture containing a monomer (A) having a structure represented by the general formula (1) and a (meth) acrylamide-based monomer (B), With this structure, it is possible to obtain excellent adhesiveness to inorganic materials such as metals, active materials, and glass even when impregnated with water or an organic solvent. Thereby, when the polymer (P) is used as a binder for an electrode, excellent charge / discharge cycle characteristics as an electricity storage device can be obtained.

<Monomer (A)>
The monomer (A) used in the present invention has a structure represented by the general formula (1).
General formula (1)
(R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, or a methoxy group, and at least one of R _{1 to} R ₄ is a hydroxyl group.)

Examples of the monomer (A) used in the present invention include, but are not limited to, m-coumaric acid, p-coumaric acid, and m-coumaric acid, in which one of R _{1 to} R ₄ is a hydroxyl group. Sinapic acid, ferulic acid, and those in which two of R _{1 to} R ₄ are hydroxyl groups include 2,4-dihydroxycinnamic acid, 2,3-dihydroxycinnamic acid, 2,5-dihydroxycinnamic acid, 3, 5-dihydroxycinnamic acid, caffeic acid and the like. These may be used alone or in combination of two or more kinds in any combination.

The monomer (A) used in the present invention is particularly excellent in water-resistant adhesiveness in that it is particularly excellent in adhesiveness to inorganic materials, and is excellent in charge-discharge cycle characteristics when used as an electricity storage device. , R _{1 to} R ₄ , it is preferable that at least two adjacent groups are hydroxyl groups, and examples of such a monomer (A) include 2,3-dihydroxycinnamic acid and caffeic acid.

The amount of the monomer (A) used in the present invention is 2 to 50% by weight, preferably 5 to 40% by weight, based on 100% by weight of the monomer mixture.

<(Meth) acrylamide monomer (B)>
The monomer (B) used in the present invention is selected from known (meth) acrylamide monomers. Since the monomer (B) has excellent adhesion to inorganic materials and high resistance to acids, alkalis, and oxidation-reduction, excellent performance can be obtained when used as an electricity storage device.

Known (meth) acrylamide monomers include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (Me ) Acrylamide, crotonamide, maleamide, fumaramido, mesaconamide, citraconamide, itaconamide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- Aliphatic (such as [3- (N ′, N′-dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethaneamide, N-vinylacetamide (Meth) acrylamide;
Hydroxyl-containing (N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. (Meth) acrylamide;
N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxyoctyl ( (Meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N -Ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-isopropoxy Methyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide , N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) acryl Amide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetan-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetan-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamide containing an N-alkoxy group such as (meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;
Quaternary salt compounds such as dimethylaminopropylacrylamide methyl chloride quaternary salt; and acryloylmorpholine. These may be used alone or in combination of two or more kinds in any combination. Of these, acrylamide monomers are preferred from the viewpoint of excellent copolymerizability.

  The amount of the monomer (B) used in the present invention is 50 to 98% by weight, preferably 60 to 90% by weight, based on 100% by weight of the monomer mixture.

  As the polymer (P) of the present invention, other than the monomer (A) and the monomer (B), other monomers (C) may be used as long as the effects of the present invention are not impaired.

Examples of the monomer (C) that can be used in the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, and indene;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) Alkyl (meth) acrylates such as acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate monomer;
(Meth) acrylate monomers having an alicyclic structure, such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
(Meth) acrylate monomers having an aromatic ring such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
Carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and cinnamic acid;
Acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride and citraconic anhydride;
Styrenesulfonic acid, sodium styrenesulfonate, ammonium styrenesulfonate, lithium styrenesulfonate, 2-acrylamide 2-methylpropanesulfonic acid, sodium 2-acrylamide 2-methylpropanesulfonate, methallylsulfonic acid, sodium methallylsulfonate Sulfonic acid group-containing monomers such as, allylsulfonic acid, sodium allylsulfonic acid, ammonium allylsulfonic acid, vinylsulfonic acid, allyloxybenzenesulfonic acid, sodium allyloxybenzenesulfonic acid, and ammonium allyloxybenzenesulfonic acid;
Phosphoric acid group-containing monomers such as 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and dibutyl-2-acryloyloxysiethyl phosphate. ;
Hydroxyl-containing (meth) acrylate monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
Pentamethylpiperidinyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, and diethylaminostyrene And amino group-containing monomers such as tetramethylpiperidinyl (meth) acrylate;
Fluorinated alkyl group-containing monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
Keto group-containing monomers such as 2-acetoacetoxyethyl (meth) acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;
γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltributoxysilane, vinylmethyldimethoxysilane and other alkoxysilyl group-containing monomers;
Polyethylene glycol mono (meth) acrylate (manufactured by NOF Corporation, Blenmer PE-90, 200, 350, 350G, AE-90, 200, 400, etc.) Polyethylene glycol / polypropylene glycol mono (meth) acrylate (manufactured by NOF Corporation, Blenmer Polyethylene oxide group-containing monomers such as 50 PEP-300, 70 PEP-350, etc., methoxypolyethylene glycol mono (meth) acrylate (manufactured by NOF Corporation, Blemmer PME-400, 550, 1000, 4000 etc.);
Allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Glycerin dimethacrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Data) acrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, monomers having two or more ethylenically unsaturated groups such as diallyl maleate and the like. These may be used alone or in combination of two or more kinds in any combination.

  As the other monomer (C) used in the present invention, a monomer having an acryloyl group is preferable from the viewpoint of excellent copolymerizability.

  The amount of the other monomer (C) used in the present invention is preferably at most 30% by weight, more preferably at most 20% by weight, based on 100% by weight of the monomer mixture.

  The polymer (P) used in the present invention can be obtained by polymerizing the above monomer mixture by a known polymerization technique. Known polymerization techniques include, for example, (living) radical polymerization, (living) anionic polymerization, (living) cationic polymerization, coordination polymerization and the like. It is preferable to use (living) radical polymerization from the viewpoint that it is unlikely to affect battery characteristics when a power storage device is used.

  When performing the above polymerization, the polymerization may be performed by diluting the monomer mixture with a solvent. As the solvent, known solvents can be used, for example, ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as dioxane and tetrahydrofuran; -Aliphatic hydrocarbon solvents such as hexane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, and isopropanol; amide solvents such as dimethylformamide; and water. No. These may be used alone or in combination of two or more kinds in any combination. Considering the heat generated during the reaction, it is preferable to use a solvent during the polymerization.

  As the polymer (P) used in the present invention, a known polymerization initiator can be used at the time of the above polymerization reaction. Known polymerization initiators include, for example, azo initiators and peroxides. Examples of the azo initiator include 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobisisobutyronitrile, and the like. Oxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, sodium persulfate, ammonium persulfate, etc. Are listed. These may be used alone or in combination of two or more kinds in any combination.

  The amount of the polymerization initiator used in the present invention is preferably 0.02 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer mixture. The reaction temperature during the polymerization can be appropriately adjusted, but is generally about 50 to 150 ° C.

  For the polymer (P) used in the present invention, a known chain transfer agent can be used to adjust the number average molecular weight described below. Known chain transfer agents include, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid, butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol Octadecanethiol, cyclohexylmercaptan, thiophenol, octyl thioglycolate, octyl 3-mercaptopropionate and the like. These may be used alone or in combination of two or more kinds in any combination.

  The number average molecular weight of the polymer (P) used in the present invention is preferably 3,000 or more from the viewpoint of excellent adhesion to inorganic materials and excellent performance when used as an electricity storage device. Preferably, it is more preferably in the range of 6,000 or more. The number average molecular weight of the polymer (P) used in the present invention is determined by gel permeation chromatography (GPC) using polystyrene as a molecular weight standard and tetrahydrofuran as a developing solvent when the sample is soluble in tetrahydrofuran. When it is insoluble in water and soluble in water, the value is measured by GPC using polyethylene glycol as a molecular weight standard and a phosphate buffer as a developing solvent.

The glass transition temperature of the polymer (P) used in the present invention is preferably from 60 to 200 ° C. from the viewpoint of excellent adhesion to inorganic materials and excellent performance when used as an electricity storage device. Preferably, it is more preferably in the range of 80 to 180 ° C. The glass transition temperature of the polymer (P) used in the present invention can be determined by a DSC measurement according to JIS K7121.

<Coating composition, ink composition (R)>
Since the polymer (P) used in the present invention is particularly excellent in adhesion to inorganic materials, the solvent (D), the resin (E), and the additive (F) may be added together with the polymer (P) if necessary. ), And by dissolving and dispersing using the pigment (Q), it can be suitably used as a coating composition or an ink composition.

