CN103187175B - Electrolytic capacitor driving electrolytic solution - Google Patents
Electrolytic capacitor driving electrolytic solution Download PDFInfo
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- CN103187175B CN103187175B CN201210563093.XA CN201210563093A CN103187175B CN 103187175 B CN103187175 B CN 103187175B CN 201210563093 A CN201210563093 A CN 201210563093A CN 103187175 B CN103187175 B CN 103187175B
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Abstract
The present invention provides electrolytic capacitor driving electrolytic solution, and it is that can suppress the electrolyte containing PVA resinoids that electrolyte is deteriorated, safe and voltage-resistent characteristic is also excellent.Electrolytic capacitor driving electrolytic solution of the invention is characterised by, containing the solvent with ethylene glycol as main component, carboxylic acid or its salt and the degree of polymerization be 50 ~ 2000, saponification degree be 20.0 ~ 99.5 moles of %, sodium contents as 10ppm below polyvinyl alcohol resin.
Description
Technical field
The present invention relates to the aluminium electrolutic capacitor driving electrolytic solution (letter below of the mesohigh with ethylene glycol as primary solvent
Referred to as electrolyte), more specifically, the present invention provides through using the polyvinyl alcohol resin (letter below that is substantially free of sodium
Referred to as PVA resinoids) and deterioration, safe electrolyte can be suppressed.
Background technology
In recent years, the requirement to the security of electrolytic capacitor is increased, and thereupon, improving proof voltage also becomes important.
In order to improve the proof voltage, the macromolecular compound such as PVA resinoids is added in the electrolytic solution come improve proof voltage (patent document 1,
2)。
The representational industrially preparing process of PVA resinoids is following method：Make vinyl acetate as shown in following formula (2)
Radical polymerization is carried out in methanol solvate, and soap is carried out to the polyvinyl acetate for obtaining with NaOH in methanol solution
Change reaction.
In above-mentioned manufacture method, it is set to carry out radical polymerization using initiators such as azo, peroxides during polymerization
Close, now, such as shown in following formula (3), a part occurs chain transfer reaction, and thus, chain reaction is transferred to the ester of vinyl acetate
Base end.Long chain branches are referred to as, but the branch is cut off in saponification.Now, the end of the polymer chain of branch
Structure when saponification is carried out using NaOH, as end remain carboxylic acid sodium structure.
In addition, when using NaOH in saponification, generating as the sodium acetate of its accessory substance, a part is with impurity
Form is mixed in product.
When these sodium compositions are present in electrolyte, there are the following problems：Electrolyte pH can be made to change, as sealing
The reason for deterioration of the peripheral components such as agent, the oxide film thereon being formed on electrode are deteriorated.
Patent document 1：Japanese Unexamined Patent Application 60-91618 publications
Patent document 2：Japanese Unexamined Patent Publication 09-298130 publications
The content of the invention
In view of above-mentioned present situation, it is an object of the invention to provide suppressing the deterioration of electrolyte, safe and proof voltage is special
The also excellent electrolyte containing PVA resinoids of property.
The present inventor has been repeated further investigation, as a result find, by using containing with ethylene glycol as main component
Solvent, carboxylic acid or its salt and sodium content are the electrolyte of the polyvinyl alcohol resin of below 10ppm, can solve the problem that above mentioned problem,
And then research is repeated, so as to complete the present invention.
That is, the present invention relates to following invention.
[1] a kind of electrolytic capacitor driving electrolytic solution, it is characterised in that containing molten with ethylene glycol as main component
Agent, carboxylic acid or its salt and the degree of polymerization are the poly- second that 50 ~ 2000, saponification degree is 20.0 ~ 99.5 moles of %, sodium content is below 10ppm
Enol resinoid.
[2] electrolytic capacitor driving electrolytic solution as described above described in [1], it is characterised in that the degree of polymerization be 50 ~ 2000,
Saponification degree is 20.0 ~ 99.5 moles of %, sodium content for the polyvinyl alcohol resin of below 10ppm is urged by the saponification without sodium
Compound of being birdsed of the same feather flock together to aliphatic vinyl ester in the presence of agent carries out saponification and obtains.
