JP2011210412A - Sealing agent composition for organic electrolyte battery, and organic electrolyte battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing agent composition capable of maintaining a stable performance for a long period.SOLUTION: The sealing agent composition includes: a 1,3-butadiene polymer (polymer A); a block copolymer including a conjugated diene based monomer block (polymer B); and an age resistor of 0.001-3 parts by weight against the 1,3-butadiene polymer (polymer A) of 100 parts by weight.

Description

  The present invention is used for an organic electrolyte battery, and in particular, a sealing agent composition for an organic electrolyte battery capable of maintaining excellent hermeticity under high temperature conditions for a long period of time, and an organic electrolyte using this sealing agent composition It relates to batteries.

  Lithium secondary batteries are often used as power sources for small electronic devices such as notebook computers, mobile phones, and PDAs. As the usage range of these small electronic devices is expanded, demands for the performance and safety of lithium secondary batteries (hereinafter sometimes simply referred to as batteries) are increasing. These batteries are usually used repeatedly by charging and discharging operations, but due to repeated charging and discharging, the internal pressure of the battery rises due to volume fluctuations and heat generation of the electrodes due to charging and discharging, and the electrolyte leaks to the outside. Sometimes. In this case, not only deterioration of battery characteristics occurs, but also dangers such as ignition and corrosion of equipment are problematic. In addition, since the electrolyte used in lithium secondary batteries is organic and extremely hates water, lithium secondary batteries completely prevent water from entering the battery and prevent electrolyte leakage. However, it is required to have a high hermeticity to prevent completely.

  For example, a lithium secondary battery is housed in a metal container in order to seal the power generation element, but in order to prevent a short circuit between the positive electrode and the negative electrode, it is necessary to insulate between the positive electrode terminal and the negative electrode terminal. In general, a gasket made of an insulating material is used at the opening of a metal container containing a power generation element for insulation and sealing between the positive and negative electrodes. As an insulating material, it is known to use a resin insulating gasket (see, for example, Japanese Patent Laid-Open No. 53-084122).

  In order to further reinforce the sealing with such an insulating gasket, it has also been proposed to use an insulating gasket and a sealant in combination (for example, JP-A-55-030148, JP-A-55-016352, (See Kaiho 59-112565). The sealing agent is applied to an insulating gasket or a metal container, and the insulating gasket is attached to the metal container, thereby improving the sealing property between the insulating gasket and the metal container.

  Examples of such a sealant include pitch materials such as coal tar and asphalt, and materials obtained by adding a polymer as a modifier to pitch materials (for example, Japanese Patent Laid-Open Nos. 56-032671 and 58- In addition to pitch-based materials, butyl rubber (for example, Japanese Patent Laid-Open No. 55-030148) is also available. For example, a polyolefin-based adhesive (for example, see JP-A-56-032672), a polyvinylidene fluoride resin (for example, see JP-A-1-040469) has been proposed.

  However, these sealing agents are likely to deteriorate under high temperature conditions, and batteries to be mounted on electric appliances and the like more widely in the future require stability at higher temperatures. For example, Patent Document 1 discloses a good sealing material. A diene rubber having a weight average molecular weight of 10,000 to 1,500,000 has been proposed. Patent Document 2 proposes a sealing agent in which a block polymer and a diene rubber are combined.

JP-A-10-55789 JP 2000-243359 A

  By the way, as described above, an organic electrolyte battery such as a lithium secondary battery has been mainly used for small electronic devices such as notebook computers and mobile phones. However, in recent years, an automobile such as an electric vehicle or a hybrid electric vehicle is used. Organic electrolyte batteries have begun to be used for batteries. When used in small electronic devices, the device is used for a relatively short period, whereas when used in an electric vehicle, it is assumed that the device will be used for a long time. In addition, the sealing agent is required to maintain stable performance for a long period of time.

  Accordingly, an object of the present invention is to provide a sealing agent composition that can exhibit stable performance over a longer period than conventional sealing agents.

  Based on this knowledge, the present inventors have found that when a predetermined proportion of an anti-aging agent is contained in the sealant, the function of the sealant can be stably maintained for a long period of time. The invention has been completed.