<Solvent (D)>
As the solvent (D) used in the present invention, the above-mentioned known solvents are used. For example, ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as dioxane and tetrahydrofuran; and aliphatic solvents such as n-hexane, cyclohexane, and methylcyclohexane. Examples thereof include hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol and isopropanol, amide solvents such as dimethylformamide, and water. These may be used alone or in combination of two or more kinds in any combination.

<Resin (E)>
Examples of the resin (E) used in the present invention include, but are not limited to, polyester resins, polyether resins, polycarbonate resins, polyurethane resins, polyamide resins, and acrylic resins. Resins such as vinyl acetate resin, vinyl chloride resin, polydiene resin and polyolefin resin are preferably used. As a use form, it is preferable to use in a state of being dissolved or dispersed in the above-mentioned solvent (D). For dissolving or dispersing, a dispersion stabilizer or a pH adjuster, which is mentioned as an additive (F) described below, may be used.

  The amount of the resin (E) used in the present invention is preferably 20% by weight or less, more preferably 10% by weight, based on 100% by weight of the sum of the polymer (P) and the resin (E).

The polyester resin used in the present invention can be produced by an esterification reaction between a known polybasic acid or its ester-forming derivative and a known polyhydric alcohol.

Known polybasic acids or ester-forming derivatives thereof are not limited to the following, but include, for example, oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, and the like. Aliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as cyclohexyl dicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, trimellitic acid, and trivalent or higher polycarboxylic acids such as pyromellitic acid; Ester-forming derivatives such as acid anhydrides, lower alkyl esters, and acid halides are exemplified. These may be used alone or in combination of two or more kinds in any combination.

Examples of known polyhydric alcohols include, but are not limited to, linear alkyls such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. -Containing diols, branched alkyl-containing diols such as 1,2-propanediol, neopentylene glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, and 1,4-bis Alicyclic ring-containing diols such as (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, and aromatic ring-containing diols such as xylylene glycol, bis (2-hydroxyethyl) benzene and bis (hydroxyethoxy) benzene , Glycerin, trimethylolpropane, trialkano Triethanolamine, pentaerythritol, diglycerol, triglycerol, dipentaerythritol, sorbitol, sorbitan, polyhydric alcohols such as trihydric or higher such as sorbide like. These may be used alone or in combination of two or more kinds in any combination.

Commercially available polyester resins used in the present invention include, but are not limited to, for example, the Byron series manufactured by Toyobo, the Vylonal series, the Elitel series manufactured by Unitika, and the Ryo Kagaku Kogyo Co., Ltd. Plus coat series.

  The polyether resins used in the present invention include the above-mentioned polyhydric alcohols, bisphenols (bisphenol A, bisphenol S, bisphenol F), alkylene oxide adducts such as dihydroxynaphthalene, polyethylene glycol, polypropylene glycol, and polyethylene-propylene glycol. And polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, etc., by subjecting them to ring-opening polymerization or ring-opening copolymerization.

Commercial products of the polyether resin used in the present invention are not limited to the following, but include, for example, Alcox series manufactured by Meisei Chemical Industry Co., Ltd.

  The polycarbonate resin used in the present invention can be produced by reacting the above-mentioned polyhydric alcohol with a known carbonic acid diester.

Commercial products of the polycarbonate resin used in the present invention are not limited to the following, but include, for example, a Teflon series manufactured by Idemitsu Co., Ltd.

  The polyurethane resin used in the present invention includes the above-mentioned known polyhydric alcohols and carboxyl group-containing polyols, tertiary amino group-containing polyols, polyester polyols, polyether polyols, polycarbonate polyols, polylactone polyols, polydiene polyols and the like. It can be obtained by reacting a polyol such as a hydride, a polyisocyanate, and optionally an amine.

  Specific examples of the carboxyl group-containing polyol used in the present invention include, for example, dimethylolpropionic acid, dimethylolbutanoic acid, and the like.

  Specific examples of the tertiary amino group-containing polyol used in the present invention include, for example, alkyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, and the like.

  The polyester polyol used in the present invention is a hydroxyl-terminated polyol obtained by the same production method as the above-mentioned polyester resin.

Specific examples of the polyester polyol used in the present invention, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyhexamethylene adipate polyol, pohexamethylene isophthalate polyol, poly neopentylene adipate polyol, polyethylene propylene adipate polyol, Polyethylene butylene adipate polyol, polybutylene hexamethylene adipate polyol, poly (polyoxytetramethylene) adipate polyol, poly (3-methylpentylene adipate) polyol, polyethylene azelate polyol, polyethylene sebacate polyol, polybutylene azelate polyol, poly Butylene sebacate polyol, poly neopentylene terephthalate poly Lumpur, and the like. Commercially available products include the Kuraray polyol P series and N series manufactured by Kuraray Co., Ltd., the San Ester series manufactured by Sanyo Chemical Industries Co., Ltd., and the Teslac series manufactured by Hitachi Chemical Co., Ltd.

  The polyether polyol used in the present invention is a hydroxyl-terminated polyol obtained by the same production method as the above-mentioned polyether-based resin.

Commercial products of the polyether polyol used in the present invention include, for example, Sannics PP series, GP series, Newpole BPE series manufactured by Sanyo Chemical Industries, Adeka polyether P series, BPX series manufactured by ADEKA, and Japan. BA series and BA-P series manufactured by Emulsifier Co., Ltd. are exemplified.

  The polycarbonate polyol used in the present invention is a hydroxyl-terminated polyol obtained by the same production method as the above-mentioned polycarbonate resin.

Examples of the polycarbonate polyol used in the present invention include polyhexamethylene carbonate polyol, polypentamethylene carbonate polyol, polytetramethylene carbonate polyol, and poly (tetramethylene / hexamethylene) carbonate polyol. Commercially available products include Kuraray polyol C series manufactured by Kuraray Co., Ltd., Duranol T series and G series manufactured by Asahi Kasei Chemicals Co., Ltd., and Praxel CD series manufactured by Daicel Corporation.

The polylactone polyol used in the present invention is a hydroxyl-terminated polyol produced by ring-opening polymerization of a lactone monomer such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, using the above-mentioned polyhydric alcohol as an initiator. is there.

Examples of the polylactone polyol used in the present invention include polycaprolactone polyol, polyvalerolactone polyol, and the like. Examples of commercially available products include Praxel H series manufactured by Daicel, and Polylite OD series manufactured by DIC.

  As the polyisocyanate used in the present invention, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, Diisocyanates such as bis (4-isocyanatecyclohexyl) methane or hydrogenated diphenylmethane diisocyanate and compounds derived therefrom, that is, isocyanurate, adduct, biuret, uretdione, allophanate, isocyanate residue of the diisocyanate (A low polymer obtained from a diisocyanate and a polyol) or a composite thereof. These may be used alone or in combination of two or more kinds in any combination.

Examples of the amine used in the present invention include aliphatic monoamines such as monoethylamine, n-propylamine, diethylamine, di-n-propylamine, and di-n-butylamine; alicyclic rings such as cyclohexylamine and N-methylcyclohexylamine. Aromatic monoamines such as aliphatic monoamines, benzylamines and dibenzylamines; hydroxyl-containing aliphatic monoamines such as monoethanolamine and diethanolamine; aliphatic diamines such as ethylenediamine, 1,2-propylenediamine and hexamethylenediamine; isophoronediamine Alicyclic diamines such as dicyclohexylmethane-4,4'-diamine, isopropylidenedicyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane and 1,3-bisaminomethylcyclohexane; Novis propylamine, aliphatic polyamines such as methyl iminobispropylamine. These may be used alone or in combination of two or more kinds in any combination.

The polyamide-based resin used in the present invention is obtained by subjecting the above-mentioned polyhydric alcohol, polybasic acid and polyamine to salt formation and then performing an amidation reaction.

  Commercially available polyamide resins used in the present invention include, but are not limited to, the tomide series manufactured by T & K TOKA, the Veggiem Green series manufactured by Tsukino Foods, and the like. .

  The acrylic resin used in the present invention is manufactured by using a known monomer exemplified as the above-mentioned monomer (B) and monomer (C) and by a known polymerization method such as solution polymerization, suspension polymerization, and emulsion polymerization. Can be. In addition, when performing suspension polymerization or emulsion polymerization, a known dispersant listed as an additive (F) described below may be used.

  Commercially available acrylic resins used in the present invention include, but are not limited to, Alon series manufactured by Toagosei Co., Ltd., Jurimar series, Alphon series, Paracron series manufactured by Negami Kogyo Co., Neocryl series manufactured by Kusumoto Kasei, and the like.

The vinyl acetate-based resin used in the present invention is obtained by, but not limited to, vinyl acetate monomer alone or by polymerizing the vinyl acetate monomer with a polymerizable unsaturated monomer. Examples of the polymerizable unsaturated monomer include those exemplified as the aforementioned unsaturated monomer. These may be used alone or in combination of two or more kinds in any combination.