[3] electrolytic capacitor driving electrolytic solution as described above described in [2], it is characterised in that the saponification catalysis without sodium
Agent is phosphazene compound.
[4] electrolytic capacitor driving electrolytic solution as described above described in [2], it is characterised in that the saponification catalysis without sodium
Agent is the quaternary phosphonium hydroxides ammonium compounds represented by following formulas (1),
R1R2R3R4N+OH- (1)
In above formula (1), R1~R4It is each independently alkyl, benzyl or the phenyl of carbon number 1 ~ 16.
[5] electrolytic capacitor driving electrolytic solution as described above described in [2], it is characterised in that the saponification catalysis without sodium
Agent is guanidine compound or amidine compound.
[6] electrolytic capacitor driving electrolytic solution as described above described in [2], it is characterised in that the saponification catalysis without sodium
Agent is sour saponification catalyst.
[7] electrolytic capacitor driving electrolytic solution as described above described in [6], it is characterised in that sour saponification catalyst is choosing
More than a kind in the group of free formic acid, acetic acid, citric acid, lactic acid, butanedioic acid and nitric acid composition.
[8] a kind of manufacture method of electrolytic capacitor driving electrolytic solution, for manufacturing any one of above-mentioned [1] ~ [7] institute
The electrolytic capacitor driving electrolytic solution stated, it is characterised in that comprising following operation：By using the saponification catalyst without sodium
It is the work of the polyvinyl alcohol resin of below 10ppm that compound of being birdsed of the same feather flock together to aliphatic vinyl ester carries out saponification and manufactures sodium content
Sequence；And dissolve in the solvent with ethylene glycol as main component carboxylic acid or its salt and sodium content as 10ppm below polyethylene
The operation of alcohol resinoid.
Invention effect
During using electrolytic capacitor driving electrolytic solution of the invention, it is not easy to which the performance degradation of electrolyte occurs, and
By adding polyvinyl alcohol resin, using the teaching of the invention it is possible to provide safe and voltage-resistent characteristic electrolyte high.
Specific embodiment
Below, electrolytic capacitor driving electrolytic solution of the invention is described in detail.
The solvent used as main component in electrolyte of the invention is ethylene glycol, is not damaging the model of effect of the present invention
In enclosing, it is also possible to mix other solvents.As the solvent mixed in ethylene glycol, can illustrate for example：The glycols such as propane diols；
γ-The lactones such as butyrolactone, METHYLPYRROLIDONE；N-METHYLFORMAMIDE, N,N-dimethylformamide, N- ethyl formyls
The amide-types such as amine；The carbonates such as ethylene carbonate, propylene carbonate；The nitriles such as acetonitrile；Dimethyl sulfoxide；Ethers；Ketone；Ester
Class；Sulfolane and its derivative；Water etc..These other solvents can be used alone one kind, it is also possible to be used in mixed way two or more.
As the carboxylic acid used in electrolyte of the invention, it is not particularly limited, can enumerates for example：Formic acid, acetic acid, the moon
Cinnamic acid, stearic acid, capric acid, benzoic acid, salicylic acid, maleic acid, phthalic acid, fumaric acid, butanedioic acid, glutaric acid, azelaic acid,
Decanedioic acid, 2- methyl azelaic acid, 1,6- decane dicarboxylic acids, 5,6- decane dicarboxylic acids, 7- vinyl hexadecene -1,16- dicarboxyls
Acid etc..
In addition, as the salt of carboxylic acid, being not particularly limited, in addition to ammonium salt, can also enumerate for example：Methylamine, ethamine,
The primary amine salts such as tert-butylamine；The secondary amine salts such as dimethylamine, ethyl dimethylamine, diethylamine；Trimethylamine, diethyl methyl amine, dimethylamine, three
The tertiary ammonium salts such as ethamine；The quaternary ammonium salts such as tetramethyl-ammonium, triethyl methyl ammonium, tetraethyl ammonium；ImidazolesFuse salts such as salt etc..As carboxylic
The content of acid or its salt, as long as do not damage effect of the present invention being just not particularly limited, relative to electrolyte entirety, usually 0.05
~ 10.0 mass %, preferably 0.1 ~ 8.0 mass %.For these carboxylic acids and carboxylate, one kind is can be used alone, it is also possible to mixed
Close using two or more.
