JP2516845B2 - Battery - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to batteries.

[0002]

2. Description of the Related Art Conventionally, ABS resin has been used as a battery case and lid material for a small sealed lead-acid battery, and a polyolefin-based synthetic resin is cheaper than ABS resin. Not used. This is because the ABS resin can be firmly adhered by the adhesive, whereas the polyolefin-based synthetic resin has poor adhesion and cannot be firmly adhered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a battery using a polyolefin-based synthetic resin battery case and a lid.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.

That is, according to the present invention, in a battery having a structure in which the fitting portion between the battery case and the lid and the opening portion of the external terminal lead-out portion located in the lid are sealed with a curable sealant,
The container and the lid are made of a polyolefin-based synthetic resin having the following composition, and the fitting portion of the container and the lid and the opening of the lid are previously irradiated with ultraviolet rays having an action wavelength near 185 nm. Provided is a battery which is treated and then sealed with a curable sealant. (A) A1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer, A2: epoxy group-containing monomer, A3: hydroxyl group-containing monomer, A4: amino group-containing monomer, A5: alkenyl cyclic imino ether derivative and A6 : Modified polyolefin synthetic resins 1 to 10 obtained by reacting at least one monomer selected from polyfunctional unsaturated monomers with a polyolefin synthetic resin.
0% by weight, (B) Unmodified polyolefin resin 0 to 99% by weight

Next, the present invention will be described with reference to the drawings. FIG.
FIG. 3 is an explanatory sectional view of a battery of the present invention. In the figure, 1 is a polyolefin synthetic resin battery case, 2 is a polyolefin synthetic resin lid, 3 is an anode column, 4 is a cathode column, 5 is an anode external terminal, 6 is a cathode external terminal, and 7 and 8 are 0 rings. , 9 are electrode plates. F represents a sealing agent.

In the battery of the present invention, the battery case 1 and the lid body 2 are made of the polyolefin-based synthetic resin having the above composition, and at least the surface of the battery case 1 and the lid body to which the sealing agent is applied is specified. Ultraviolet rays are being irradiated.

The polyolefin resins constituting the modified polyolefin synthetic resin (A) and the unmodified polyolefin synthetic resin (B) include the following. (1) Polyolefins such as polypropylene (hereinafter abbreviated as “PP”), polyethylene (hereinafter abbreviated as “PE”), polybutene, polymethylpentene, and the like. (2) Copolymers of α-olefins such as ethylene-propylene (for example, ethylene propylene rubber, hereinafter abbreviated as EPR). (3) Alloys among the above polymers or with other polymers,
Blends, etc.

If necessary, additives such as antioxidants, weathering agents, lubricants, nucleating agents, plasticizers, antistatic agents, flame retardants and color pigments may be added to these resins.

The modified polyolefin synthetic resin (A) includes A ₁ : a carboxylic acid group, a carboxylic acid ester group or an acid anhydride group-containing monomer, A ₂ : an epoxy group-containing monomer, A ₃ : a hydroxyl group-containing monomer, A ₄ : amino group-containing monomers, a _5: alkenyl cyclic imino ether derivative and a _6: polyolefin resin obtained by reacting at least one monomer selected from among polyfunctional unsaturated monomers are exemplified. Also use. Examples of the monomers A _{1 to} A ₆ include the following.

A ₁ : carboxylic acid group-containing monomers include maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, sorbic acid, mesaconic acid, citraconic acid, angelic acid, vinylacetic acid and their anhydrides. Things can be mentioned. Examples of the anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. A ₂ : As the epoxy group-containing monomer, glycidyl (meth) acrylate, acryl glycidyl ether,
Examples thereof include vinyl glycidyl ether. A ₃ : Examples of the hydroxyl group-containing monomer include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate. A ₄ : As the amino group-containing monomer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth)
Examples thereof include tertiary amino group-containing monomers such as acrylate. A ₅ : As an alkenyl cyclic imino ether derivative,
Examples include those represented by the following structural formulas.