  Commercial products of the vinyl acetate resin used in the present invention include, but are not limited to, Novatec series manufactured by Mitsubishi Chemical Corporation and Mersen series manufactured by Tosoh Corporation.

The vinyl chloride resin used in the present invention is obtained by, but not limited to, vinyl chloride monomer alone or by polymerizing the vinyl chloride monomer with a polymerizable unsaturated monomer. Examples of the unsaturated monomer include those exemplified as the aforementioned unsaturated monomer.

  Commercial products of the vinyl chloride resin used in the present invention are not limited to the following, but include, for example, Solvain series and Vinibran series manufactured by Nissin Chemical Industry Co., Ltd.

  The polydiene-based resin used in the present invention is not limited to the following, but is obtained by copolymerizing a diene monomer typified by polybutadiene or polyisoprene alone or with a monomer such as styrene or acrylonitrile. Can be In particular, those obtained by block copolymerization are generally used as thermoplastic elastomers. These obtained polydiene resins may be used as they are, or may be those subjected to a hydrogenation reaction in order to increase heat resistance.

  Commercial products of the polydiene-based resin used in the present invention are not limited to the following, for example, TR series, SIS series, TRD series, DYNARON series manufactured by JER, Diene series manufactured by Asahi Kasei, Examples include the Toughen series, the Asaprene series, the ToughTech series, and the Nipol LX series manufactured by Zeon Corporation.

  The polyolefin resin used in the present invention can be obtained by homopolymerizing or copolymerizing an α-olefin monomer such as ethylene, propylene, and butene. As the polyolefin resin, a resin grafted with a monomer such as maleic anhydride or a (meth) acrylic acid monomer, or a chlorinated or chlorosulfonated resin may be used.

  Commercially available polyolefin resins used in the present invention include, but are not limited to, for example, Unistor series manufactured by Mitsui Chemicals, Supercron series, Auroraen series manufactured by Nippon Paper Industries, Unitika Ltd. Arrow base series, Sumitomo Seika's Sixen series, JSR's EXCELLINK series, and the like.

  The number average molecular weight of the resin (E) used in the present invention is not limited to the following, but is preferably 5,000 or more, and more preferably 10,000 or more. The number average molecular weight of the resin (E) used in the present invention is measured by gel permeation chromatography (GPC) using polystyrene as a molecular weight standard and tetrahydrofuran as a developing solvent when the sample is soluble in tetrahydrofuran. In the case of being insoluble in water and soluble in water, the value is measured by GPC using polyethylene glycol as a molecular weight standard and a phosphate buffer as a developing solvent.

  The glass transition temperature of the resin (E) used in the present invention is not limited to the following, but is preferably in the range of -130 to 250C. The glass transition temperature of the resin (E) used in the present invention can be determined by DSC measurement according to JIS K7121.

<Additive (F)>
Examples of the additive (F) used in the present invention include known additives, such as a curing agent, a dispersion stabilizer, a leveling agent, an antifoaming agent, a slip agent, an antistatic agent, a flame retardant, and a viscosity modifier. , An anti-blocking agent, a pH adjuster, a preservative, a tackifier and the like. These may be used alone as long as the effects of the present invention are not impaired, or two or more of them may be used in any combination.

<Pigment (Q)>
The pigment (Q) used in the present invention is not particularly limited, and organic and inorganic pigments intended for design properties used in general printing inks can be used. For example, azo pigments, phthalocyanine pigments, perylene pigments, nitroso pigments, perinone pigments, carbon black, titanium black, zinc white, red iron oxide, aluminum, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, Lithopon, cadmium yellow, cadmium red, graphite, molybdenum orange, zinc chromate, strontium chromate, white carbon, clay, talc, calcium carbonate, manganese violet, mica, talc, zeolite, kaolin, bentonite, smectite, clay, metallic silica Acid salts, metal oxides, metal hydroxides, metal sulfates and the like. These may be used alone or in combination of two or more kinds in any combination.

  When the polymer (P) used in the present invention is used as an electricity storage device, the pigment (Q) may be a known conductive pigment or a pigment such as an active material generally used as an electrode material of a secondary battery. Can be used.

  Examples of the conductive pigment used in the present invention include acetylene black, ketjen black, furnace black, carbon black such as thermal black, among which acetylene black and ketjen black are preferable, and acetylene black is more preferable. is there.

As the positive electrode active material used in the present invention, metal compounds such as metal oxides and metal sulfides capable of doping or intercalating ions can be used. For example, transition metal oxides such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , composite oxides of lithium and transition metals such as lithium nickelate, lithium cobaltate, lithium manganate, lithium phosphate, TiS ₂ , transition metal sulfides such as FeS, and the like. These may be used alone or in combination of two or more kinds in any combination.

  The negative electrode active material used in the present invention is not particularly limited as long as it is capable of doping ions.Examples thereof include metal oxides such as lithium titanate, lithium vanadate, and lithium silicate, and amorphous carbonaceous materials. Materials, artificial graphite such as highly graphitized carbon material, carbonaceous material such as natural graphite, carbon black, mesophase carbon black, resin fired carbon material, carbon fiber material and the like. These may be used alone or in combination of two or more kinds in any combination.

  The size of these active materials is preferably in the range of 0.05 to 1000 μm, and more preferably in the range of 0.1 to 200 μm. Further, the dispersion particle size when the active material is used as the ink composition is preferably 0.5 to 100 μm. The term “dispersed particle size” as used herein refers to a particle size (D50) at which 50 parts by weight is obtained when the volume ratio of the particles from the fine particle size is integrated in the volume particle size distribution. Can be measured by a particle size distribution analyzer.

<Printing method>
As a printing method of the polymer (P) used in the present invention, a known printing method for a substrate described below is used, for example, a dip coating method, a spray coating method, a bar coating method, a knife coating method, A roll coating method, a roll knife coating method, a blade coating method, a die coating method, a gravure coating method, an offset coating method, an inkjet printing method, and the like are exemplified. If necessary, preliminary drying of the base material or drying after coating may be performed using a known device such as a hot air oven, an electric oven, or an infrared heater. When the polymer (P) used in the present invention is used as a power storage device, the same printing method and drying method can be used.

<Substrate>
Examples of the substrate used in the present invention include, but are not limited to, a polyester substrate, a nylon substrate, a polyethylene substrate, a polypropylene substrate, a polyvinyl acetal substrate, a polyacetate substrate, and a polyacetate substrate. Plastic base materials such as vinyl chloride base materials and cellulose base materials, evaporated plastic base materials obtained by subjecting these plastic base materials to metal evaporation such as aluminum, aluminum foil, copper foil, SUS base materials, glass, and inorganic base materials such as ITO Examples include natural materials such as wood, paper, cotton, hemp, silk, and wool. Among them, polyester substrates, nylon substrates, cellulose substrates, vapor-deposited plastic substrates, inorganic substrates, and natural substrates can provide excellent water-resistant adhesion. The thickness of the substrate is usually about 25 to 10000 μm. The polymer (P) used in the present invention is particularly excellent in adhesion to an inorganic substrate. Therefore, when using an inorganic substrate such as a metal-deposited plastic, aluminum alloy, copper foil, SUS substrate, glass, or ITO, Particularly excellent effects can be obtained.

<Current collector>
When the polymer (P) used in the present invention is used as a power storage device, the material and shape of the current collector are not particularly limited, and a material optimal for various power storage devices can be appropriately selected. Examples of the material of the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel. In particular, when the power storage device is a lithium ion battery, aluminum is preferably used as the positive electrode current collector, and copper is preferably used as the negative electrode current collector.

As the shape of the current collector used in the present invention, a flat foil is generally used, but a current collector having a roughened surface, a perforated foil current collector, and a mesh current collector are used. Alternatively, a current collector or the like subjected to a conductive coating treatment can also be used.

<Electrode>
When the polymer (P) used in the present invention is used as an electricity storage device, the electrode is made of an active material and / or a conductive pigment as the polymer (P) and the pigment (Q), a resin (E) as needed, and an additive. It can be obtained by forming a coating film containing (F) on the above-mentioned current collector. In addition, mechanical processing such as pressing can be performed from the viewpoint of improving the performance of the power storage device.

<Power storage device>
By using the above electrode for at least one of the positive electrode and the negative electrode, a power storage device such as a secondary battery or a capacitor can be obtained.

<Electrolyte>
The case of a lithium ion secondary battery will be described as an example. As the electrolytic solution, a solution in which an electrolyte containing lithium is dissolved in a non-aqueous solvent is used.