Thus, according to the present invention,
(1) 1,3-butadiene polymer (polymer A), block copolymer (polymer B) containing a conjugated diene monomer block, and 100 parts by weight of the 1,3-butadiene polymer (polymer A) A sealing agent composition for an organic electrolyte battery comprising 0.001 to 3 parts by weight of an anti-aging agent,
(2) The sealing composition for an organic electrolyte battery according to (1), wherein the 1,3-butadiene polymer (polymer A) has a weight average molecular weight of 20,000 to 800,000,
(3) The sealant composition for an organic electrolyte battery according to (1) or (2), wherein the anti-aging agent is an antioxidant,
(4) The sealing agent composition according to any one of (1) to (3), further comprising an organic solvent having 5 to 15 carbon atoms,
(5) In any one of (1) to (4), between the insulating gasket and the metal container, and / or between the insulating gasket and the sealing body, mounted on the opening of the metal container containing the power generation element. An organic electrolyte battery provided with a sealant layer using the organic electrolyte battery sealant composition of
(6) The battery according to (5), wherein the organic electrolyte battery is a lithium secondary battery.

  The organic electrolyte battery sealing agent composition according to the present invention can maintain stable performance for a long period of time as compared with conventional sealing agents. Moreover, the lifetime of the organic electrolyte battery using the sealing agent composition for an organic electrolyte battery can be extended.

  Embodiments according to the present invention will be described below.

[Sealant composition]
The sealing composition for an organic electrolyte battery according to the present invention includes a 1,3-butadiene polymer (polymer A), a block copolymer (polymer B) containing a conjugated diene monomer block, and 1,3-butadiene. It contains 0.001 to 3 parts by weight of an anti-aging agent with respect to 100 parts by weight of the polymer (polymer A).

(Polymer A)
As the polymer A, a 1,3-butadiene homopolymer obtained by polymerizing a 1,3-butadiene monomer is used. As the polymerization method, known methods such as solution polymerization and emulsion polymerization can be used. The 1,3-butadiene polymer may be a high cis butadiene polymer containing a lot of cis-1,4 bonds or a low cis butadiene polymer containing a lot of trans-1,4 bonds. For example, a 1,3-butadiene polymer having a desired ratio of cis-1,4 bonds can be obtained by a catalyst used in solution polymerization. At this time, examples of the catalyst include a Ziegler catalyst and a lithium catalyst.

  Further, the proportion of cis-1,4 bonds in the 1,3-butadiene polymer (Polymer A) is preferably 80% by weight or more, and more preferably 90% by weight or more. When the ratio of the cis-1 / 4 bond is in the above range, the flexibility of the sealing agent layer can be increased.

  Moreover, the polystyrene conversion weight average molecular weight (henceforth a weight average molecular weight or Mw) calculated by the gel permeation chromatography using n-hexane of a 1, 3- butadiene polymer (polymer A) is as follows. It is preferably 20,000 to 800,000, more preferably 50,000 to 700,000, and particularly preferably 70,000 to 600,000.

(Polymer B)
The block copolymer used in the sealant of the present invention is a polymer block of a conjugated diene monomer (hereinafter sometimes referred to as a diene block) and a polymer block of a monomer other than the conjugated diene monomer (hereinafter referred to as other block). A diblock or multiblock polymer containing at least a block). Moreover, the shape may be linear or branched. Such a block polymer used in the present invention does not necessarily need to be a complete block polymer, and may contain a partially incomplete block or a randomly polymerized portion. It may be contained by weight% or more, preferably 70% by weight or more, more preferably 80% by weight or more. Each block constituting the block polymer used in the present invention may be a block substantially obtained by polymerization of the monomer.

  The diene block / other block ratio (weight) is 95/5 to 5/95, preferably 95/5 to 30/70, more preferably 95/5 to 65/45. By setting the ratio (weight) of the diene block / other blocks within the above range, the adhesion to the adherend is further improved, and pelletization and powdering are possible, which facilitates weighing and facilitates the sealing agent composition. Can be manufactured.

  Examples of the diene monomer include butadiene, isoprene, and 1,3-pentadiene, and examples of the monomer other than the diene monomer include aromatic vinyl monomers. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and divinylbenzene. These may be used alone or in combination of two or more.