[0012]

Embedded image

Here, n is 1, 2 or 3, preferably 2 or 3, and more preferably 2. R ¹ ,
R ² and R ³ each represent a C _{1 to} C ₁₂ alkyl group or hydrogen, and the alkyl group may have an inert substituent. R ⁴ is a C ₁ -C ₁₂ alkylene group. Specific examples include 2-vinyl- or 2-isopropenyl-2-oxazoline, 2-vinyl- or 2-
Examples include isopropenyl-5,6-dihydro-4H-1,3-oxazine.

A ₆ : As the polyfunctional unsaturated monomer, polyfunctional methacrylate monomers represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., divinylbenzene, triallyl isocyanurate, diallyl phthalate. , Polyfunctional vinyl monomers typified by vinyl butyrate, N, N'-m-phenylene bismaleimide, bismaleimides typified by N, N'-m-phenylene bismaleimide, p-quinone dioxime And other dioximes.

There are various methods for obtaining a modified polyolefin synthetic resin by reacting the above-mentioned monomers, and the typical ones are a copolymerization method and a graft modification method. The copolymerization method is generally a method of radically copolymerizing an olefin such as ethylene and the above monomer under high pressure. Examples of the modified polyolefin obtained by such a copolymerization method include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-glycidyl. Various types such as a methacrylate copolymer (EGMA) are commercially available.

The graft modification method is generally a method in which the above monomer is graft-reacted with a polyolefin synthetic resin in the presence of a radical initiator. Examples of the radical initiator include at least one selected from hydroperoxide, dialkyl peroxide, diacyl peroxide, ketone peroxide, peroxy ester and the like. The method of reacting these monomers with the polyolefin-based synthetic resin is not particularly limited, and a known method is used. For example, there is a method in which a polyolefin and a monomer are dispersed or dissolved in an organic solvent such as xylene or o-chlorobenzene, the above initiator is added, and the mixture is heated and stirred to react. Further, a method of kneading and extruding a polyolefin, a monomer and an initiator with an extruder and reacting them without using a solvent is simple and economically advantageous.

As a general rule, it is preferable that the amount of the monomer added to the polyolefin-based synthetic resin is large, but there is a limit in the reaction process, and it is usually 0.05 to 20% by weight. If the added amount is less than 0.05% by weight, sufficient adhesive force cannot be obtained when the molded product is adhered, and if the added amount exceeds 20% by weight, gelation, coloring, etc. occur, which is not preferable.

In the present invention, the modified polyolefin synthetic resin (A) may be used alone, but in order to further improve the intended purpose of the present invention, an unmodified polyolefin synthetic resin (B) is blended. You can also

When a mixture of the modified polyolefin synthetic resin (A) and the unmodified polyolefin synthetic resin (B) is used, the amount of the unmodified polyolefin synthetic resin (B) used is in the range of 0 to 99% by weight. It is arbitrarily selected. For example, when using a modified polyolefin synthetic resin with a high monomer reaction amount, sufficient adhesive force is often obtained even if a large amount of unmodified polyolefin synthetic resin is added, and conversely a modified polyolefin resin with a low reaction amount is used. When using, the sufficient adhesive force may not be obtained unless the unmodified polyolefin-based synthetic resin is blended or a small amount is blended. When the unmodified polyolefin resin is also used alone, when the weight of the battery increases, the adhesive force between the battery case and the lid becomes insufficient, and the intended purpose of the present invention cannot be achieved.