Examples of the non-aqueous solvent include, but not particularly limited to, carbonates such as ethylene carbonate, butylene carbonate, fluorovinylene carbonate, and fluoromethylvinylene carbonate;
lactones such as γ-butyrolactone, γ-valerolactone, γ-octanoic lactone;
Grimes such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan, 4-methyl-1,3-dioxolan, 1,2-methoxyethane, 1,2-ethoxyethane, 1,2-dibutoxyethane;
Esters such as methyl formate, methyl acetate and methyl propionate;
Sulfoxides such as dimethyl sulfoxide and sulfolane;
Examples thereof include nitriles such as acetonitrile. These may be used alone or in combination of two or more kinds in any combination.

  Further, the above-mentioned electrolytic solution may be used as a gelled polymer electrolyte held in a polymer matrix. The polymer matrix is not particularly limited, and examples thereof include an acrylic resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, and a polysiloxane having a polyalkylene oxide segment. These may be used alone or in combination of two or more kinds in any combination.

<Separator>
The separator of the power storage device is not particularly limited, and examples thereof include a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, and a polyamide nonwoven fabric. These may be those whose surfaces have been subjected to a coating treatment.

<Structure and configuration of power storage device>
The structure of the electricity storage device is not particularly limited, but usually, a positive electrode and a negative electrode, and a separator is provided as necessary, and the shape includes a paper type, a cylindrical type, a button type, a laminated type, and the like. It can be appropriately selected according to the purpose of use.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

<Measurement of number average molecular weight>
The number average molecular weight was measured by gel permeation chromatography (GPC) using the polymer (P) and the resin (E) as samples. When the sample is soluble in tetrahydrofuran, the column temperature was set to 40 ° C. by using an HLC-8220 GPC system manufactured by Tosoh Corporation to which two columns of TSKgel superHZM-N were connected as a measuring instrument, using tetrahydrofuran as an eluent. It was measured under the condition of 0.35 ml per minute. Samples were prepared by dissolving 2 mg of material in 5 ml of the above eluent. The number average molecular weight was calculated in terms of standard polystyrene.
When the sample is insoluble in tetrahydrofuran and soluble in water, SC-2020GPC manufactured by Tosoh Corporation connected to two G3000PWXL (manufactured by Tosoh Corporation) columns using 20 mM phosphate buffer as an eluent. The measurement was carried out at a column temperature of 40 ° C. and a flow rate of 0.5 ml per minute by the system. Samples were prepared by dissolving 2 mg of material in 5 ml of the above eluent. The number average molecular weight was calculated in terms of standard polyethylene glycol.

<Measurement of glass transition temperature>
The glass transition temperature was determined by measuring with a differential scanning calorimeter (DSC) using the polymer (P) and the resin (E) as samples. A robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) was connected to “SSC5200 Disk Station” (manufactured by Seiko Instruments Inc.) and used for measurement. As the measurement sample, a polymer (P) and a resin (E) which were sufficiently dried were used. 10 mg of the measurement sample was set in the above differential scanning calorimeter, kept at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −140 ° C. using liquid nitrogen. Thereafter, the temperature was increased at a rate of 10 ° C./min, and the temperature was increased to 250 ° C. to perform DSC measurement. The glass transition temperature was determined from the obtained DSC chart.

<Nonvolatile content>
The nonvolatile content was determined from the weight ratio before and after drying at 200 ° C. for 10 minutes in an electric oven.

<Production of polymer (P)>
Polymer (P) was produced according to the method shown below. Table 1 shows the amounts of the raw materials used in the production and the properties of the obtained compounds.

<Example 1> Production of polymer (P-1) Trans-p-coumaric acid (Tokyo Kasei) was injected into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping tube, and a nitrogen introduction tube while blowing nitrogen gas. 3 parts, 20 parts of acrylamide (Tokyo Kasei), 62 parts of N-isopropylacrylamide (Tokyo Kasei), 15 parts of ethyl acrylate (Tokyo Kasei), and 259. Five parts and 300 parts of dimethylformamide were charged and heated to 60 ° C. Then, 0.5 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., 10-hour half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and a polymerization initiator aqueous solution was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours to obtain a polymer (P-1) solution having a nonvolatile content of 15%.
The polymer (P-1) thus obtained has a number average molecular weight of 16,000, a glass transition temperature of 105 ° C., a blending amount of the monomer (A) of 3% with respect to 100% of the monomer mixture, and a blending of the monomer (B). The amount was 85%.

<Example 2> Production of polymer (P-2) While blowing nitrogen gas into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping tube, and a nitrogen introduction tube, sinapinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. 45 parts, 45 parts of acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 parts of N-isopropylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 251.5 parts of ion-exchanged water, and 300 parts of dimethylformamide are charged and heated to 60 ° C. Warmed. Then, 0.5 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., 10-hour half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and a polymerization initiator aqueous solution was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours. Thereafter, 8 parts of dimethylaminoethanol was added as a neutralizing agent, and the mixture was stirred for 30 minutes until the mixture became uniform to obtain a polymer (P-2) solution having a nonvolatile content of 15%.
The polymer (P-2) thus obtained has a number average molecular weight of 14,000, a glass transition temperature of 141 ° C., a blending amount of the monomer (A) of 45% with respect to 100% of the monomer mixture, and a blending of the monomer (B). The amount was 55%.

Example 3 Production of Polymer (P-3) While blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, trans-ferulic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 60 parts of acrylamide (manufactured by Tokyo Chemical Industry), 18 parts of N-methylolacrylamide (manufactured by Tokyo Chemical Industry), 2 parts of ethyl acrylate (manufactured by Tokyo Chemical Industry), and 269.3 of ion-exchanged water. And 300 parts of dimethylformamide, and the temperature was raised to 60 ° C. Thereafter, as a polymerization initiator, 4 parts of V-50 (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., 10-hour half-life temperature 57 ° C.) is dissolved in 20 parts of ion-exchanged water, and a polymerization initiator aqueous solution is added. The temperature was raised, and the reaction was carried out at 80 ° C. for 6 hours to obtain a polymer (P-3) solution having a nonvolatile content of 15%.
The polymer (P-3) thus obtained has a number average molecular weight of 5,000, a glass transition temperature of 141 ° C., a blending amount of the monomer (A) of 20% with respect to 100% of the monomer mixture, and a blending of the monomer (B). The amount was 78%.

Example 4 Production of Polymer (P-4) While blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, trans-ferulic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 55 parts of acrylamide (Tokyo Kasei), 10 parts of N-isopropylacrylamide (Tokyo Kasei), 3 parts of styrene (Tokyo Kasei), and 2 parts of acrylonitrile (Tokyo Kasei). Parts, 247.5 parts of ion-exchanged water and 300 parts of dimethylformamide, and the temperature was raised to 60 ° C. Then, 0.5 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., 10-hour half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and a polymerization initiator aqueous solution was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours. Thereafter, 12 parts of dimethylaminoethanol was added as a neutralizing agent, and the mixture was stirred for 30 minutes until the mixture became uniform to obtain a polymer (P-4) solution having a nonvolatile content of 15%.
The polymer (P-4) thus obtained has a number average molecular weight of 17,000, a glass transition temperature of 147 ° C., a blending amount of the monomer (A) of 30% with respect to 100% of the monomer mixture, and a blending of the monomer (B). The amount was 65%.

Example 5 Production of Polymer (P-5) Caffeic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) while blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube. 10 parts, 50 parts of N-isopropylacrylamide (manufactured by Tokyo Chemical Industry), 15 parts of hydroxyethylacrylamide (manufactured by Tokyo Chemical Industry), 20 parts of ethyl acrylate (manufactured by Tokyo Chemical Industry), 2-hydroxyethyl methacrylate 5 parts (manufactured by Tokyo Chemical Industry Co., Ltd.), 258.4 parts of ion-exchanged water, and 300 parts of dimethylformamide were charged, and the temperature was raised to 60 ° C. Thereafter, 0.3 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and an aqueous solution of the polymerization initiator was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours to obtain a polymer (P-5) solution having a nonvolatile content of 15%.
The polymer (P-5) thus obtained has a number average molecular weight of 20,000, a glass transition temperature of 72 ° C., a blending amount of the monomer (A) of 10% with respect to 100% of the monomer mixture, and a blending of the monomer (B). The amount was 65%.