  Specific examples of the block polymer used in the present invention include diblock type block polymers such as styrene-butadiene block polymer and styrene-isoprene block polymer, styrene-butadiene-styrene block polymer, and styrene-isoprene-styrene block polymer. , Triblock type block polymers such as styrene-butadiene-isoprene block polymer, styrene-butadiene-styrene-butadiene block polymer, styrene-isoprene-styrene-isoprene block polymer, styrene-butadiene-isoprene-styrene block polymer, Examples thereof include multiblock type styrene-containing block polymers such as styrene-butadiene-styrene-isoprene block polymers. Of course, these polymers may be used alone, or two or more types may be mixed and used by appropriately setting the mixing ratio according to the purpose. Moreover, these hydrogenated substances or partial hydrogenated substances may be used.

  The production method of the block polymer is not particularly limited and may be a known method, but a living polymerization method using a lithium polymerization initiator will be described as an example of the production method. An aromatic vinyl monomer is first polymerized in a hydrocarbon solvent in the presence of a lithium polymerization initiator to form an aromatic vinyl block, and then a diene monomer is added to form the diene block. An aromatic vinyl block is subsequently formed. Furthermore, a linear block polymer is obtained by sequentially polymerizing an aromatic vinyl monomer and a diene monomer, respectively. Of course, after forming a block of butadiene as a diene monomer, a block of isoprene that is a diene monomer can be further formed, so that a block of the same type of monomer can be formed continuously. In this method for producing a linear block polymer, branching is achieved by reacting with a polyfunctional compound (coupling agent) having 2 to 7 reactive groups that reacts with lithium derived from a polymerization initiator bonded to a terminal. -Like block polymer can be obtained.

  The weight average molecular weight calculated by gel permeation chromatography using the block polymer n-hexane described above is 20,000 to 1,000,000, preferably 50,000 to 500,000, more preferably. 100,000 to 400,000. By making a weight average molecular weight into the said range, it can be made to melt | dissolve easily in the organic solvent used when preparing a sealing compound composition. Moreover, since the sealing agent composition can be adjusted to a viscosity suitable for application, the thickness of the sealing agent layer can be easily controlled. Furthermore, the strength of the sealing agent layer can be increased, and when the insulating gasket is attached, the sealing agent layer can be hardly cracked.

  In the sealing agent composition according to the present invention, it is preferable to blend 3 to 50 parts by weight of polymer B with respect to 100 parts by weight of polymer A. By blending the polymer B in the above range, the adhesion to the insulating gasket is further improved.

(Anti-aging agent)
Since 1,3-butadiene polymer (polymer A) contains a double bond in the main chain, it is known that it is inferior in ozone resistance as compared with a polymer not containing a double bond such as polyethylene and polypropylene. In addition, since a part of the sealing agent layer formed by applying and drying a sealing agent composition containing an organic solvent and a polymer is in contact with the electrolytic solution, the addition of a material that adversely affects the battery performance may lower the battery performance. There is.

  Examples of the anti-aging agent include an antioxidant, a heat anti-aging agent, an anti-bending crack agent, and an ozone deterioration preventing agent. Among these, an antioxidant is preferable in that the sealing performance can be maintained for a longer period of time, and among the antioxidants, the phenolic compound and the phosphite compound do not dissolve in the electrolytic solution, and the electrolytic solution is adversely affected. It is more preferable in that the function can be exhibited in a small amount without affecting. Among the antioxidants, naphthylamine compounds, diphenylamine compounds and the like may react with the electrolyte solution or elute into the electrolyte solution when in contact with the electrolyte solution. Moreover, an additive that exhibits a function by blooming on the surface of wax or the like is not preferable.

  Specific examples of the phenol compound include styrenated phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, n-octadecyl-3- ( 4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 2,4-dimethyl-6- (1-methylcyclohexyl) phenol, 2-t-butyl-6- (3-t-butyl 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydro-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentyl Phenyl acrylate, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4 ′ Butylidenebis (3-methyl-6-tert-butylphenol) 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-bis (3,5-di-tert-butyl-4-hydroxy) Benzyl) furfide, 2,4-bis [(octylthio) methyl] -o-cresol, 2,4-bis (phenylthiomethyl) -3-methyl-6-tert-butylphenol, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] -methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} 1,1-dimethyl Til] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2′-methylene-bis- (6-α-methyl-benzyl-p-cresol), tris (3,4 Di-t-butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 3,9-bis [2- {3 -(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2-t- Butyl-6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 4,4′-thio-bis (3-methyl-6-tert-butylpheno) Le), and the like.

