JPH0982292A - Battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery having the high hardenability of an insulation material to such an extent as free from discoloration, and the high level of a rust preventing function and insulation reliability by filling or covering space between positive and negative electrode terminals with a hardening material having a visible light photo-curing composition to the prescribed composition. SOLUTION: The inner space of a metallic battery case 1 used as a positive terminal in common is filled with a positive electrode active substance and a negative electrode active substance via a separator. A bottom plate 7 as a negative terminal is spot welded to the end of a current collector rod, and held with the metallic battery case 1 in a caulked state via a gasket 6. Furthermore, a recess formed between the metallic battery case 1 common to the positive terminal and the bottom plate 7 as the negative terminal is filled with a hardening material having a visible light photo-curing composition. This hardening material is composed of a radical polymerization vinyl compound, an ultraviolet absorbent, a visible light polymerization initiator and pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery in which a specific visible light curable composition is filled or coated between the terminals of a positive electrode terminal and a negative electrode terminal, and the field of electricity, electrons or the use thereof. Can be prized in.

[0002]

2. Description of the Related Art In some dry batteries, a positive electrode terminal is formed around an outer periphery of a negative electrode terminal via an insulating member. In this case, the insulating member is used to prevent a short circuit due to contact between the negative electrode terminal and the positive electrode terminal with a conductive material such as metal, or a liquid short circuit due to deposition of dew condensation or the like. Particularly in the case of high-power batteries such as alkaline batteries, lithium batteries, and nickel-cadmium batteries, a short circuit between the positive electrode terminal and the negative electrode terminal causes a large current to flow, causing trouble not only in the battery itself but also in the battery peripheral members. For example, in the case of contact short-circuit with a conductive material, the battery sealing part may be deformed due to the heat generation of the battery itself and the pressure increase inside the battery, the built-in electrolyte may be exposed to damage the equipment to be used, or the condensed water In the case of a liquid short circuit caused by, the electrolysis of water occurs and the metal terminals are corroded.

As an insulating method for avoiding these troubles, a method of fitting a molding resin between the negative electrode terminal and the positive electrode terminal, or a composition such as a solvent type, a two-component curing type or an ultraviolet curing type composition is used for the insulating portion. There is a method of curing after coating or filling. In the method of fitting the molding resin, it is necessary to manufacture a molding resin that conforms to the shape of the battery, and if the dimensional accuracy of the molding resin is poor, the yield in the fitting process will deteriorate, and the production cost and productivity of the battery will be a problem. There is. On the other hand, in the method of applying the composition to the insulating part or filling the insulating part and then curing the composition to form an insulator, when a solvent-type composition is used, a heating and drying step for evaporating the solvent is required. Since the evaporating solvent leads to environmental pollution, a device for recovering the solvent is required, resulting in high battery manufacturing cost and long curing time, which is problematic in terms of productivity.
When a two-component curable composition is used, a two-component mixing operation is required, resulting in poor workability. In addition, when the control accuracy of the mixing ratio is poor, the composition causes curing failure, resulting in insulation failure. Connect. Further, since the curing time is long, there is a problem in productivity.

On the other hand, the ultraviolet curable composition is
As shown in JP-A-2-236950 and the like, it is a one-component curing type, and since it is instantly cured by irradiating the composition with ultraviolet rays, it is excellent in workability and productivity.

[0005]

However, when the ultraviolet curable composition is used to insulate between the negative electrode terminal and the positive electrode terminal of a dry battery, it is usually between the negative electrode terminal and the positive electrode terminal on the periphery thereof. Generally, the recesses to be formed are filled with an ultraviolet curable composition and cured by irradiation with ultraviolet rays. However, since the transmittance of ultraviolet rays is poor, there is a risk that the lower layer portion of the recesses may be defective in curing. In particular, in order to confirm whether or not the composition is surely filled in the insulating portion, or when using a composition colored in blue or red due to the necessity of design, the pigment used as the colorant is In addition, the transparency of ultraviolet rays is deteriorated, so that the filled composition causes curing failure. Further, the composition containing the pigment is usually blended with an ultraviolet absorber in order to prevent the fading, but an ultraviolet curable composition containing the ultraviolet absorber is more likely to cause poor curability, and also fading. The suppressive effect was not sufficient. A battery in which the ultraviolet-curable composition has a curing failure has a gas barrier property against water vapor that the filled resin part originally should have when the filled resin part is peeled off or is left in a humid environment due to, for example, a drop impact. Since this deteriorates, the concentration of water in the resin becomes higher at the lowermost filling layer where the curing failure is severe, that is, at the metal interface of the battery body, causing problems of corrosion and short circuit. In addition, it is difficult to say that the ultraviolet ray of the light source used for the ultraviolet ray curable composition is necessarily safe, and it is not sufficient from the working environment. The present inventors have conducted earnest studies to find a battery in which the insulating material used is excellent in curability, the insulator does not cause discoloration, and is excellent in rust prevention and insulation reliability.