Example 6 Production of Polymer (P-6) Caffeic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) while blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube. 15 parts, 65 parts of acrylamide (manufactured by Tokyo Chemical Industry), 10 parts of N-methylolacrylamide (manufactured by Tokyo Chemical Industry), 5 parts of N-isopropylacrylamide (manufactured by Tokyo Chemical Industry), and styrene (manufactured by Tokyo Chemical Industry) , 3 parts of acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 258.4 parts of ion-exchanged water, and 300 parts of dimethylformamide, and the temperature was raised to 60 ° C. Thereafter, 0.3 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and an aqueous solution of the polymerization initiator was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours to obtain a polymer (P-6) solution having a nonvolatile content of 15%.
The polymer (P-6) thus obtained has a number average molecular weight of 24,000, a glass transition temperature of 148 ° C., a blending amount of the monomer (A) of 15% with respect to 100% of the monomer mixture, and a blending of the monomer (B). The amount was 80%.

<Comparative Example 1> Production of Polymer (P'-7) While blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. 75 parts, 20 parts of N-isopropylacrylamide (manufactured by Tokyo Chemical Industry), 3 parts of styrene (manufactured by Tokyo Chemical Industry), 2 parts of acrylonitrile (manufactured by Tokyo Chemical Industry), 258.4 parts of ion-exchanged water, and dimethylformamide Was charged, and the temperature was raised to 60 ° C. Thereafter, 0.3 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and an aqueous solution of the polymerization initiator was added. The mixture was heated to 80 ° C. and reacted at 80 ° C. for 6 hours to obtain a polymer (P′-7) solution having a nonvolatile content of 15%.
The polymer (P′-7) thus obtained has a number average molecular weight of 24,000, a glass transition temperature of 155 ° C., a compounding amount of the monomer (A) of 0% relative to 100% of the monomer mixture, and a monomer (B) of 100%. The blending amount was 95%.

<Comparative Example 2> Production of Polymer (P'-8) While blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, caffeic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 20 parts of acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 258.4 parts of ion-exchanged water, and 300 parts of dimethylformamide, and the temperature was raised to 60 ° C. Thereafter, 0.3 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and an aqueous solution of the polymerization initiator was added. The mixture was heated to 80 ° C., and reacted at 80 ° C. for 6 hours to obtain a polymer (P′-8) solution having a nonvolatile content of 15%.
The polymer (P′-8) thus obtained has a number average molecular weight of 18,000, a glass transition temperature of 135 ° C., a blending amount of the monomer (A) of 75% with respect to 100% of the monomer mixture, and a monomer (B) of 100%. The blending amount was 20%.

<Comparative Example 3> Production of Polymer (P'-9) While blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube, caffeic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 20 parts of acrylic acid (manufactured by Tokyo Chemical Industry), 10 parts of ethyl acrylate (manufactured by Tokyo Chemical Industry), 40 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry), and ion-exchanged water. 258.4 parts and 300 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged, and the temperature was raised to 60 ° C. Thereafter, 0.3 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and an aqueous solution of the polymerization initiator was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours to obtain a polymer (P′-9) solution having a nonvolatile content of 15%.
The polymer (P′-9) thus obtained has a number average molecular weight of 26,000, a glass transition temperature of 89 ° C., a compounding amount of the monomer (A) of 20% with respect to 100% of the monomer mixture, and a monomer (B) of 100%. The blending amount was 0%.

<Comparative Example 4> Production of Polymer (P'-10) Cinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) while blowing nitrogen gas into a reactor equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube. ), 55 parts of acrylamide (Tokyo Kasei), 20 parts of N-isopropylacrylamide (Tokyo Kasei), 3 parts of styrene (Tokyo Kasei), and 2 parts of acrylonitrile (Tokyo Kasei). , 258.4 parts of ion-exchanged water and 300 parts of dimethylformamide, and the temperature was raised to 60 ° C. Thereafter, 0.3 part of V-50 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 57 ° C.) was dissolved in 10 parts of ion-exchanged water, and an aqueous solution of the polymerization initiator was added. The temperature was raised to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours to obtain a polymer (P′-10) solution having a nonvolatile content of 15%.
The polymer (P′-10) thus obtained has a number average molecular weight of 30,000, a glass transition temperature of 152 ° C., a compounding amount of the monomer (A) of 0% with respect to 100% of the monomer mixture, and a monomer (B) of 100%. The blending amount was 75%.

<Adhesion evaluation of coating film>
Using the solutions of the polymers (P-1) to (P'-10) obtained in Examples and Comparative Examples as coating agents, coating films were prepared according to the following method, and the adhesion was evaluated.

A coating agent shown in Table 1 was applied to a glass substrate having an ITO film on a 100 mm square surface (hereinafter referred to as an ITO substrate) using a bar coater so that the thickness of the coating film after drying was about 3 μm. Then, by drying in a hot air oven at 150 ° C. for 10 minutes, a coating film was formed on the substrate.
In accordance with JIS K5400 cross-cut peeling method, 100 cuts of 1-mm grid-like cuts are made on the coating film with a cutter knife, and cellophane tape CT28 (manufactured by Nichiban Co., Ltd.) is attached to the coated substrate and peeled off at a stretch. The number of squares in the coating film remaining without peeling was counted, and the adhesion was evaluated according to the following criteria, where n was the number of remaining squares.
◎: n = 100. excellence.
〇: n = 90 or more and less than 100. Good.
Δ: n = 80 or more and less than 90. Practical.
X: n = less than 80. Not practical.

The meanings of the abbreviations in Table 1 are as follows.
p-Coumaric acid: trans-p-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
Sinapic acid: Sinapic acid (Tokyo Kasei)
Ferulic acid: trans-ferulic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
Caffeic acid: Caffeic acid (Tokyo Kasei)
Cinnamic acid: trans-cinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
AM: Acrylamide (Tokyo Kasei)
NMAM: N-methylol acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
NIPAM: N-isopropylacrylamide (Tokyo Kasei Co., Ltd.)
HEAA: hydroxyethylacrylamide (Tokyo Kasei)
AA: Acrylic acid (Tokyo Kasei)
EA: Ethyl acrylate (Tokyo Kasei)
St: Styrene (Tokyo Kasei)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
AN: Acrylonitrile (Tokyo Kasei)
V-50: Water-soluble cationic azo polymerization initiator (Fuji Film Wako Pure Chemical Industries, Ltd.)
DMF: dimethylformamide (Tokyo Kasei)
DMAE: Dimethylaminoethanol (Tokyo Kasei)

As shown in Table 1, since the polymer (P) containing no monomer (A) was used in Comparative Example 1, the adhesive strength at the interface between the ITO substrate and the coating film was weak, and the adhesion was deteriorated.

  In Comparative Example 2, since the polymer (P) containing the monomer (A) in an amount of more than 50% by weight was used, the adhesive strength at the interface between the ITO substrate and the coating film was low, and the adhesion was deteriorated.

  In Comparative Example 3, since the polymer (P) containing no monomer (B) was used, the adhesive strength at the interface between the ITO substrate and the coating film was low, and the adhesiveness was deteriorated.

Comparative Example 4 uses a polymer (P) containing a monomer similar to the structure of general formula (1) but having a structure in which R _{1 to} R ₄ do not have a hydroxyl group. The adhesive strength at the interface between the substrate and the coating film was weak, and the adhesion was poor.

On the other hand, in Examples 1 to 6, a polymer (A) having a structure represented by the general formula (1) and a polymer satisfying the content of the monomer (B) composed of a (meth) acrylamide-based monomer in a suitable range Since P) was used, the adhesive strength at the interface between the ITO substrate and the coating film was strong, and had excellent performance in the adhesion test.

Among them, Example 6 was most excellent in adhesion.
In Example 6, since the general formula (1) uses a polymer (P) in which at least two of R _{1 to} R ₄ adjacent to each other are hydroxyl groups, ITO is compared with Examples 1 to ₄ in which R _{1 to} R ₄ are not so. The interface between the substrate and the coating film was firmly adhered and showed excellent adhesion.
Further, in Example 6, the glass transition temperature of the polymer (P) used was in a suitable range of 80 to 180 ° C., and therefore, excellent adhesiveness was exhibited as compared with Example 5 out of the range.

<Production of ink composition (R) for negative electrode of lithium ion battery>
According to the method shown below, an ink composition (R) for a negative electrode of a lithium ion battery was produced. Table 2 shows the amounts of the raw materials used.

<Example 7> Production of ink composition (R-1) Using a planetary stirrer (manufactured by Shinky Inc., product name "Awatori Rentaro"), polymer (P-1) was placed in a non-volatile content in a container dedicated to the stirrer. Was mixed with artificial graphite in an amount of 96 parts, ion-exchanged water was added to a non-volatile content of 50%, kneaded at 2000 rpm for 10 minutes, and then defoamed for 2 minutes. Thus, an ink composition (R-1) for a lithium ion battery negative electrode having a nonvolatile content of 50% was obtained.