For the sodium content that is used in electrolyte of the invention is for the PVA resinoids of below 10ppm, from can suppress
The deterioration of electrolyte, in it make use of the capacitor using the electrolyte of PVA resinoids electrode degradation be inhibited, with good
Life characteristics at high temperature and voltage-resistent characteristic it is also excellent from the viewpoint of, as long as sodium content is below 10ppm, preferably sodium contains
Amount is less than 10ppm, from from the viewpoint of making the effect above higher, more preferably below 5ppm, more preferably below 1ppm.
It should be noted that " sodium content is the PVA resinoids of below 10ppm " refers to the sodium content of the quality criteria in PVA resinoids
It is below 0.001 mass %.In the present invention, sodium content uses polarisation Zeeman atomic absorption spectrophotometer Z-5300 (Hitachi's systems
Make manufactured) determine.
The manufacture method of the PVA resinoids for being used in electrolyte of the invention, as long as make sodium content for 10ppm with
Under preparation method, be not particularly limited, be industrially preferably as follows method：Make aliphatic vinyl ester (mainly acetic acid second
Alkene ester) carry out polymerisation in solution in methanol solvate, and to obtaining in the presence of the saponification catalyst or sour saponification catalyst
Aliphatic vinyl ester compound of birdsing of the same feather flock together carries out saponification.
As the polymerization initiator for making aliphatic vinyl ester be used when being polymerized, it is not particularly limited, usually using even
Nitrogen compound, peroxide type initiators etc..
In addition, in order to prevent aliphatic vinyl ester during polymerization from hydrolyzing, tartaric acid, citric acid, acetic acid can be added
Deng organic acid.
It should be noted that in order to adjust the degree of polymerization, it is possible to use the chain such as 2 mercapto ethanol, 1- lauryl mercaptans, acetaldehyde turns
Move agent.
In addition, not damaging in the range of effect of the present invention, it is possible to use by aliphatic vinyl ester with can be with
The copolymer of other unsaturated monomers of its copolymerization carries out PVA resinoids obtained from saponification, other unsaturated monomers example
Such as it is：The unsaturated monomers containing carboxyl such as (methyl) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid；Malaysia
The unsaturated dibasic acid monoalkyl esters such as sour mono-methyl, monomethyl itaconate；Acrylamide, DMAA, diformazan ammonia
Base ethyl acrylamide, acrylamide, dimethylamino propyl acrylamide, N-isopropylacrylamide, N- methylols third
The amide-containing unsaturated monomers such as acrylamide, N- vinyl acetamides, DAAM；The halogenations such as vinyl chloride, PVF
Vinyl；The unsaturated monomer with glycidyl such as allyl glycidyl ether, GMA；N- second
Alkenyl -2-Pyrrolidone, N- vinyl -3- propyl group -2-Pyrrolidone, N- vinyl -5- N-methyl-2-2-pyrrolidone Ns, N- ethene
Base -5,5- dimethyl -2-Pyrrolidone, N- vinyl -3,5- dimethyl -2-Pyrrolidone, N- pi-allyls -2-Pyrrolidone etc.