[0006]

In order to solve the above problems, the present inventors have found that a battery manufactured using a specific composition is effective, and completed the present invention. That is, the present invention, between the terminals of the positive electrode terminal and the negative electrode terminal, is filled or covered with a cured product of a visible light curable composition comprising a radically polymerizable vinyl compound, an ultraviolet absorber, a visible light polymerization initiator and a pigment. It is a battery. Hereinafter, the battery of the present invention will be described in detail.

[0007] 1. Visible light curable composition The visible light curable composition used in the present invention has a visible light curable composition comprising a radically polymerizable vinyl compound, an ultraviolet absorber, a visible light polymerization initiator and a pigment as an essential component. Is. Each component will be described below. 1-1. Radical Polymerizable Vinyl Compound As the radical polymerizable vinyl compound, which is the main component of the visible light curable composition, various compounds can be used. Specifically, a compound having an ethylenic double bond, (meth) acrylic acid, (meth) acrylate; vinyl ester such as vinyl acetate and vinyl propionate; vinyl ether such as methyl vinyl ether, ethyl vinyl ether and cyclohexyl vinyl ether; styrene. , Alkenylbenzenes such as vinyltoluene, α-methylstyrene, chloromethylstyrene and stilbenzene; N-vinylpyrrolidone and the like. In this specification, acrylic acid and / or methacrylic acid are referred to as (meth) acrylic acid, and acrylate and / or methacrylate are referred to as (meth) acrylate.

In the present invention, it is preferable to use (meth) acrylic acid or (meth) acrylate as the radically polymerizable vinyl compound because of excellent curability. Examples of the (meth) acrylate include the following a to f.

A. (Meth) acrylate of monohydric alcohol It is a (meth) acrylate of monohydric alcohol or alcohol obtained by adding alkylene oxide to monohydric alcohol. Specifically, methyl (meth) acrylate and 2-
Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, arylalkyl (meth) acrylates such as benzyl (meth) acrylate, cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, and tetrahydrofuran Examples include aryl (meth) acrylates such as furyl (meth) acrylate and phenyl (meth) acrylate. In addition to these, there are (meth) acrylates represented by the following general formula (1).

[0010]

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In the formula (1), R ¹ is hydrogen or a methyl group, and R ² is an alkyl group having 1 to 20 carbon atoms, a vinyl group, an aryl group or an alkoxyalkyl group. Preferred specific examples of this (meth) acrylate include methoxycarbonylmethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, heptoxycarbonylmethyl (meth) acrylate, and isopropoxycarbonylmethyl (meth) acrylate.

Further, there is a (meth) acrylate represented by the following general formula (2).

[0013]

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In the formula (2), R ¹ is the same group as in the formula (1), R ³ is a linear or branched alkylene group having 1 to 4 carbon atoms, and n is 0 or 1 to Indicates an integer of 10. Specific preferred examples of this (meth) acrylate include dicyclopentenyl (meth) acrylate, dicyclopentenyloxymethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentenyloxypropyl (meth) acrylate. Etc.

B. Polyol (meth) acrylate Usually, a mono- or poly (meth) acrylate of a polyol having a valence of 2 or more and a polyol having a valence of 2 or more and an alkylene oxide added thereto or a polyalkylene glycol. The following are mentioned as a specific example of these (meth) acrylates.

B-1. Mono (meth) acrylate of Polyol As examples of this, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate and 3-chloro-2-hydroxypropyl ( There are hydroxyalkyl (meth) acrylates such as (meth) acrylate.

B-2. Poly (meth) acrylate of polyol As this example, 1,2-propylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di- Examples include cyclopentenyl di (meth) acrylate, hydrogenated dicyclopentadienyl di (meth) acrylate, and tris [2- (meth) acryloyloxyethyl] isocyanurate.