<Examples 8 to 12>, <Comparative Examples 5 to 8>
Production of Ink Compositions (R-2) to (R-10) Ink compositions for a negative electrode of a lithium ion battery having a non-volatile content of 50% in the same manner as in Example 1 except for the raw materials and amounts shown in Table 2 Compounds (R-2) to (R-10) were obtained.

The meanings of the abbreviations in Table 2 are as follows.
TRD-2001: Styrene butadiene latex TRD-2001 (manufactured by JSR, glass transition temperature -2 ° C, number average molecular weight cannot be measured due to insolubility of developing solvent)
CMC: Carboxymethylcellulose (Tosoh Corporation)

<Production of ink composition (R) for positive electrode of lithium ion battery>
According to the method described below, an ink composition (R) for a positive electrode of a lithium ion battery was produced. Table 3 shows the amounts of the raw materials used.

<Example 13> Production of ink composition (R-11) Using a planetary stirrer (manufactured by Shinky Inc., product name "Awatori Rentaro"), polymer (P-1) was placed in a non-volatile content in a container dedicated to the stirrer. 8 parts, 86 parts of LiFePO ₄ , 5 parts of Denka Black (Acetylene Black, manufactured by Denka), and polytetrafluoroethylene 30-J (60% aqueous dispersion of DuPont-Mitsui Fluorochemicals) as a nonvolatile component. One part was added, ion-exchanged water was added so that the non-volatile content concentration became 50%, kneading was performed at 2000 rpm for 10 minutes, and then defoaming was performed for 2 minutes. Thus, an ink composition (R-11) for a lithium ion battery positive electrode having a nonvolatile content of 52% was obtained.

<Examples 14 to 18>, <Comparative Examples 9 to 12>
Production of Ink Compositions (R-12) to (R-20) Ingredients and blending amounts shown in Table 3, except that in the same manner as in Example 13, an ink composition for a lithium ion battery positive electrode having a nonvolatile content of 52% was used. Compounds (R-12) to (R-20) were obtained.

The meanings of the abbreviations in Table 3 are as follows.
Denka Black: Acetylene Black Denka Black (manufactured by Denka)
30-J: polytetrafluoroethylene 30-J (manufactured by DuPont Fluorochemicals, Mitsui)
CMC: Carboxymethylcellulose (Tosoh Corporation)

<Production of ink composition (R) for negative electrode of lithium ion capacitor>
According to the method shown below, an ink composition (R) for a negative electrode of a lithium ion capacitor was produced. Table 4 shows the amounts of the raw materials used.

<Example 19> Production of ink composition (R-21) Using a planetary stirrer (manufactured by Shinky Inc., product name "Awatori Rentaro"), polymer (P-1) was placed in a non-volatile content in a container dedicated to the stirrer. 5 parts, 90 parts of graphite, 5 parts of Denka Black (Denka Corporation, acetylene black), and ion-exchanged water so as to have a non-volatile content of 50%, and kneading is performed at 2000 rpm for 10 minutes. After that, degassing was performed for 2 minutes. Thus, an ink composition (R-21) for a lithium ion capacitor negative electrode having a nonvolatile content of 33% was obtained.

<Examples 20 to 24>, <Comparative Examples 13 to 16>
Production of Ink Compositions (R-22) to (R-30) Ingredients and blending amounts shown in Table 4, except that the ink composition for a lithium capacitor negative electrode having a nonvolatile content of 33% was the same as in Example 19, except that (R-22) to (R-30) were obtained.

The meanings of the abbreviations in Table 4 are as follows.
Denka Black: Acetylene Black Denka Black (manufactured by Denka)
TRD-2001: Styrene butadiene latex TRD-2001 (manufactured by JSR, glass transition temperature -2 ° C, number average molecular weight cannot be measured due to insolubility of developing solvent)
HEC: hydroxyethyl cellulose (Tosoh Corporation)

<Production of ink composition (R) for positive electrode of lithium ion capacitor>
According to the method described below, an ink composition (R) for a positive electrode of a lithium ion capacitor was produced. Table 5 shows the amounts of the raw materials used.

<Example 25> Production of ink composition (R-31) Using a planetary stirrer (manufactured by Sinky, product name "Awatori Rentaro"), polymer (P-1) was placed in a non-volatile content in a container dedicated to the stirrer. 9 parts, activated carbon 85 parts, Denka Black (Denka Corporation, acetylene black) 5 parts, polytetrafluoroethylene 30-J (Mitsui DuPont Fluorochemicals Co., Ltd., 60% aqueous dispersion) as non-volatile components 1 Parts, and ion-exchanged water was added so as to have a non-volatile content of 32%, kneaded at 2000 rpm for 10 minutes, and then defoamed for 2 minutes. Thus, an ink composition (R-31) for a lithium ion capacitor positive electrode having a nonvolatile content of 33% was obtained.

<Examples 26 to 30>, <Comparative Examples 17 to 20>
Preparation of Ink Compositions (R-32) to (R-40) Ingredients and blending amounts shown in Table 5, except that in the same manner as in Example 19, an ink composition for a lithium capacitor positive electrode having a nonvolatile content of 33% was used. (R-32) to (R-40) were obtained.

The meanings of the abbreviations in Table 5 are as follows.
Denka Black: Acetylene Black Denka Black (manufactured by Denka)
30-J: polytetrafluoroethylene 30-J (manufactured by DuPont Fluorochemicals, Mitsui)
CMC: Carboxymethylcellulose (Tosoh Corporation)

<Production of electrode (S) for negative electrode of lithium ion battery>
An electrode (S) for a negative electrode of a lithium ion battery was manufactured according to the method described below. Table 6 shows the ink composition (R) used.

<Example 31>
The ink composition (R-1) was applied to a current collector made of copper foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed in a vacuum state at 120 ° C. for 6 hours to produce a lithium ion battery negative electrode (S-1) having a coating thickness of about 70 μm.

<Examples 32 to 36>, <Comparative Examples 21 to 24>
Production of Lithium-ion Battery Negative Electrodes (S-2) to (S-10) Using the ink composition (R) shown in Table 6, the other steps were the same as in Example 31 except for using the ink composition (R). S-2) to (S-10) were obtained.

<Production of electrode (S) for positive electrode of lithium ion battery>
According to the method shown below, a positive electrode (S) for a lithium ion battery was manufactured. Table 7 shows the ink composition (R) used.

<Example 37>
The ink composition (R-11) was applied to a current collector made of an aluminum foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed in a vacuum at 120 ° C. for 6 hours to produce a positive electrode (S-11) for a lithium ion battery having a coating thickness of about 85 μm.

<Examples 38 to 42>, <Comparative Examples 25 to 28>
Production of Lithium Ion Battery Negative Electrodes (S-12) to (S-20) Using the ink composition (R) shown in Table 7, except that the ink composition (R) was the same as in Example 37, S-12) to (S-20) were obtained.

<Production of electrode (S) for negative electrode of lithium ion capacitor>
According to the method described below, a lithium ion capacitor negative electrode (S) was manufactured. Table 8 shows the ink composition (R) used.

<Example 43>
The ink composition (R-21) was applied to a current collector made of copper foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed in a vacuum at 120 ° C. for 6 hours to produce a lithium ion capacitor negative electrode (S-21) having a coating thickness of about 45 μm.

<Examples 44 to 48>, <Comparative Examples 29-32>
Preparation of Lithium-Ion Capacitor Negative Electrodes (S-22) to (S-30) Using the ink composition (R) shown in Table 8, the other procedure was the same as in Example 43, except for the lithium-ion battery negative electrode ( S-22) to (S-30) were obtained.

<Production of positive electrode for lithium ion capacitor>
According to the method described below, a lithium ion capacitor positive electrode (S) was manufactured. Table 9 shows the ink composition (R) used.

<Example 49>
The ink composition (R-31) was applied to a current collector made of aluminum foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed at 120 ° C. for 6 hours in a vacuum state to produce a lithium ion capacitor positive electrode (S-31) having a thickness of about 60 μm.

<Examples 50 to 54>, <Comparative Examples 33 to 36>
Preparation of Lithium Ion Capacitor Electrodes (S-32) to (S-40) Using the ink composition (R) shown in Table 9 and otherwise as in Example 49, the lithium ion battery negative electrode ( S-32) to (S-40) were obtained.

<Adhesion test>
Using the cutter knife, the electrodes (S) manufactured in Examples 31 to 54 and Comparative Examples 21 to 36 were each cut into six grids vertically and horizontally using a cutter knife from the ink coating side of the electrodes to the depth reaching the current collector. A cut was made. A cellophane tape CT28 (manufactured by Nichiban) was adhered from above the cut and immediately peeled off, and the degree of detachment of the ink film was visually evaluated. The evaluation criteria are shown below.
A: No peeling. excellence.
：: Slight peeling. Practical.
Δ: About half peeled off. Not practical.
X: Almost all peeled. Not practical.