The polyolefin synthetic resin of the above composition used in the present invention preferably contains an inorganic filler (C) and / or a rubber-like substance (D) in order to further improve the adhesive strength and the like. As the filler (C), various conventionally known granular, flat, scale-like, needle-like, spherical, hollow and fibrous substances are used. Specifically, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, magnesium hydroxide, aluminum hydroxide, clay, diatomaceous earth, talc, alumina, silica, glass powder,
Iron oxide, metal powder, graphite, silicon carbide, silicon nitride,
Boron nitride, aluminum nitride, carbon black, wollastonite, mica, sericite, bilophyllite, metal flakes, graphite, silas balloon, perlite, glass fiber, carbon fiber, whiskers, metal fiber, silicon carbide fiber, etc. It can be illustrated. These fillers may be surface-treated with a silane coupling agent, an organic titanate coupling agent, a fatty acid or a metal salt thereof in order to improve the dispersibility. The fillers may be used alone or as a mixture, and the type and amount are selected according to the purpose. This compounding amount is the synthetic resin component (A) + (B) 1
3 to 150 parts by weight, preferably 5 to 100 parts by weight
To 130 parts by weight, more preferably 10 to 100 parts by weight. When the content is less than 3 parts by weight, the effect of improving the adhesive strength is not sufficient, and when it exceeds 150 parts by weight, the mechanical strength, particularly the impact strength is significantly lowered, which is not preferable.

As the rubber-like substance (D), ethylene / propylene random copolymer rubber, ethylene / propylene / diene random copolymer rubber, 1,2-polybutadiene, styrene / butadiene / styrene block copolymer rubber or its Hydrogenated product, styrene / isoprene / styrene block copolymer rubber or its hydrogenated product, polyisobutylene rubber, styrene / butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, polyurethane rubber, polyester elastomer, polyamide elastomer, natural There are rubbers, among which ethylene / propylene random copolymer rubber, ethylene / propylene /
Diene random copolymer rubber is preferred. These may be used alone or in combination. When a rubber-like substance having a strong polarity and poor compatibility with the polyolefin-based synthetic resin is used, it is preferable to use a compatibilizing agent suitable for the system. The compounding amount of the rubber-like substance is 3 to 100 parts by weight with respect to 100 parts by weight of the resin component (A) + (B). If the amount is less than 3 parts by weight, the effect of improving the adhesive strength is not sufficient, and if it exceeds 100 parts by weight, the heat resistance and the like are significantly deteriorated, which is not preferable.

The sealing agent used in the present invention is basically a curable adhesive, and epoxy, polyurethane and reactive acrylic adhesives are particularly preferable. The epoxy adhesive is mainly composed of an epoxy resin and a curing agent, preferably an amine compound. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin. , Alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, prom-containing epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene glycol glycidyl ether, pentaerythritol polyglycidyl ether, etc. Examples thereof include aliphatic epoxy resins and urethane-modified epoxy resins, and these epoxy resins may be used as a mixture of two or more kinds.

Further, if necessary, a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl ether of an aliphatic alcohol, etc. may be blended to reduce the viscosity.

As the amine compound which is a preferable curing agent used for the epoxy resin, for example, aliphatic amines such as diethylenetriamine, triethylenetetramine and diethylaminopropylamine; menthenediamine,
Aliphatic polyamines such as isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine; Aliphatic polyamines containing aromatic rings such as metaxylenediamine; first, second, Third
Polyethyleneimine having a primary amine nitrogen in one molecule;
Aromatic polyamines such as metaphenylenediamine, methylenedianiline, and diaminodiphenylsulfone; the above-mentioned aliphatic polyamines, aliphatic polyamines containing aromatic rings, polyamine compounds such as aromatic polyamines, etc., by known modification methods, for example, epoxy compounds Modified polyamines formed by the addition reaction of, acrylonitrile, a Michael addition reaction with an acrylic ester, a Mannich reaction with a methylol compound, and the like; 2-methylimidazole, 2
-Ethyl-4 methylimidazole, 1-cyanoethyl-
Imidazole compounds such as 2-methylimidazole;
Tertiary amines such as trisdimethylaminophenol;
Examples include tri-2-ethylhexyl acid salt of trisdimethylaminomethylphenol.