Further, bisphenol A type poly (meth) acrylate represented by the following general formula (3) can be mentioned.

[0019]

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In the formula (3), R ¹ is the same group as in the formula (1), R ⁴ and R ⁵ are hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ and R ⁷ are carbon numbers. 2-8 hydrocarbon groups are shown, and n and m show the integer of 1-10. However, in one molecule, R ⁴ and R ⁵ , R ⁶ and R ⁷ , and n
And m may be the same or different. This (meta)
Specific preferred examples of the acrylate include 2,2-bis (4-methacryloxydiethoxyphenyl) propane,
2,2-bis (4-acryloxydiethoxyphenyl)
Propane, 2,2-bis (4-methacryloxytriethoxyphenyl) propane, 2,2-bis (4-acryloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloxyhexaethoxyphenyl) propane, 2,2-bis (4-acryloxyheptaethoxyphenyl) propane, 2,2-bis (4-methacryloxyoctaethoxyphenyl) propane, 2,2-bis (4
-Acryloxydipropoxyphenyl) propane, 2,
2-bis (4-methacryloxytripropoxyphenyl) propane, 2,2-bis (4-acryloxydibutoxyphenyl) propane, 2,2-bis (4-methacryloxyoctabutoxyphenyl) propane, 2- (4 −
Methacryloxydiethoxyphenyl) -2- (4-methacryloxytriethoxyphenyl) propane, and 2-
(4-acryloxydipropoxyphenyl) -2- (4
-Acryloxytriethoxyphenyl) propane and the like.

In addition to these, poly (meth) acrylate of polyalkylene glycol can be mentioned, and specific examples thereof include diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diglycerol di (meth) acrylate and diglycerol tetra (meth) acrylate Etc.

C. Polyester (meth) acrylate Usually, it can be obtained by esterifying a polyhydric alcohol with a polybasic acid or anhydride [hereinafter referred to as polybasic acid (anhydride)] and (meth) acrylic acid. Are polyester di (meth) acrylates of maleic acid (anhydride) and ethylene glycol, di (meth) acrylates of polyester diols of phthalic acid (anhydride) and diethylene glycol, tetrahydrophthalic acid (anhydride) and diethylene glycol. Polyester diol di (meth) acrylate, adipic acid and triethylene glycol polyester diol di (meth) acrylate, tetrahydrophthalic acid (anhydride) and trimethylol propane polyester polyol poly (meth) acrylate To mention it can.

D. Epoxy (meth) acrylate Epoxy resins having two or more epoxy groups in the molecule, various phenol novolac resins obtained from phenol, cresol, butylphenol, octylphenol or nonylphenol, and epoxy resins obtained by the reaction of epichlorohydrin with (meth) ) Acrylic acid or carboxyl group-containing (meth) acrylate, or
It can be obtained by reacting a mixture of either (meth) acrylic acid or carboxyl group-containing (meth) acrylate with a polybasic acid. An example of this is a (meth) acrylate represented by the following general formula (4).

[0024]

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In the formula (4), R ¹ is the same group as in the formula (1), R ⁸ is a hydrocarbon group having 2 to 18 carbon atoms, and R ⁹ is a hydrocarbon group having 1 to 18 carbon atoms. . A preferable specific example of this (meth) acrylate is 2-hydroxy-3.
-Phenoxypropyl (meth) acrylate, cyclohexanoxy-β-hydroxypropyl (meth) acrylate, tetrahydrofurfuroxy-β-hydroxypropyl (meth) acrylate, nonyloxy-β-hydroxypropyl (meth) acrylate and the like. In addition to these, (meth) acrylic acid addition product of bisphenol A diglycidyl ether, (meth) acrylic acid addition product of neopentyl glycol diglycidyl ether and (meth) acrylic acid addition product of 1,6-hexanediol diglycidyl ether The thing etc. can be mentioned.

E. Urethane (meth) acrylate It can be obtained by reacting a polyhydric alcohol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate, and examples thereof include adipic acid, sebacic acid,
Polyester diols of organic polybasic acids such as maleic acid and terephthalic acid with polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butylene glycol and 1,6-hexanediol, and tolylene diisocyanate, 4,4′- Diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, isophorone diisocyanate and 1,6-hexamethylene diisocyanate, and addition reaction products of 2-hydroxyethyl (meth) acrylate, and polyether diols such as polypropylene glycol and polytetramethylene glycol. Tolylene diisocyanate, 4,
Examples thereof include addition reaction products of 2-hydroxyethyl (meth) acrylate with diisocyanates such as 4'-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, isophorone diisocyanate and 1,6-hexamethylene diisocyanate.