Unsaturated monomer containing 2-Pyrrolidone ring；Methyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, normal-butyl
Vinyl ethers, IVE, tert-Butyl vinyl ether, lauryl vinyl ether, dodecyl vinyl, octadecane
The alkyl vinyl ethers such as base vinyl ethers；The nitriles such as acrylonitrile, methacrylonitrile；Allyl alcohol, dimethallyl alcohol, isopropyl alkene
The hydroxyl unsaturated monomer such as base allyl alcohol, hydroxyethyl vinylethers, hydroxy butyl vinyl ether；Allyl acetic acid ester, dimethyl
The acetyl-containing unsaturated monomers such as allyl acetic acid ester, isopropenyl allyl acetic acid ester；(methyl) methyl acrylate, (methyl)
Ethyl acrylate, acrylic acid-2-ethyl caproite, n-butyl acrylate etc. (methyl) esters of acrylic acid；Trimethoxyvinyl silicon
The vinyl silanes classes such as alkane, tributyl vinyl silanes, diphenyl methyl vinyl silanes；Polyoxyethylene (methyl) acrylic acid
Polyoxy alkylidene (methyl) esters of acrylic acids such as ester, polyoxypropylene (methyl) acrylate；Polyoxyethylene (methyl) acrylamide,
Polyoxypropylene (methyl) acrylamide etc. polyoxy alkylidene (methyl) acrylic amide；Polyoxyethylene vinyl ethers, polyoxypropylene
The polyoxy alkylidene vinyl ethers such as vinyl ethers；Polyoxyethylene allyl ether, polyoxypropylene allyl ether, polyoxyethylene butyl
The polyoxyalkylene alkyl vinyl ethers such as vinyl ethers, polyoxypropylene butyl vinyl ether；Ethene, propylene, n-butene, 1- oneself
The alpha-olefines such as alkene；3,4- dihydroxy -1- butylene, the acyloxy -1- butylene of 3,4- bis-, 3- acyloxy -4- hydroxyl-1-butenes, 4-
The butylene classes such as acyloxy -3- hydroxyl-1-butenes, bis- acyloxy of 3,4- -2-methyl-1-butene alkene；4,5- dihydroxy -1- amylenes, 4,
The amylenes such as the acyloxy -1- amylenes of 5- bis-, 4,5- dihydroxy -3- Methyl-1-pentenes, the acyloxy -3- Methyl-1-pentenes of 4,5- bis-
Class；The hexene classes such as 5,6- dihydroxy -1- hexenes, the acyloxy -1- hexenes of 5,6- bis-；N, N- dimethyl allylamine, N- pi-allyl piperazines
Piperazine, 3- piperidines ethyl acrylate, 2- vinylpyridines, 4-vinylpridine, 2- methyl -6- vinylpyridines, 5- ethyl -2- second
The amine unsaturated monomers such as alkenyl pyridine, 5- butylene yl pyridines, 4- amylenes yl pyridines, 2- (4- pyridine radicals) allyl alcohol；Diformazan ammonia
Base ethyl propylene acid esters methyl chloride quaternary ammonium salt, N, N- dimethylamino propyl acrylamide methyl chlorides quaternary ammonium salt, N, N- diformazans
The unsaturated monomers with quaternary ammonium compound such as aminopropyl acrylamide toluene sulfonic acide quaternary ammonium salt；The fragrance such as styrene same clan
Unsaturated monomer；2- acrylamide-2-methyl propane sulfonics or its alkali metal salt, ammonium salt or organic amine salt, 2- acrylamide -1- first
Base propane sulfonic acid or its alkali metal salt, ammonium salt or organic amine salt, 2- Methacrylamide -2- methyl propane sulfonic acids or its alkali metal salt,
Ammonium salt or organic amine salt, vinyl sulfonic acid or its alkali metal salt, ammonium salt or organic amine salt, allyl sulphonic acid or its alkali metal salt,
Ammonium salt or organic amine salt, methallyl sulfonic acid or its alkali metal salt, ammonium salt or organic amine salt etc. contain sulfonic unsaturation
Monomer；Allylin, 2,3- diacetoxy -1- allyloxys propane, 2- acetoxyl group -1- allyloxy -3- hydroxyls
Base propane, 3- acetoxyl group -1- allyloxy -3- hydroxy propanes, 3- acetoxyl group -1- allyloxy -2- hydroxy propanes, glycerine
Mono vinyl ether, glycerine list isopropenyl ethers, acryloyl morpholine, vinylethylene carbonate etc..In the PVA classes of these modifications by copolymerization
In resin, from from the viewpoint of the favorable solubility of ethylene glycol, the modified PVA resinoids of polyoxy alkylidene are preferably used.