Commercially available versamide (manufactured by Henken Hakusui), thomaide (manufactured by Fuji Kagaku Kogyo), sunmide (manufactured by Sanwa Chemical Industry), laccamide (Dainippon Ink and Chemicals Ind. Co., Ltd.) are mainly produced by condensation reaction of dimer acid and polyamine. Polyamide polyamines known by trade names such as (manufactured by) are listed. Furthermore, those that can be cured at 70 to 80 ° C,
For example, JP-A-60-4524 and JP-A-62-2652
It is also possible to use a latent curing agent disclosed in JP-A No. 3-254731. For the epoxy resin, in addition to the above main components, if necessary, an inorganic filler, for example, powder of silica, quartz glass, mica, calcium carbonate, alumina, talc, clay, graphite, carbon black, etc. Can also be added. Further, in order to improve the curability, known curing accelerators such as phenol, nonylphenol, salicylic acid and triphenylphosphite can be used.

The polyurethane adhesive contains an isocyanate component and a polyol component as basic components, and if necessary, auxiliary components such as a catalyst, a stabilizer, a pigment, a filler and a tackifier are mixed. Isocyanate component,
In addition to aliphatic isocyanates, alicyclic isocyanates and aromatic isocyanates, modified products thereof are included. Examples of the aliphatic isocyanate include hexamethylene diisocyanate, and examples of the alicyclic isocyanate include isophorone diisocyanate. As the aromatic isocyanate,
For example, tolylene diisocyanate, xylylene diisocyanate, diphenyl methane diisocyanate, polymeric diphenyl methane diisocyanate, triphenyl methane triisocyanate, tris (isocyanate phenyl) thiophosphate, etc. are mentioned. Examples of the modified isocyanate include urethane prepolymer, hexamethylene diisocyanate burette, hexamethylene diisocyanate, trimer, and isophorone diisocyanate trimer.

Examples of the polyol component include low molecular weight polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and trimethylolpropane; polyethylene glycol, polypropylene glycol, polytetra Polyether polyols such as methylene glycol and ethylene oxide / propylene oxide copolymers; polycaprolactone, poly β-methyl-δ-butyrolactone, polyesters from diols and dibasic acids, and the like. Other examples include hydroxyl group-containing liquid polybutadiene, castor oil, polycarbonate diol, and acrylic polyol.

As auxiliary components, coupling agents such as silane coupling agents and titanium coupling agents; tackifiers such as terpene resins, phenol resins, terpenes, rosin resins and xylene resins; calcium carbonate, clay, titanium oxide, Examples include fillers and thixotropic agents such as carbon black and aerosil; stabilizers such as ultraviolet absorbers, antioxidants, heat resistance stabilizers and hydrolysis resistance stabilizers.

In the present invention, the urethane adhesive can be used in either one-component type or two-component type.

The reactive acrylic adhesive used in the present invention is a liquid adhesive containing an acrylic monomer or oligomer as a main component, and is hardened by anionic polymerization, radical polymerization or redox polymerization upon adhesion. Various types of reactive acrylic adhesives have been known in the past, for example, an anionic polymerization type instant adhesive containing 2-cyanoacrylic acid ester as a main component,
Redox polymerization type acrylic adhesives (SGA) containing methacrylic acid ester as a main component, radical polymerization type UV curing adhesives containing polyfunctional acrylic acid ester and polyfunctional methacrylic acid ester as a main component by UV irradiation are available. Can be mentioned.

In the present invention, prior to the bonding work, the surface of the container and the lid to which the sealing agent is applied is irradiated with ultraviolet rays. In this case, the irradiation light is in the region near 185 nm.
It is a special ultraviolet ray with. Irradiation wave of such short wavelength
By irradiating long ultraviolet rays, the subsequent bonding work
Will be more effective. The material of the UV irradiation lamp is 185
Those having a high transmittance of ultraviolet rays in the vicinity of nm are preferable, and synthetic quartz glass having a higher purity than natural quartz glass is preferable.