F. Other (meth) acrylate In addition to the above (meth) acrylate, the following general formula (5) or
There is a (meth) acrylate represented by (6).

[0028]

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[0029]

[Chemical 6]

In the formulas (5) and (6), R ¹ is the same group as in the formula (1), R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms, and m is an integer of 1 to 10. Yes, n is 1 or 2. Specific preferred examples of this (meth) acrylate include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, and 3-chloro-2-acid phosphooxypropyl (meth) acrylate.

The visible light curable composition used in the present invention is
One or more of the above radically polymerizable vinyl compounds may be mixed and used.

As the radical-polymerizable vinyl compound of the visible light curable composition used in the present invention, a combination of a compound having two or more ethylenic double bonds and a compound having two or more mercapto groups is used. To do
It is preferable that the surface drying property is excellent because the polymerization inhibition by oxygen during curing is small. Hereinafter, a compound having two or more ethylenic double bonds and a compound having two or more mercapto groups will be described.

I. Compound Having Two or More Ethylenic Double Bonds As the compound having two or more ethylenic double bonds, various compounds can be used. Specifically, divinyl aromatic compounds such as divinylbenzene and divinyltoluene, The above-mentioned di- or poly (meth) acrylate, diallyl malate, diallyl phthalate, triallyl isocyanurate, diallyl compound or dimethallyl compound such as trimethallyl isocyanurate and trimethylpropane diallyl ether, and triethylene glycol divinyl ether and cyclohexane dimethanol dimethanol. Examples thereof include divinyl ether such as vinyl ether. Two or more compounds having two or more ethylenic double bonds can be used in combination.

Ii. Compounds having two or more mercapto groups As the compounds having two or more mercapto groups, various compounds can be used, and preferred examples thereof include esters of a compound having a carboxyl group and a mercapto group with a polyhydric alcohol, and ethane. Dithiols, aliphatic polythiols such as propanedithiol and hexamethylenedithiol, aromatic polythiols such as xylenedithiol, polythiols in which halogen atoms of epihalohydrin adducts of alcohols are substituted with mercaptan groups, hydrogen sulfide reaction products of polyepoxy compounds, and Examples thereof include triazine thiol compounds. The compound having two or more mercapto groups has a molecular weight of 80 to 150.
It is preferable to use 000.

In the ester of the above-mentioned compound having a carboxyl group and a mercapto group and a polyhydric alcohol,
Examples of the compound having a carboxyl group and a mercapto group include mercaptoacetic acid, α-mercaptopropionic acid and β
-Mercaptopropionic acid and thioglycolic acid. Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and hydroquinone, diethylene glycol and triethylene. Polyalkylene glycols such as glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, aliphatic polyols such as dipentaerythritol and sorbitol, bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct and other bisphenol A type alcohols, xylene Recall, 4,4'-dihydroxydiphenyl methane, and aromatic polyols pyrogallol tris-hydroxyethyl diisocyanate isocyanurate, bis-hydroxyethyl hydantoin, thio diethanol, and triethanol amine. Specific examples of the ester of a compound having a carboxyl group and a mercapto group and a polyhydric alcohol include ethylene glycol bis (mercapto acetate), ethylene glycol bis (mercapto propionate), polyethylene glycol bis (mercapto acetate), polyethylene glycol bis. (Mercaptopropionate), trimethylolethane tris (mercaptoacetate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis (Mercaptoacetate), pentaerythritol tetrakis (mercaptopropionate), dipentaerythritol hexakis Mercaptoacetate),
Examples thereof include dipentaerythritol hexakis (mercaptopropionate) and trishydroxyethyl isocyanurate tris (mercaptopropionate). Two or more compounds having two or more mercapto groups can be used in combination.

The weight ratio of the compound having two or more ethylenic double bonds to the compound having two or more mercapto groups is preferably 1:10 to 10: 1, more preferably 1: 3 to 3: 2. It is 1. This ratio is 1:10 to 1
If it deviates from 0: 1, the surface dryness may not be sufficiently improved.