  Examples of phosphites include tris (nonylphenyl) phosphite, triphenyl phosphite, and tris (2,4-di-tert-butylphenyl) phosphite.

  Examples of the naphthylamine compounds include octylated diphenylamine, alkylated diphenylamine, 4,4′-bis (dimethylbenzyl) diphenylamine, and phenyl-α-naphthylamine diarylamine antioxidants, diphenyl-p-phenylenediamine, and dinaphthyl-p. A diaryl-p-phenylenediamine anti-aging agent such as phenylenediamine, and N-isopropyl-N′-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine, N- (3-methacryloyloxy-2-hydroxypropyl) -N′-phenyl-p-phenylenediamine, N- (methacryloyl) -N′-phenyl-p-phenylenediamine and other alkyl / aryl-p-phenylenediases Emissions-based anti-aging agents.

  Examples of the diphenylamine compound include p-isopropoxy / diphenylamine, N, N′-diphenyl / ethylenediamine, and octylated diphenylamine. Examples of the p-phenylenediamine compound include N, N′-diphenyl-p-phenylenediamine, N— Examples thereof include isopropyl-N′-phenyl-p-phenylenediamine, N, N′-bis (1-methylheptyl) -p-phenylenediamine, and the like.

  These anti-aging agents may be used singly or in combination of two or more, but it is preferable to use two or more in combination from the viewpoint that the function can be expressed with a small amount. When combining two types of anti-aging agents, the same types of anti-aging agents may be combined or different types of anti-aging agents may be combined. Among them, a combination of a phenolic anti-aging agent and another phenolic anti-aging agent, a combination of a phenolic anti-aging agent and a phosphite-based anti-aging agent, a combination of a phenolic anti-aging agent and a thioether anti-aging agent, etc. Is a preferred example.

  Further, these anti-aging agents are preferably contained in an amount of 0.001 to 3 parts by weight, 0.01 to 2 parts by weight, and 0.05 to 1.5 parts by weight, based on 100 parts by weight of the polymer A. More preferred. By including an anti-aging agent in this range, it is possible to prevent aging such as cracking, discoloration, curing, and softening due to the action of oxygen, sunlight, heat, bending, ozone, etc., and to prolong the life significantly. If the amount of the anti-aging agent is less than 0.001 part by weight, the effect of extending the life is difficult to be exhibited.

(Other ingredients)
In addition to the above-mentioned 1,3-butadiene polymer (Polymer A), block copolymer (Polymer B) and anti-aging agent, the sealing agent composition of the present invention further comprises components such as a dispersant and an ultraviolet absorber. May be included. These are not particularly limited as long as they do not deteriorate the performance of an insulating gasket described later, do not react with the electrolyte, and do not dissolve in the electrolyte.

  Examples of the dispersant include an anionic compound, a cationic compound, a nonionic compound, and a polymer compound. A dispersing agent is selected according to the electrode active material and electrically conductive agent to be used. The content ratio of the dispersant in the sealant composition is preferably 0.01 to 5% by weight. When the content ratio of the dispersant is within the above range, the sealing agent composition is excellent in stability, can be applied uniformly, and liquid leakage can be prevented with a thin film.

  Examples of ultraviolet absorbers include organic substances such as benzotriazole ultraviolet absorbers, bezoate ultraviolet absorbers, benzophenone ultraviolet absorbers, acrylate ultraviolet absorbers, metal complex ultraviolet absorbers, and salicylic acid esters, or fine particles. Inorganic materials such as zinc oxide, cerium oxide, and titanium oxide can be used. The content ratio of the ultraviolet absorber in the sealant composition is preferably 0.01 to 2% by weight. When the ultraviolet absorber is within this range, deterioration due to ultraviolet rays can be prevented.