When the surfaces of the battery case and the lid are irradiated with the ultraviolet rays, the distance between the surface of the battery case and the lid to which the sealing agent is applied and the lamp is about 1 to 50 cm, more preferably 5 to 3 cm.
A range of 0 cm is preferred. If the irradiation distance is less than 1 cm, the surface of the battery case and the lid may be chemically deteriorated due to excessive irradiation. If this distance exceeds 50 cm, the irradiation intensity may be insufficient and sufficient adhesive force may not be obtained. Irradiation time is arbitrary, but if it is too short, sufficient adhesive force may not be obtained, and if it is too long (especially when irradiation distance is short), it may cause excessive irradiation and cause deterioration. Therefore, about 20 seconds to 5 minutes is a realistic processing time.

In the present invention, before applying the sealing agent,
For the purpose of degreasing, cleaning, etc., the surface of the battery case and lid is usually treated with an alcohol-based or mineral oil-based solvent, but
By further contacting with an organic solvent described below in advance and then irradiating with an ultraviolet ray, a stronger adhesive force can be obtained.

As the organic solvent to be used, one having an ultraviolet absorbing property is preferable. This ultraviolet absorbing solvent may be one having an ultraviolet absorbing structure in the molecule itself, or one obtained by dissolving an additive having an ultraviolet absorbing structure in the solvent. As an example of the former, benzene,
Aromatic hydrocarbon solvents such as toluene, xylene, decalin, tetralin, carbon tetrachloride, trichloroethylene,
There are halogenated hydrocarbon solvents such as tetrachloroethylene, chloroform, trichloroethane, tetrachloroethane, trichlorotrifluoroethane, brombenzene, dichlorobenzene, etc., and acrylic ester solvents, and the latter examples include acetophenone. Aromatic hydrocarbons, halogenated hydrocarbons, acrylates, in which photosensitizers such as azo-based derivatives, benzophenone-based derivatives, benzoin-based derivatives and diazonium salt-based derivatives are dissolved
There is a solvent such as acrylamide. As a method of bringing the organic solvent into contact with the battery case and the lid surface, there are methods such as dipping method, spraying, coating, etc.When contacting the battery case and the lid with the solvent, ultrasonic waves are applied. It is also possible to promote the sorption of the solvent on the surface.

In the present invention, when the surface of the battery case or the lid is brought into contact with the solvent, the solvent may be at room temperature, but the effect is enhanced by heating it. The heating temperature is preferably as high as possible, but excessive heating causes volatilization and evaporation to become violent, so about 30 to 80 ° C. is recommended. Another preferred method of contacting with the solvent is to heat the container and the lid itself. This can minimize the volatilization and evaporation of the solvent. The heating temperature of the battery case and the lid is also preferably higher, but if they are too high, they may be deformed or melted, so about 30 to 100 ° C. is preferable. The time of contact with the solvent is 5 seconds to 20 minutes, preferably 10 seconds to 5 minutes. If it is 5 seconds or less, a substantial solvent treatment effect cannot be expected, and even if it is contacted for 20 minutes or more, the effect is not improved and it is economically disadvantageous.

[0036]

EFFECTS OF THE INVENTION The battery of the present invention has the advantage that it is cheaper than the conventional ABS resin because the battery case and the lid are made of the polyolefin-based vanishing resin having the above-mentioned specific composition. Is the sealant joint in the tank and lid clear?
Since the ultraviolet rays of a specific wavelength have been irradiated, the adhesion at the joint is strong, and when using the battery,
The joint between the battery case and the lid will not come off.

[0037]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. All parts and% shown below are based on weight.