1-2. UV Absorber As the UV absorber to be contained in the composition used in the present invention, various UV absorbers can be used, such as benzotriazole, hindered amine and benzoate. As benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole (commercially available products include TINUVIN P, manufactured by Ciba-Geigy), 2- [2
-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
(3,5-di-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
t-octylphenyl) benzotriazole, methyl-
Condensation product of 3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight about 300) (commercially available, TINUVIN 213, Ciba Geigy) Products, etc.) and hydroxyphenylbenzotrizole derivatives (commercially available products include TINUVIN 571 and Ciba Geigy products). Hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2- (3,5
-Di-t-butyl-4-hydroxybenzyl) -2-n
-Bis (1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonate, dimethyl succinate.1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6,
6-Tetramethylpiperidine polycondensate (commercially available products include TINUVIN 622LD, manufactured by Ciba Geigy), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5- Triazine-2,4-diyl}
{(2,2,6,6-tetramethyl-4-piperidyl)
Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)} imino] (as a commercial product,
CHIMASSORB 944LD, CHIMASSORB 944FD, manufactured by Ciba Geigy, etc.), and N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N
-(1,2,2,6,6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate (commercially available products include CHIMASSORB 119FL and Ciba Geigy) There is. As benzoate, 2,
4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like. In the composition used in the present invention, the ultraviolet absorber may contain two or more kinds.

The blending amount of the ultraviolet absorber is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If it is less than 0.01% by weight, the effect of suppressing fading is not sufficient, and if it exceeds 10% by weight, it is not only costly but also the effect of suppressing fading does not significantly change.

1-3. Visible Light Polymerization Initiator In the visible light curable composition used in the present invention, various visible light polymerization initiators can be used as long as they are compounds that generate radicals upon irradiation with visible light. Specific examples include camphorquinones, butanedione, α-diketones such as benzyl and acenaphthophenone, acylphosphine oxide compounds, and thio compounds such as methylthioxanthone. Of these, camphorquinones and acylphosphine oxide compounds are preferably used in the invention because of their excellent curability.

The camphorquinones are represented by the following general formula
Examples thereof include compounds represented by (7).

[0041]

[Chemical 7]

In the formula (7), R ¹¹ is a methyl group, a carboxyl group, a methoxycarbonyl group, a 2-bromoethoxycarbonyl group or a chlorocarbonyl group. General formula
Specific examples of the compound represented by (7) include camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid and 7,7-dimethyl-2. , 3-dioxo [2.2.1] heptane-1
-Carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxo [2.2.1] heptane-1
-Carboxy-methyl ester and 7,7-dimethyl-
2,3-Dioxobicyclo [2.2.1] heptane-1
-Carboxylic acid chlorides. In the present invention, it is particularly preferable to use camphorquinone because the composition has an excellent polymerization rate and the obtained cured product has excellent transparency.

Examples of the acylphosphine oxide compound include compounds represented by the following general formula (8).

[0044]

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In the formula (8), R ¹² , R ¹³ and R ¹⁴ are hydrogen or a methyl group, and they may be the same or different in one molecule, and R ¹⁵ and R ¹⁶ are phenyl groups. Or a methoxy group, which may be the same or different in one molecule. Specific examples of the compound represented by the general formula (8) include benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide and 2,2. 4,6-trimethylbenzoylmethoxyphenylphosphine oxide and 2,
4,6-trimethylbenzoyldiethoxyphosphine oxide and the like can be mentioned. In the present invention, especially 2, 4, 6
It is more preferable to use -trimethylbenzoyldiphenylphosphine oxide because of its excellent polymerizability.

The content of the visible light polymerization initiator in the composition is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If this ratio is less than 0.01% by weight, the visible light curability becomes insufficient, and if it exceeds 10% by weight, the photocurability is not improved even if the content is exceeded. High costs will be incurred.

1-4. Pigment The visible light curable composition used in the present invention preferably contains a pigment as a coloring component. Various pigments can be used. For example, titanium oxide, zinc white,
Lithbon, lead white, cadmium yellow, yellow lead, chrome permillion, chrome orange, ocher, amber, red iron oxide, yellow iron oxide, cadmium red, red lead, navy blue, ultramarine, cobalt blue, chromium oxide, carbon black and iron Inorganic pigments such as black, benzyl yellow, Hansa yellow G, permanent red 4R, para red, phthalocyanine blue, aniline black, permanent yellow HR, violet BL, quinacridone, fast orange GRL and other organic pigments, and lilyl red, alizarin lake , Pigment Scarlet 3
B, Brilliant Carmine 6B, Permanent Red F
5R, lake red C, rhodamine lake B, rhodamine lake B, rhodamine lake Y, peacock blue lake, red No. 3 aluminum lake, yellow No. 5 aluminum lake and blue No. 2 aluminum lake.