Aliphatic vinyl ester with can be able to be with the copolymerization ratios of the unsaturated monomer of aliphatic vinyl ester copolymerization
Arbitrarily, typically copolymerization is carried out by 0.1 ~ 10 mole of scope of % of the ratio of the unsaturated monomer in usual copolymer resins.
Additionally, carrying out glycerol polymerization with side by the PVA resinoids that make as above to obtain and acrylic acid, methacrylic acid etc.
Additional functionality on chain and carried out post-modification PVA resinoids, by the method that reacts PVA resinoids and ketene dimer,
The post-modifications such as the acetoacetylation PVA for obtaining such as the method for making PVA resinoids be reacted with acetoacetic ester to carry out ester exchange
PVA resinoids can also be used as the PVA resinoids in the present invention.
Additionally, for PVA resinoids of the invention, not damaging in the range of effect of the present invention, it is also possible to pass through
Part carries out the reaction such as urethane, acetal, etherificate, grafting, Phosphation to make it be modified.
When aliphatic vinyl ester is polymerized, the shape of aggregation container, the species of polymerization stirrer and polymerization temperature,
Pressure in aggregation container etc. can use known method.
In the PVA resinoids for generally industrially obtaining, NaOH is used during due to saponification, therefore, generally with impurity
Form contains the sodium acetate of accessory substance during as saponification, and intramolecular in PVA resinoids also contains sodium.In order to subtract
Sodium content in few these PVA resinoids, can enumerate following methods：[1] compound of being birdsed of the same feather flock together to aliphatic vinyl ester carries out acid
Saponification is saponification and be made after PVA resinoids the mixing with the alcohols such as methyl alcohol, ethanol or these alcohols and water, methyl acetate etc.
The method that solvent is cleaned；[2] PVA resinoids is dissolved in water equal solvent and be passed to acid after being made PVA resinoid solution
Type amberlite lipid layer is come the method that removes sodium ion；[3] compound of being birdsed of the same feather flock together to aliphatic vinyl ester made during saponification
Saponification catalyst using without sodium saponification catalyst method, industrially preferably [3] method.That is, in the present invention
In, sodium content for below 10ppm PVA resinoids preferably by using the saponification catalyst without sodium to aliphatic vinyl ester
Compound of birdsing of the same feather flock together carries out saponification and obtains.[1] in method, it is difficult to fully reduce sodium content, due to largely being made using cleaning fluid
The cost recovery of cleaning fluid is raised.[2] in method, although sodium amount can be made to be reduced to the level of needs, but due to leading to it
Cross the relation of amberlite lipid layer and need the control of the concentration of the PVA resinoids in the aqueous solution less than 10 mass %, thus
Producing rate variance, will can not also be adjusted to desired cooperation sometimes in the present invention to water is added in electrolyte.
The saponification catalyst used when compound carries out saponification as birdsing of the same feather flock together to aliphatic vinyl ester, can enumerate：Hydrogen-oxygen
Change sodium, sodium alkoxide, tetra-alkyl ammonium hydroxide, benzyl trialkylammonium hydroxides, ring amidine class and (refer to Japanese Unexamined Patent Application 62-225504
Publication), guanidine compound (with reference to Japanese Unexamined Patent Publication 08-12721 publications), amidine compound is (with reference to Japanese Unexamined Patent Publication 08-27218
Number publication), the saponification catalyst such as phosphazene compound (with reference to Japanese Unexamined Patent Publication 2001-81130 publications)；Hydrochloric acid, sulfuric acid, phosphorus
The acid saponification catalyst such as acid, acetic acid, citric acid, lactic acid, p-methyl benzenesulfonic acid, α-or beta-naphthalenesulfonic-acid, 3,4- acid dimethyls, makees
The saponification catalyst without sodium used when compound carries out saponification to be birdsed of the same feather flock together to aliphatic vinyl ester in the method for above-mentioned [3],
Saponification catalyst is preferably quaternary ammonium hydroxide, guanidine compound or the amidine compound that phosphazene compound, following formulas (1) are represented.