Examples 1 to 18 (A) Modified polyolefin synthetic resin, (B) Unmodified polyolefin synthetic resin, (C) Inorganic filler, and (D) Rubber-like substance were blended as shown in Table 1. A composition was obtained using a kneading extruder (NVC-50, manufactured by Nakatani Kikai Co., Ltd.). A plate having a thickness of 3 mm was molded from this composition using an injection molding machine (Toshiba Machinery Co., Ltd., IS-100).

Next, this molded plate was cut into a width of 10 mm, wiped with isopropyl alcohol, and then a low pressure mercury lamp (SUV-110 manufactured by Sen Special Light Source Co., Ltd.).
And the distance between the light source and the surface of the molded plate was kept at 5 cm, and irradiation was performed for 2 minutes in an air atmosphere. However, the low-pressure mercury lamp used here is manufactured using synthetic quartz having a light transmittance of 85% or more at a wavelength of 185 nm.

Next, the following adhesives (E1 to E3) were applied to this irradiated molded plate and wiped with acetone to obtain a mild steel plate (JIS G3141, 125 × 25 × 1.6 m).
m) were laminated with an overlap of 7 mm, clamped with a clip, and heat-treated at 80 ° C. for 1 hour. The tensile shear adhesive strength of the test piece thus obtained at 25 ° C. was measured, and the results are shown in Table 1. In addition, the measurement of the tensile shear adhesive strength, using an Instron universal testing machine,
The crosshead speed was 5 mm / min.

Comparative Examples 1 to 4 The synthetic resin molded plates shown in Table 1 were irradiated and adhered by the same method as in the above-mentioned Examples, and the tensile shear adhesive strength of the obtained test pieces was measured. Table 1 shows the results.

Comparative Examples 5 to 6 Tensile shear bond strengths of the test pieces of the synthetic resin molded plates shown in Table 1 when bonded without being irradiated with ultraviolet rays are shown in Table 1.
Shown in The contents of the polyolefin-based synthetic resin, the filler, the rubber-like substance and the adhesive used in this example and the comparative example are shown below. (A) Modified polyolefin synthetic resin (A1) Maleic anhydride modified polypropylene: polypropylene (PP) (MFR = 1.5 g / 10 min) 10
Modified PP obtained by graft-reacting maleic anhydride 0.2 part with 0 part by a extrusion method in the presence of 0.05 part of a radical initiator (dicumyl peroxide). Acid addition 0.1%
(Relative to PP). (A2) Maleic anhydride-modified polyethylene: High-density polyethylene (PE) (MFR = 5 g / 10 min) 100
Modified PE obtained by graft reaction of 0.25 part of maleic anhydride with 0.02 part of a radical initiator (dicumyl peroxide) by an extrusion method. Acid addition 0.2%
(Relative to PE). (A3) Maleic anhydride-modified ethylene / propylene copolymer rubber: ethylene / propylene copolymer (EPR)
20 parts of maleic anhydride to 100 parts of (ML1 + d (100)) as a radical initiator (dicumyl peroxide)
Modified EPR graft-reacted by a solution method (in a xylene solution) in the presence of 4 parts. Acid addition amount 2% (based on EPR). (A4) Ethylene-ethyl acrylate copolymer: trade name "Nisseki Lexlon EEA, A4250" (Nippon Petrochemical Co., Ltd.) (A5) Ethylene-glycidyl methacrylate copolymer, trade name "Nisseki Lexpearl RA" (Japan Petrochemical Co., Ltd.) (A6) Ethylene-hydroxyethylmethacrylate copolymer (A7) Ethylene-dimethylaminomethacrylate copolymer (A8) Oxazoline-modified polyethylene (B) Unmodified polyolefin synthetic resin (B1) PP: trade name " Nisseki Polypro J650G "(M
FR = 8 g / 10 min) (Nippon Petrochemical Co., Ltd.) (B2) High-density PE: Product name “Nisseki Stafren E65
0 "(MFR = 5 g / 10 min) (Nippon Petrochemical Co., Ltd.) (C) Inorganic filler (C1) Talc: Product name" FFR "(Asada Milling Co., Ltd.) (C2) Calcium carbonate: Product name" BSK -5 "(manufactured by Dowa Calfine Co., Ltd.) (D) Rubber-like substance (D1) EPR: trade name" EP02P "(manufactured by Japan Synthetic Rubber Co., Ltd.) (D2) EPR: trade name" EP57P "(Japan Synthetic Rubber Co., Ltd.) (D3) Hydrogenated product of styrene-butadiene-styrene block copolymer rubber: Trade name "Clayton G1657" (manufactured by Shell Chemical Co., Ltd.) (E) Sealing agent (adhesive) (E1) Epoxy adhesive: Bisphenol A type epoxy resin, trade name "Araldite AW106" 100 parts by weight and curing agent, trade name "Hardener HV953U" 8
A mixture of 0 parts by weight (all manufactured by Nagase Ciba Co., Ltd.). Both were mixed just before coating. (E2) Urethane adhesive: Product name "URALANE5
772A (main agent) "," URALANE 5772B (hardener) ", mixing ratio of main agent and hardener = 100/23 (parts by weight), (FURANE PRODUCTS CO.) (E3) reactive acrylic adhesive: trade name" Hard Rock E-510K-07 "(manufactured by Denki Kagaku Kogyo Co., Ltd.)