The content of the pigment is 0.00 in the composition.
1 to 10% by weight is preferable, and more preferably 0.01 to
5% by weight. When this ratio is less than 0.001% by weight, the degree of coloring of the cured product is low, and it is difficult to confirm whether or not the composition has been applied. When it exceeds 10% by weight, the visible light transmittance is high. Deteriorates, which leads to poor curing of the resin.

1-5. Other Compounds In the visible light curable composition, if desired, amine compounds such as 4-dimethylaminobenzoic acid and sensitizers such as Michler's ketone such as bisdiethylaminobenzophenone; organic peroxides; oil red and Sudan I etc. Oil-soluble dye,
Azo dyes such as Orange II and Ceriton Fast Yellow G, quinone imine dyes such as Rhodamine B, indigoid dyes such as Induslen Brilliant Pink R, anthran quinone dyes such as Sun Red No 1 and Sun Red LN,
Fluorescent dyes such as White Flow B, Red No. 2, Red No. 3, Red No. 106, Yellow No. 5, Blue No. 1, Akamin F
Dyes such as food colorings such as R-100 and vermilion No. 101; radical polymerization stabilizers; thickeners and the like can be added in a conventionally used ratio.

2. Battery The present invention is a battery in which a space between the positive electrode terminal and the negative electrode terminal is filled or covered with a cured product of the visible light curable composition. Examples of the method for producing the battery of the present invention include a method in which a visible light-curable composition is applied or filled in a recess formed between a negative electrode terminal and a positive electrode terminal on the outer periphery thereof, and visible light is irradiated. . The present invention has various battery forms, for example, alkaline dry batteries, silver oxide batteries, air batteries,
Examples thereof include cylindrical batteries such as lithium batteries and nickel-cadmium batteries, and button-shaped batteries.

[0051]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the alkaline dry battery of the present invention will be described with reference to FIGS. In FIG. 1, reference numeral 1 denotes a metal battery case that also serves as a positive electrode terminal, and a positive electrode active material 2 and a negative electrode active material 4 are filled in the interior thereof via a separator 3. Reference numeral 5 is a negative electrode current collector rod, and 6 is a gasket for sealing the opening of the battery case 1. The bottom plate 7, which is the negative electrode terminal, is spot-welded to the end portion of the collector rod 5, and the battery case 1 is connected via the gasket 6.
It is crimped and retained. FIG. 2 is an enlarged view of the portion A of FIG. The concave portion between the positive electrode terminal 1 and the negative electrode terminal 7 is filled with a cured product 9 of the visible light curable composition.

[0052]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. ○ Example A visible light curable composition was prepared by blending a radically polymerizable vinyl compound having the composition shown in Table 1, an ultraviolet absorber, a visible light polymerization initiator and a pigment. ○ Evaluation 1) Photocuring depth and corrosiveness The composition is applied to the iron plate surface in a film thickness of 2 mm, a Moritex MXE-150 is used as a light irradiating device, an ultraviolet ray cut filter U-360 is used, and a light amount produced by Ushio Inc. 3,000mJ by measuring device (optical sensor 435nm)
The composition was irradiated with the amount of light to cure the composition to prepare a test body. The test piece is placed in a high temperature and high humidity state of 80 ° C × 95 ° C RH for 24 hours.
After being left for a period of time, the hardening depth and corrosion state of the coated iron plate portion were observed. Table 1 shows the results. In Table 1,
The curing depths ◯, Δ, and × have the following meanings. ○: The whole is hardened, △: The lower part is uncured, ×; The inner and lower parts are uncured 2) Fading property The composition is applied to the surface of the iron plate with a film thickness of 0.1 mm and irradiated with light in the same manner as above to form the composition. The product was cured to prepare a test piece.
A test piece is tested for weather resistance [UVCON UC-1 type,
(Manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 200 hours, and the fading degree of the cured product was visually observed. Table 1 shows the results.