These saponification catalyst can be used alone one kind, it is also possible to be applied in combination two or more.It should be noted that this specification
In saponification catalyst " be free of sodium " refer to constitute be free of sodium (Na) atom and its group in molecule such as NaOH (NaOH)
Also sodium atom is free of in compound.Without sodium atom refer to contain in forms such as impurity in the catalyst in the composition of saponification catalyst
Some sodium for about below 500ppm.As such saponification catalyst, the sodium for about 100ppm for preferably being contained with Impure forms with
Under saponification catalyst, the even more preferably about saponification catalyst of below 50ppm is most preferably substantially free of the saponification catalysis of sodium
Agent.
R1R2R3R4N+OH- (1)
In above formula (1), R1~R4It is each independently alkyl, benzyl or the phenyl of carbon number 1 ~ 16.
As phosphazene compound, it is not particularly limited, for example preferably 2- tertbutylimidos -2- lignocaine -1,3-
The a word used for translation phosphorus English of dimethyl perhydro -1,3,2- two (2-tert- Block チ Le イ ミ ノ -2- ジ エ チ Le ア ミ ノ -1,3- ジ メ チ Le-ペ
Le Ha ロ イ De -1,3,2- ジ ア ザ ホ ス ホ リ Application), tertbutylimido-three (dimethylamino) phosphorane, tertbutylimido -
Three (pyrrolidinyl) phosphoranes, the λ of 1- ethyls -2,2,4,4,4- five (dimethylamino) -25,4λ5- connect two (phosphine nitriles), the 1- tert-butyl group -4,
Double [three (dimethylamino) phosphoranediyl amino] -2 λ of 4,4- tri- (dimethylamino) -2,2-5,4λ5- connect two (phosphine nitriles).
In the quaternary ammonium hydroxide that above-mentioned formula (1) represents, the alkyl of carbon number 1 ~ 16 can be that straight chained alkyl can also
It is the branched alkyl of carbon number 2 ~ 16.In addition, benzyl and phenyl can have the carbon numbers such as 1 ~ 5 methyl, ethyl, propyl group
1 ~ 6 low alkyl group or halogen atom etc. replace base.As the quaternary ammonium hydroxide that formula (1) is represented, specifically, preferred tetramethyl
Base ammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, benzyltrimethylammonium hydroxide, four
Benzyl ammonium hydroxide, methyl tributyl ammonium hydroxide, cetyltrimethylammonium hydroxide, phenyl trimethicone ammonium hydroxide etc..
As guanidine compound, it is not particularly limited, preferably for example：1,1,3,3- trimethyls guanidine, 1- cyanoethyls -1,3,3- three
Methylguanidine, 1- benzyl -1,3,3- trimethyls guanidine, 7- methyl isophthalic acids, 5,7- tri- azabicyclo [4.4.0] decene -5.
As amidine compound, it is not particularly limited, preferably for example：6- dimethylamino -1,8- diazabicyclos [5.4.0] ten
One carbene -7,6- lignocaine -1,8- diazabicyclo [5.4.0] endecatylene -7,6- dipropyl amino -1,8- diazabicyclos
[5.4.0] endecatylene -7,6- dibutylamino -1,8- diazabicyclo [5.4.0] endecatylene -7.
In these catalyst, more preferably phosphazene compound, quaternary ammonium hydroxide, particularly preferred TMAH, benzyl
The quaternary ammonium hydroxides such as trimethylammonium hydroxide.
Solvent composition when saponification catalyst amount without sodium is according to species, the saponification of the compound for being used and contain
Water rate and it is different, when carrying out saponification in methanol solvate, birdsed of the same feather flock together compound relative to aliphatic vinyl ester, preferably 0.5 ~
500 milliequivalents, more preferably 1 ~ 100 milliequivalent.