  The sealing agent composition of the present invention may comprise an organic solvent that dissolves the 1,3-butadiene polymer (polymer A) and the block copolymer (polymer B) described above. This composition is applied to a metal container or an insulating gasket and dried to provide a seal that enhances the sealing property between the insulating gasket and the metal container.

(Organic solvent)
The organic solvent is not particularly limited as long as the 1,3-butadiene polymer (polymer A) and the block copolymer (polymer B) can be dissolved, but considering volatility and ease of drying, An organic solvent having 5 to 15 carbon atoms is preferable, and an organic solvent having 6 to 12 carbon atoms is more preferable.

  Specific examples of the organic solvent include n-hexane, heptane, n-octane, isooctane, n-nonane, decane, decalin, α-pinene, β-pinene, δ-pinene, 1-chlorooctane, chlorodecane, cyclohexane, cyclohexane Heptane, methylcyclopentane, 2-methylcyclohexane, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexane, chlorocyclohexane, cyclohexene, cycloheptene, benzene, toluene, o-xylene, m-xylene, p-xylene, styrene , Chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, ethylbenzene, propylbenzene, diisopropenylbenzene, butylbenzene, isobutylbenzene, n-amylbenzene, cumene, etc. Substitutable hydrocarbons: 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, benzyl alcohol, 4-t-butylcatechol , Cyclopentanol, and other alcohols, 2-pentanone, 2-hexanone, 3-hexanone, cyclopentanone, cyclohexanone, cycloheptanone, 2,6-dimethyl-4-heptanone, 4-methyl-2-pentanone, Ketones such as isophorone; propyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether, methyl n-amyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether, etc. Tells; Esters such as butyl formate, pentyl formate, isopropyl acetate, n-propyl acetate, n-butyl acetate, s-butyl acetate, t-butyl acetate, ethyl lactate, butyl lactate, methyl benzoate, ethyl benzoate; Amines such as o-toluidine, m-toluidine, p-toluidine, dimethylaniline, piperidine; amides such as N-methylpyrrolidone; sulfur-containing compounds; nitrile group-containing compounds such as adiponitrile; Ring compounds; nitrogen-containing heterocyclic compounds such as pyridine; cellosolve acetates such as ethyl cellosolve acetate; glycols; diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether And ethylene glycol alkyl ethers such as tilether; lactones such as γ-valerolactone and γ-caprolactone; and lactams such as δ-valerolactam.

  Among these organic solvents, aromatic hydrocarbon solvents such as toluene and xylene, and saturated hydrocarbon solvents such as n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane are particularly preferable examples.

  The content of the total polymer component consisting of the 1,3-butadiene polymer (Polymer A) and the block copolymer (Polymer B) in the sealing agent composition of the present invention is 1% by weight to 50% with respect to the organic solvent. % By weight, preferably 3% by weight to 40% by weight, more preferably 5% by weight to 20% by weight. By setting the content of all polymer components in the sealing agent composition within the above range, it is possible to obtain a viscosity suitable for coating, and the control of the thickness of the sealing agent layer after coating and drying is facilitated.

  Furthermore, an additive such as a colorant can be added to the sealing agent composition of the present invention as necessary. The colorant that can be added is preferably one that does not react with the electrolyte and does not dissolve in the electrolyte, and includes various organic and inorganic pigments. Among these, carbon black, particularly carbon black having a particle size of 0.1 μm or less such as furnace black and channel black is preferable. When such a colorant is added, it must be dissolved or dispersed sufficiently uniformly in the composition. When using a granulated or agglomerated structure, a ball mill, a sand mill, an ultrasonic wave, etc. It is better to disperse with. The addition amount of such an additive such as a colorant may be any amount as necessary, but is usually 0.01% to 20% by weight, preferably 1,3-butadiene polymer (polymer A). Is 0.01 wt% to 5 wt%, more preferably 0.02 wt% to 3 wt%. When the additive amount exceeds 20% by weight, the flexibility of the sealing agent is reduced, which may cause cracks.