[0053]

[Table 1]

(* 1) Epoxy acrylate: Lipoxy SP-1509 [manufactured by Showa Highpolymer Co., Ltd.] (* 2) DMBI: isoamyl 4-dimethylaminobenzoate (* 3) Lucillin TPO: 2,4,6-trimethyl Benzoyldiphenylphosphine oxide (manufactured by BASF) (* 4) TINUVIN P: 2- (5-methyl-2-human benzyloxyphenyl) benzotriazole (manufactured by Ciba-Geigy Co., Ltd.) (* 5) TINUVIN 571: Human oxyphenyl benzotriazole Derivatives [Ciba Geigy Co., Ltd.] (* 6) Pigment Red: DYNAMIC SZ-7121 Red [Dainippon Seika Co., Ltd.] (* 7) Pigment Blue: Bu-51 [Dainippon Seika Co., Ltd.]

Comparative Example A UV-curable composition was prepared by blending a radically polymerizable vinyl compound having the composition shown in Table 2, an ultraviolet absorber, an ultraviolet polymerization initiator and a pigment (Comparative Examples 1 to 5). Further, a visible light curable composition containing no ultraviolet absorber was prepared by blending the radically polymerizable vinyl compound having the composition shown in Table 3, a visible light polymerization initiator and a pigment (Comparative Examples 6 to 8). In Comparative Examples 1 to 5, MX-30 manufactured by Moritex was used as a light irradiation device, and a visible light cut filter L-40 was used.
Using a light measurement device made by USHIO INC. (Optical sensor 3
A test piece was prepared in the same manner as in Example except that the ultraviolet ray having a light amount of 3,000 mJ was irradiated at 65 nm), and evaluated in the same manner as in Example. In Comparative Examples 6 to 8, test pieces were prepared in the same manner as in the example, and evaluated in the same manner as in the example. The results of Comparative Examples 1 to 5 are shown in Table 2, and the results of Comparative Examples 6 to 8 are shown in Table 3.

[0056]

[Table 2]

(* 1) Epoxy acrylate: Lipoxy SP-1509 [manufactured by Showa Highpolymer Co., Ltd.] (* 2) Drocur 1173: 2-Human Doxy-2-methyl-1-phenylpropan-1-one [Ciba Geigy ( Co., Ltd.) (* 3) TINUVIN P: 2- (5-methyl-2-human oxyphenyl) benzotriazole (Ciba Geigy Co., Ltd.) (* 4) TINUVIN 571: human oxyphenyl benzotrisole derivative [Ciba Geigy Co., Ltd.] (* 5) Pigment Red: DYNAMIC SZ-7121 Red [Dainippon Seika Co., Ltd.] (* 6) Pigment Blue: Bu-51 [Dainippon Seika Co., Ltd.]

[0058]

[Table 3]

(* 1) DMBI: isoamyl 4-dimethylaminobenzoate (* 2) Lucillin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF) (* 3) Pigment red: DYNAMIC SZ -7121 Red [Dainippon Seika Co., Ltd.] (* 4) Pigment Blue: Bu-51 [Dainippon Seika Co., Ltd.]

[0060]

INDUSTRIAL APPLICABILITY The battery of the present invention has a high curing reliability and rust preventive property of the visible light curable composition used, so that it has high insulation reliability and can be cured by irradiation with a slight amount of light. Therefore, it is excellent in workability and productivity, and since it is possible to confirm whether or not the composition is applied to the battery because the composition contains a pigment, it is also excellent in quality control. The color does not easily fade, and since visible light that is safe for the human body can be used, it has an excellent effect of improving the working environment.

[Brief description of drawings]

FIG. 1 is an example of an embodiment of an alkaline dry battery of the present invention.

FIG. 2 is an enlarged view of a portion A in FIG.

[Explanation of symbols]

 1: Battery Case (Positive Electrode Terminal) 2: Positive Electrode Active Material 3: Separator 4: Negative Electrode Working Material 5: Current Collector Rod 6: Gasket 7: Bottom Plate (Negative Electrode Terminal) 8: Exterior Label 9: Cured Product of Visible Light Curable Composition

Claims (1)

[Claims] 1. A cured product of a visible light curable composition comprising a radically polymerizable vinyl compound, an ultraviolet absorber, a visible light polymerization initiator and a pigment is filled or covered between the positive electrode terminal and the negative electrode terminal. battery.