<Flexibility test>
The electrodes (S) manufactured in Examples 31 to 54 and Comparative Examples 21 to 36 were formed into a strip shape, and wound around the current collector side so as to be in contact with a metal rod having a diameter of 3 mm. Was visually evaluated. The evaluation criteria are shown below.
◎: No cracking or peeling. excellence.
〇: Cracks are seen but no peeling. Practical realization.
Δ: Cracks were observed, and some peeling was observed. Not practical.
X: Cracks were observed and most of the layers were peeled. Not practical.

<Repeated deformation test>
The electrodes (S) manufactured in Examples 31 to 54 and Comparative Examples 21 to 36 were formed into strips, and the current collector side was wound so as to be in contact with a metal rod having a diameter of 3 mm. Removed and returned to strip shape. After repeating this operation 50 times, the ink film was visually evaluated for cracking and peeling. The evaluation criteria are shown below.
◎: No cracking or peeling. excellence.
〇: Cracks are seen but no peeling. Practical.
Δ: Cracks were observed, and some peeling was observed. Not practical.
X: Cracks were observed and most of the layers were peeled. Not practical.

As shown in Tables 6 to 9, Comparative Examples 21, 25, 29, and 33 use a polymer (P) containing no monomer (A), and thus have an adhesive strength at the interface between the current collector and the ink film. Was weak, and adhesion and flexibility were deteriorated.

  In Comparative Examples 22, 26, 30, and 34, the polymer (P) containing the monomer (A) in an amount of more than 50% by weight was used, so that the adhesive strength at the interface between the current collector and the ink film was weak, and the adhesion was low. Sex and flexibility deteriorated.

  In Comparative Examples 23, 27, 31, and 35, since the polymer (P) containing no monomer (B) was used, the adhesive strength at the interface between the current collector and the ink film was low, and the adhesion and flexibility were low. It got worse.

Comparative Examples 24, 28, 32 and 36 use a polymer (P) containing a monomer similar to the structure of the general formula (1) but having a structure in which R _{1 to} R ₄ have no hydroxyl group. As a result, the adhesive strength at the interface between the current collector and the ink film was weak, and the adhesion and flexibility deteriorated.

On the other hand, in Examples 31 to 54, a polymer (A) having a structure represented by the general formula (1) and a polymer satisfying the content of the monomer (B) composed of a (meth) acrylamide-based monomer in a suitable range ( Since P) was used, the adhesive strength at the interface between the current collector and the ink film was strong, and the performance was well-balanced in the adhesion test, flexibility test, and repeated deformation test.

Above all, Examples 36, 42, 48 and 54 showed excellent performance in all tests.
In Examples 36, 42, 48, and 54, the general formula (1) uses a polymer (P) in which at least two of R _{1 to} R ₄ adjacent to each other are hydroxyl groups. -34, 37-40, 43-46, 49-52, the interface between the current collector and the ink film was firmly adhered and showed excellent performance in the adhesion test, flexibility test, and repeated deformation test. .
In Examples 36, 42, 48, and 54, the glass transition temperature of the polymer (P) used was in a suitable range of 80 to 180 ° C, and thus Examples 35, 41, 47, and 53 were out of the range. It showed superior performance in the repeated deformation test.

<Production of counter electrode for evaluation of lithium ion battery>
<Production Example 1> counter 1 of producing a planetary stirrer with (Thinky Co., product name "Awatori Rentaro"), a stirrer special container, LiFePO ₄ and 86 parts of Denka Black (Denka Co., acetylene black) 5 parts, polytetrafluoroethylene 30-J (manufactured by DuPont Fluorochemicals, Mitsui, 60% aqueous dispersion) as a non-volatile content, 5 parts, and carboxymethyl cellulose (manufactured by Daicel Co., Ltd.) so as to be 4 parts. Ion-exchanged water was added to a concentration of 50%, and kneaded at 2000 rpm for 10 minutes, followed by defoaming for 2 minutes. Thus, a counter electrode ink composition 1 having a nonvolatile content of 50% was obtained.
Next, the above-mentioned ink composition for counter electrode 1 was applied to a current collector made of aluminum foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed in a vacuum at 120 ° C. for 6 hours to produce a lithium-ion battery evaluation counter electrode 1 having a coating thickness of about 85 μm.

<Production Example 2> Production of Counter Electrode 2 A TRD-2001 (manufactured by JSR, styrene butadiene latex, 48.5%) was placed in a container dedicated to the stirrer using a planetary stirrer (manufactured by Shinky Inc., product name "Awatori Rentaro"). (Water dispersion) as a non-volatile content of 4 parts and artificial graphite to 96 parts, add ion-exchanged water to a non-volatile content of 50%, knead at 2000 rpm for 10 minutes, and then defoam for 2 minutes Was done. Thus, a lithium ion counter electrode ink composition 2 having a nonvolatile content of 50% was obtained.
Next, the ink composition 2 for a counter electrode was applied to a current collector made of an aluminum foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed in a vacuum state at 120 ° C. for 6 hours to produce a lithium-ion battery evaluation counter electrode 2 having a thickness of about 85 μm.

<Production of counter electrode for evaluation of lithium ion capacitor>
<Production Example 3> Production of Counter Electrode 3 Using a planetary stirrer (manufactured by Shinky Inc., product name "Awatori Rentaro"), 85 parts of activated carbon and DENKA black (acetylene black, manufactured by Denka Corporation) were placed in a container dedicated to the stirrer. 5 parts, 3 parts of polytetrafluoroethylene 30-J (manufactured by DuPont Fluorochemicals, Mitsui, 60% aqueous dispersion) as a non-volatile content, and 7 parts of carboxymethyl cellulose (manufactured by Daicel Co.) were mixed. Ion-exchanged water was added to a concentration of 32%, kneaded at 2000 rpm for 10 minutes, and then defoamed for 2 minutes. In this way, a lithium ion capacitor counter electrode ink composition 3 having a nonvolatile content of 32% was obtained.
Next, the above-mentioned ink composition for counter electrode 3 was applied to a current collector made of aluminum foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed at 120 ° C. for 6 hours in a vacuum state to produce a lithium ion capacitor evaluation counter electrode 3 having a thickness of about 85 μm.

<Production Example 4> Production of Counter Electrode 4 Using a planetary stirrer (manufactured by Shinky Inc., product name "Awatori Rentaro"), 90 parts of graphite and Denka Black (Acetylene Black, manufactured by Denka) were placed in a container dedicated to the stirrer. 5 parts, 2 parts of TRD-2001 (manufactured by JSR, styrene butadiene latex, 48.5% aqueous dispersion) as a non-volatile content, and 3 parts of hydroxyethyl cellulose (manufactured by Daicel Co., Ltd.), and a non-volatile content of 50 parts %, And kneaded at 2000 rpm for 10 minutes, and then defoamed for 2 minutes. Thus, a lithium ion capacitor counter electrode ink composition 4 having a nonvolatile content of 32% was obtained.
Next, the ink composition for counter electrode 4 was applied to a current collector made of aluminum foil using a doctor blade. Then, after primary drying with a hot air drier at 80 ° C. for 30 minutes, press working was performed with a roll press. Thereafter, secondary drying was performed in a vacuum state at 120 ° C. for 6 hours to produce a lithium ion capacitor evaluation counter electrode 4 having a thickness of about 85 μm.

<Manufacture of lithium-ion batteries>
A lithium ion battery was manufactured according to the method described below. Tables 10 and 11 show the electrode (S) and counter electrode used.

<Example 55>
An electrode (S-1) as a negative electrode and a counter electrode 1 as a positive electrode were punched into an HS flat cell (manufactured by Hosen Co., Ltd.) to a diameter of 16 mm, and a cell guard 2400 (Cell Guard) as a separator punched to a diameter of 18 mm therebetween. Lithium ion battery was manufactured by inserting a 1M LiPF6 solution (solvent: ethylene carbonate: diethyl carbonate = 1: 1 (volume ratio) mixed solvent) as an electrolytic solution and a porous polypropylene film (manufactured by Co., Ltd.). . In addition, all the manufacturing operations of the lithium ion battery were performed in a glove box in which argon gas was replaced.

<Examples 56 to 66>, <Comparative Examples 37 to 44>
A lithium ion battery was manufactured in the same manner as in Example 55, except that the electrode (S) and the counter electrode shown in Tables 10 and 11 were used as the positive electrode and the negative electrode.

<Manufacture of lithium-ion capacitors>
A lithium ion capacitor was manufactured according to the method described below. Tables 12 and 13 show the electrodes (S) and counter electrodes used.