  As a method for preparing the sealant composition, a method in which polymer A and polymer B are kneaded in advance is dissolved in an organic solvent, and then an anti-aging agent and other additives are added; polymer A and polymer B are sequentially added to the organic solvent. A method of adding an anti-aging agent and other additives, and then preparing a solution of polymer A and a solution of polymer B, mixing them, and then adding an anti-aging agent and other additives Is mentioned.

(Organic electrolyte battery)
The organic electrolyte battery of the present invention includes the sealing agent composition between the insulating gasket and the metal container, and / or between the insulating gasket and the sealing body, which are attached to the opening of the metal container containing the power generation element. The sealing agent layer formed in is provided. The metal container material, power generation element, and insulating gasket used in the organic electrolyte battery may be those generally used. In this organic electrolyte battery, the power generation element is housed in a metal container and sealed.

The power generation element is an electrolytic solution composed of a supporting electrolyte and an organic electrolyte solution, an active material for positive and negative electrodes, a separator, and the like. As the supporting electrolyte constituting the electrolytic solution, for example, a compound that is easily hydrolyzed by reacting with water, such as a lithium-based compound such as LiPF ₆ , LiBF ₄ , and LiClO ₄ is used. Moreover, as an organic electrolyte solution solvent, combustible organic compounds, such as propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC), are used, for example. As the insulating gasket, it is preferable to use polyolefin resins such as polyethylene, polypropylene, and ethylene copolymerized polypropylene, which are generally said to have high electrolytic solution resistance, and particularly ethylene copolymerized polypropylene because of a good balance between strength and elastic modulus. Further, as the polyolefin resin, one having a heat distortion temperature measured by JIS K7207 of 90 to 200 ° C., preferably 90 to 150 ° C., more preferably 95 to 130 ° C. may be used. If it is higher than 200 ° C, the bending elastic modulus at room temperature is too high, and deformation may occur when the insulating gasket is mounted, which may cause cracks and cracks. At temperatures below 90 ° C, the resistance of the insulating gasket at high temperatures Is inferior and the sealing performance is reduced. What is necessary is just to form the sealing agent layer of the organic electrolyte battery of this invention in the following procedure, for example. That is, the sealing agent composition of the present invention is applied to the surface of a metal container and / or the surface of an insulating gasket by feeding a predetermined amount with a metering pump such as an air-driven metering dispenser, a roller pump, or a gear pump. After coating, these coatings are naturally dried in a state where the sealing agent composition is kept horizontal so that the sealing agent composition does not shift, and the organic solvent is removed to form a thin layer. However, the application is not limited to a method using a metering pump, and can be performed manually using a brush if the amount is small. Further, it is needless to say that drying can be performed in a shorter time because forced drying is performed by a heating device, and the process can be industrially more suitable. What is necessary is just to select the thickness of the sealing agent layer provided by such a method arbitrarily with the magnitude | size of a metal container and an insulation gasket, and it is 0.1 micrometer-1000 micrometers normally. If the thickness of the layer is insufficient, problems such as electrolyte leakage and moisture intrusion may occur, or the layer may be cut. On the contrary, if the layer is thick, layer formation may be difficult.

  Examples of the organic electrolyte battery include a lithium primary battery and a lithium secondary battery. However, a high pressure inside the battery during charging is one of the causes of station leakage. In this respect, a lithium secondary battery is preferable.

  The sealing agent composition of the present invention includes electric and electronic parts using an organic electrolytic solution, such as an electric field capacitor, an electric double layer capacitor, and a lithium ion capacitor, and can be suitably used here.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In this example, “parts” and “%” are based on weight unless otherwise specified.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight. The weight average molecular weight (hereinafter referred to as Mw) is a value measured by gel permeation chromatography using n-hexane as a solvent.

(Polymerization of 1,3-butadiene polymer (Polymer A))
To a 10 liter autoclave equipped with a stirrer was added 5000 g of toluene and 810 g of butadiene, and after sufficient stirring, 0.27 mol of diethylaluminum chloride and 0.6 mmol of chromium chloride / pyridine complex were added, and polymerization was carried out at 60 ° C. for 3 hours with stirring. Thereafter, 100 ml of methanol was added to terminate the polymerization. After the polymerization was stopped, after cooling to room temperature, the polymerization solution was taken out. The resulting polymerization solution was steam-coagulated and then vacuum-dried at 60 ° C. for 48 hours to obtain 780 g of a solid polymer. Mw of the obtained polymer was 390,000.