Solvent for saponification is not particularly limited, and can enumerate for example：The non-pole of aprotic polar solvent, aprotic
Property solvent, polar aprotic solvent, rudimentary diamines or triamine compound etc..Aprotic polar solvent refers to without protic
The polar solvent of hydrogen, can enumerate for example：DMSO, dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, tetrahydrochysene
Furans, dimethyl-tetrahydrofuran, dioxane, acetone, MEK, acetonitrile, toluene, chlorobenzene etc..Aprotic is nonpolar
Solvent refers to the non-polar solven without protic hydrogen, can enumerate for example：Benzene, toluene etc..Polar aprotic solvent refers to have
The polar solvent of protic hydrogen, can enumerate for example：Water, formic acid, methyl alcohol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, acetic acid
Deng.These saponification solvents can be used alone one kind, it is also possible to be used in mixed way two or more.
The degree of polymerization for PVA resinoids of the invention is usually 50 ~ 2000, preferably 80 ~ 1000, more preferably
100~700.When the degree of polymerization is less than 50, industrially it is difficult to produce, when the degree of polymerization is more than 2000, it is difficult to be dissolved in ethylene glycol,
The viscosity of electrolyte is also raised, thus ratio resistance is become too high, therefore, it is unsuitable for low resistance purposes.The degree of polymerization passes through JISK-
Method described in 6726 (1994) is determined.
In addition, the saponification degree of PVA resinoids of the invention is usually 20.0 ~ 99.5 moles of %, preferably 30.0 ~ 99.0 rub
You are %.When saponification degree is less than 20.0 moles of %, the dissolubility reduction of ethylene glycol, thus be difficult to dissolve, in addition, more than 99.5 moles of %
When, industrially it is difficult to produce.Saponification degree is determined by the method described in JIS K-6726 (1994).
The addition of the PVA resinoids for being used in electrolyte of the invention, relative to electrolyte entirety, usually
0.1 ~ 10.0 mass %, preferably 0.2 ~ 5.0 mass %.When addition is less than 0.1 mass %, the effect for improving proof voltage is insufficient,
During more than 10.0 mass %, ratio resistance becomes too high, therefore is unsuitable for low resistance purposes.
Electrolyte of the invention can by the foregoing solvent with ethylene glycol as main component dissolve carboxylic acid or its
Salt and sodium content are manufactured for the polyvinyl alcohol resin of below 10ppm.The order by merging of each composition is not particularly limited.
In electrolyte of the invention, as long as without prejudice to effect of the present invention, then can be reducing leakage current, improve resistance to electricity
The purposes such as pressure, absorption gas add various known additives.As additive, can enumerate for example：Phosphoric acid (orthophosphoric acid), phosphorus
The phosphate cpds such as acid anhydrides, ammonium phosphate, acid phosphoric acid ester methyl acrylic ester (2- methyacryloxyethyl phosphoric acid class)；
The boronic acid compounds such as boric acid, boron oxide (boric anhydride), ammonium borate；The polyalcohols such as mannitol；With polyethylene glycol, polypropylene glycol,
The random copolymer and block copolymer of polyoxyethylene polyoxypropylene glycol are the macromolecular compound of representative；Nitro compound
Deng.
Embodiment
Below, enumerate embodiment and further specifically describe the present invention, but the present invention not by any of these embodiments
Limitation, in technological thought of the invention, those skilled in the art can largely be deformed.In following embodiment and compare
In example, the PVA for using each saponification catalyst shown in table 1 below to be manufactured as saponification catalyst in following Production Examples 1 is used
Resinoid.It should be noted that the different PVA resinoids of the degree of polymerization make vinyl acetate in above-mentioned Production Example by that can adjust
The ratio of vinyl acetate monomer when monomer carries out polymerisation in solution and the methyl alcohol as solvent and the yield that is polymerized change.Separately
Outward, when allowing to carry out copolymerization with the unsaturated monomer of vinyl acetate monomer copolymerization, also reaching desired modified amount
Mode by the unsaturated monomer be polymerized start when the initial stage disposably add or in polymerization continuous addition etc. is adjusted
The degree of polymerization.The amount and saponification time of the saponification catalyst when saponification degree of PVA resinoids carries out saponification by regulation change
Become.The PVA resinoids that will be obtained are shown in table 1 below together with saponification catalyst.It should be noted that as long as no especially saying
It is bright, then " part " and " % " expression " mass parts " in example and " quality % ".