[0043]

[Table 1]

As can be seen from the results shown in Table 1, the ultraviolet-irradiated polyolefin synthetic resin plate can be bonded with a high adhesive strength of about 70 kg / cm ² or more by means of a curable adhesive. The tensile shear adhesive strength of such a magnitude is a value sufficient to bond the battery case and the lid of the battery with practical adhesive strength.

[Brief description of drawings]

FIG. 1 is an explanatory cross-sectional view of one embodiment of a lead acid battery of the present invention.

[Explanation of Codes] 1 Battery case 2 Lid body 3 Anode column 4 Cathode column 5 Anode external terminal 6 Cathode external terminal 7,8 o-ring 9 Electrode plate group F Sealing agent

Front page continued (72) Inventor Masatoshi Kobayashi 8-11 Isogo, Isogo-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Atsushi Aoyama 2-5-11, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture (72) Inventor Hiroshi Amano Tatsuno, Hyogo Prefecture 236 Nakai, Tatsuno-cho, Nagasaki City Chiba Nagase Chiba Co., Ltd. Inspector Takeshi Ogawa (56) References JP-A-60-7056 (JP, A) JP-A-1-75078 (JP, A)

Claims (3)

(57) [Claims] 1. A battery having a structure in which a fitting portion between a battery case and a lid and an opening portion of an external terminal lead-out portion located in the lid are sealed with a curable sealing agent. It is made of a polyolefin synthetic resin having the following composition, and the fitting portion of the battery case and the lid and the opening of the lid are 185 in advance.
A battery characterized by being sealed with a curable sealing agent after being irradiated with ultraviolet rays having an action wavelength in the vicinity of nm . (A) A1 ... Carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer, A2: Epoxy group-containing monomer, A3: Hydroxyl group-containing monomer, A4: Amino group-containing monomer, A5: Alkenyl cyclic imino ether derivative and A6 : Modified polyolefin synthetic resins 1 to 10 obtained by reacting at least one monomer selected from polyfunctional unsaturated monomers with a polyolefin synthetic resin.
0% by weight, (B) Unmodified polyolefin resin 0 to 99% by weight 2. A composition containing 3 to 150 parts by weight of a (C) filler and / or 3 to 100 parts by weight of (D) a rubber-like substance based on 100 parts by weight of the resin (A) + (B). The battery according to claim 1, which is made of a material. 3. The battery according to claim 1, wherein the sealing agent is at least one selected from an epoxy adhesive, a polyurethane adhesive, and a reactive acrylic adhesive.