Further, from the result of ¹³ C-NMR spectrum, the content of the cis-1 / 4 conjugate of this polymer was 94%.

(Polymerization of block copolymer (polymer B) containing aromatic vinyl block-diene block)
In a 10 liter autoclave equipped with a stirrer, 3750 g of a mixed solvent in a ratio of n-butane / cyclohexane = 30/70 was added, 200 mmol of dibutyl ether and 100 mmol of n-butyllithium were present, and 560 g of styrene was first added at 30 ° C. for 1 hour. Subsequently, 340 g of isoprene was added, and polymerization was carried out for 1 hour 30 minutes while controlling the temperature by reflux cooling so that the reaction temperature was between 50 ° C and 60 ° C. Subsequently, 50 mmol of dimethyldichlorosilane was added to carry out a coupling reaction. Thereafter, 100 ml of methanol was added to terminate the polymerization. After the polymerization was stopped, after cooling to room temperature, the polymerization solution was taken out. The obtained polymerization solution was steam-coagulated and then vacuum-dried at 60 ° C. for 48 hours to obtain 750 g of a block copolymer. Mw of the obtained polymer was 190,000.

(Preparation of sealant composition)
100 parts by weight of polymer A, 10 parts by weight of polymer B, and 8 parts by weight of carbon were kneaded for 10 minutes at 150 ° C. using a twin-screw kneader, and then dissolved in 800 parts by weight of xylene. An inhibitor was added to obtain a sealant composition having a solid concentration of 13% by weight.

(Sealant property test)
Discoloration: The sealant composition was cast on a glass plate, dried at room temperature for 1 hour, and then vacuum dried at 80 ° C. for 1 hour to obtain a film having a thickness of 50 μm. The film was immersed in an electrolytic solution (EC + PC + DEC 1: 1: 1 molar ratio, LiPF ₆ 1 mol / L) at 60 ° C. for 100 hours. The evaluation criteria are shown in Table 1 as “◎” indicating no discoloration when the liquid is transparent, “Δ” when discoloring slightly, and “×” when discoloring brown. It is considered that the eluate from the film reacts with the anion species of the electrolytic solution to cause discoloration, so that the one without discoloration maintains the battery performance.

Heating variation: The obtained film was heated at 120 ° C. for 100 hours, and the weight variation was measured. Table 1 shows the ratio (%) of the weight increased as a heating variable. The increase in weight due to heating occurs because the polymer A and the polymer B constituting the film are oxidized, so that a smaller heating variable is preferable from the viewpoint of extending the life of the sealant.

  As shown in Table 1, the sealing agent in which 0.001 to 3 parts by weight of the anti-aging agent is blended with 100 parts by weight of the polymer A is the sealing agent in which the anti-aging agent is not blended with respect to 100 parts by weight of the polymer A and the above No discoloration is seen and the heating variable is small as compared with a sealant containing an anti-aging agent greater than the range. Therefore, Examples 1-4 can maintain the performance of a sealing agent stably.

Claims (6)

  1,3-butadiene polymer (polymer A), a block copolymer (polymer B) containing a conjugated diene monomer block, and 100 parts by weight of the 1,3-butadiene polymer (polymer A). A sealant composition for an organic electrolyte battery comprising 001 to 3 parts by weight of an anti-aging agent.   2. The sealing composition for an organic electrolyte battery according to claim 1, wherein the 1,3-butadiene polymer (polymer A) has a weight average molecular weight of 20,000 to 800,000.   The sealant composition for an organic electrolyte battery according to claim 1 or 2, wherein the anti-aging agent is an antioxidant.   Furthermore, the sealing compound composition as described in any one of Claims 1-3 which comprises a C5-C15 organic solvent.   The organic electrolysis according to any one of claims 1 to 4 between an insulating gasket and a metal container, and / or between an insulating gasket and a sealing body, which are mounted on an opening of a metal container containing a power generation element. An organic electrolyte battery provided with a sealant layer using a sealant composition for a liquid battery.   6. The battery according to claim 5, wherein the organic electrolyte battery is a lithium secondary battery.