<Example 67>
An HS flat cell (manufactured by Hosen Co., Ltd.), which is a two-pole coin cell, is prepared by punching out an electrode (S-21) which has been subjected to a half-doping treatment of lithium ions in advance as a negative electrode and a counter electrode 3 as a positive electrode to a diameter of 16 mm. A mixture of Celgard 2400 (a porous polypropylene film manufactured by Celgard) as a separator punched to 18 mm and a 1M LiPF6 solution (solvent: ethylene carbonate: dimethyl carbonate: diethyl carbonate = 1: 1: 1 (volume ratio)) as an electrolytic solution The mixed solvent) was inserted to produce a lithium ion capacitor. Lithium ion half-doping was performed by interposing a separator between a negative electrode and lithium metal in a beaker cell and doping the negative electrode with lithium ions so as to have an amount of about half the negative electrode capacity. In addition, all the manufacturing operations of the lithium ion capacitor were performed in a glove box in which argon gas was replaced.

<Examples 68 to 78>, <Comparative Examples 45 to 52>
A lithium ion capacitor was manufactured in the same manner as in Example 67, except that the electrode (S) and the counter electrode shown in Tables 12 and 13 were used as the positive electrode and the negative electrode.

<Charge / discharge retention test of lithium ion battery>
Regarding the lithium ion batteries described in Tables 10 and 11, charge / discharge measurement was performed using a charge / discharge device SM-8 (manufactured by Hokuto Densha Co., Ltd.) according to the following method, and charge / discharge retention characteristics were evaluated.

  After performing constant-current low-voltage charge (cut-off current 0.1 mA) at a charge end voltage of 4.0 V at a charge current of 1.0 mA (0.2 C), the discharge end-to-end voltage is 2.0 V at a discharge current of 1.0 mA. A low current discharge was performed until the temperature reached. These charge / discharge cycles were defined as one cycle, and charge / discharge was repeated for five cycles. The discharge capacity at the fifth cycle was defined as the initial discharge capacity. (The initial discharge capacity is maintained at 100%)

Next, constant-current constant-voltage charging (cut-off current 0.5 mA) was performed at a charging current of 5.0 mA and a charging end voltage of 4.0 V in a thermostat at 50 ° C., and then a discharge current of 5.0 mA and a discharge end current. Constant current discharge was performed until the voltage reached 2.0 V. This charge / discharge cycle was performed 200 times, and the change in the discharge capacity retention ratio was calculated. The evaluation criteria are shown below.
：: 90% or more maintenance rate. excellence.
〇: The retention rate is 85% or more and less than 90%. Excellent.
〇 △: The maintenance ratio is 80% or more and less than 85%. Practical.
Δ: The maintenance ratio is 75% or more and less than 80%. Lower practical limit.
X: The maintenance ratio is less than 75%. Not practical.

<Charge / discharge retention test after repeated deformation test of lithium ion battery>
Using the positive electrodes and the negative electrodes described in Examples 31 to 42 and Comparative Examples 21 to 28 after the repeated deformation test, lithium ion batteries having the configurations described in Tables 10 and 11 were manufactured in the same manner as in the manufacturing of the lithium ion batteries described above. did.
Using this lithium ion battery, charging and discharging were performed in the same manner as in the charge / discharge retention test, and the change in the discharge capacity retention ratio was calculated. The evaluation criteria are shown below.
：: 90% or more maintenance rate. excellence.
〇: The retention rate is 85% or more and less than 90%. Excellent.
〇 △: The maintenance ratio is 80% or more and less than 85%. Practical.
Δ: The maintenance ratio is 75% or more and less than 80%. Lower practical limit.
X: The maintenance ratio is less than 75%. Not practical.

<Charge / discharge retention test of lithium ion capacitor>
Regarding the lithium ion capacitors described in Tables 12 and 13, charge / discharge measurement was performed using a charge / discharge device SM-8 (manufactured by Hokuto Densha Co., Ltd.) according to the following method, and charge / discharge retention characteristics were evaluated.

  After performing constant-current low-voltage charge (cut-off current 0.1 mA) at a charge end voltage of 4.0 V at a charge current of 1.0 mA (0.2 C), the discharge end-to-end voltage is 2.0 V at a discharge current of 1.0 mA. A low current discharge was performed until the temperature reached. These charge / discharge cycles were defined as one cycle, and charge / discharge was repeated for five cycles. The discharge capacity at the fifth cycle was defined as the initial discharge capacity. (The initial discharge capacity is maintained at 100%)

Next, constant-current constant-voltage charging (cut-off current 0.5 mA) was performed at a charging current of 5.0 mA and a charging end voltage of 4.0 V in a thermostat at 50 ° C., and then a discharge current of 5.0 mA and a discharge end current. Constant current discharge was performed until the voltage reached 2.0 V. This charge / discharge cycle was performed 200 times, and the change in the discharge capacity retention ratio was calculated. The evaluation criteria are shown below.
：: 90% or more maintenance rate. excellence.
〇: The retention rate is 85% or more and less than 90%. Excellent.
〇 △: The maintenance ratio is 80% or more and less than 85%. Practical.
Δ: The maintenance ratio is 75% or more and less than 80%. Lower practical limit.
X: The maintenance ratio is less than 75%. Not practical.

<Charge / discharge retention test after repeated deformation test of lithium ion capacitor>
Using the positive electrodes and the negative electrodes described in Examples 43 to 54 and Comparative Examples 29 to 36 after the repeated deformation test, lithium ion batteries having the configurations described in Tables 12 and 13 were manufactured in the same manner as in the manufacturing of the lithium ion batteries described above. did.
Using this lithium ion battery, charging and discharging were performed in the same manner as in the charge / discharge retention test, and the change in the discharge capacity retention ratio was calculated. The evaluation criteria are shown below.
：: 90% or more maintenance rate. excellence.
〇: The retention rate is 85% or more and less than 90%. Excellent.
〇 △: The maintenance ratio is 80% or more and less than 85%. Practical.
Δ: The maintenance ratio is 75% or more and less than 80%. Lower practical limit.
X: The maintenance ratio is less than 75%. Not practical.

As shown in Tables 10 to 13, Comparative Examples 37 to 52 use the electrode (S) having a weak adhesion between the current collector and the ink film shown in Comparative Examples 21 to 36, and thus charge and discharge as an electricity storage device. The properties deteriorated significantly.

On the other hand, in Examples 55 to 78, a polymer (A) having a structure represented by the general formula (1) and a polymer satisfying the content of the monomer (B) composed of a (meth) acrylamide-based monomer in a suitable range ( Since P) was used, the adhesive strength at the interface between the current collector and the ink film was strong, and the charge / discharge characteristics as an electricity storage device were satisfied in a well-balanced manner.

Among them, Examples 60, 66, 72 and 78 showed excellent performance in all tests.
In Examples 60, 66, 72, and 78, General Formula (1) uses a polymer (P) in which at least two of R _{1 to} R ₄ adjacent to each other are hydroxyl groups. -58, 61-64, 67-70, 73-76, the interface between the current collector and the ink film is firmly adhered, and the charge-discharge storage characteristics and the charge-discharge storage characteristics after the repeated deformation test are excellent. Performance was shown.
In Examples 60, 66, 72, and 78, the glass transition temperature of the polymer (P) used was in a suitable range of 80 to 180 ° C, and thus Examples 59, 65, 71, and 77 were out of the range. In comparison with the above, the performance was superior in the charge / discharge storage characteristics after the repeated deformation test.

The compounds according to the present invention are widely and suitably used for dyeing and pretreatment, coating for medical equipment, building materials, etc., outdoor paints and the like, particularly for applications requiring excellent adhesion to inorganic substrates.

Claims (9)

Polymer of a monomer mixture containing 2 to 50% by weight of a monomer (A) represented by the following general formula (1) and 50 to 98% by weight of a (meth) acrylamide-based monomer (B) based on 100% by weight of the monomer mixture. A polymer (P), which is
General formula (1)
(R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, or a methoxy group, and at least one of R _{1 to} R ₄ is a hydroxyl group.) The polymer (P) according to claim 1, wherein at least two of R _{1 to} R ₄ are a hydroxyl group.   The polymer (P) according to claim 1 or 2, wherein the glass transition temperature is 60 to 200 ° C.   The polymer (P) according to any one of claims 1 to 3, wherein the number average molecular weight is 3,000 or more.   A coating agent comprising the polymer (P) according to claim 1.   A coating substrate comprising an inorganic substrate and a coating comprising the coating agent according to claim 5.   An ink composition (R) comprising the polymer (P) according to any one of claims 1 to 4 and a pigment (Q).   An electricity storage device electrode (S) having a current collector and an ink film formed from the ink composition according to claim 7. A power storage device comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the power storage device electrode (S) according to claim 7.