The Production Example of polyvinyl alcohol resin is as follows.
[Production Example 1]
Put with nitrogen in the reactor that will be provided with agitator, reflux condensing tube, nitrogen ingress pipe, thermometer and pressure gauge
After changing, the vinyl acetate monomer after 2800 mass parts deoxidations and the methyl alcohol after 800 mass parts deoxidations are put into, started under agitation
Heat up and after interior temperature is reached 60 DEG C, be dissolved with 50 mass parts of addition methyl alcohol separately after deoxidation 1 mass parts initiator (2,
2 '-azo is double (2,4- methyl pentane nitriles)) initiator solution and start polymerization.After being polymerized 5 hours at 60 DEG C, cooled down
And stop polymerization.The solid component concentration in polymeric solution now is 55.1% (yield is calculated as 71.8% to be polymerized), in addition, will
The vinylite for obtaining is made 100 moles of polyvinyl alcohol of % of saponification degree and is determined according to JIS K-6726 (1994)
Obtained from the degree of polymerization be 1710.The polymeric solution that will be obtained is supplied to tower in the demonomerization tower with multistage porous plate, from
Tower bottom is blown into methanol vapor and it is contacted with polymeric solution, so as to remove unreacted vinyl acetate monomer.Poly- acetic acid
The solid component concentration of vinyl acetate-methanol solution is 42%.By 1kg (1000 mass parts) polyvinyl acetate-methanol solution
Temperature is maintained at 40 DEG C, adds 8 mass parts tertbutylimido-three (dimethylamino) phosphoranes, carries out saponification 60 minutes.Soap
It is the gel containing solvent methanol and by-product acetic acid methyl esters to change the form at the end of reaction, and saponification degree is 88 moles of %, is evaporated into
It is divided into 58%, (alleged 1ppm represents the quality criteria in PVA resinoids to sodium composition herein less than 1ppm relative to polyvinyl alcohol
The mass % of sodium content 0.0001).After the gel polyvinyl alcohol (PVA1) is ground into the size of 3mm square, be dried and
Volatile ingredient is set to drop to 4%, by gains for experiment.
[Production Example 2 ~ 24]
Change the ingredient proportion of vinyl acetate monomer and methyl alcohol, amount of initiator, be polymerized yield, the making degree of polymerization is different
Polyvinyl acetate-methanol solution, is changed to the species shown in table 1 to carry out saponification by saponification catalyst.It is solidifying after saponification
In the case of in the case that glue can not be crushed or for liquid, directly it is dried, crushed after being dried is into about 3mm ~ about 10mm.Except this
In addition, the operation same with Production Example 1 is carried out, PVA2 ~ 24 shown in table 1 is made respectively.
[table 1]
Saponification catalyst in table 1 is as follows.
1) tertbutylimido-three (pyrrolidinyl) phosphorane
2) a word used for translation phosphorus English of 2- tertbutylimidos -2- lignocaines -1,3- dimethyl perhydros -1,3,2- two
3) TMAH
4) benzyltrimethylammonium hydroxide
5) 7- methyl isophthalic acids, 5,7- tri- azabicyclo [4.4.0] decene -5
6) 6- dipropyls amino -1,8- diazabicyclos [5.4.0] endecatylene -7
7) lactic acid
8) NaOH
[embodiment 1 ~ 12 and comparative example 1 ~ 13]
Each electrolyte of embodiment and comparative example is made by the composition of table 2.Determine the ratio resistance of each electrolyte at 30 DEG C
Spark discharge voltage at value and 85 DEG C, obtains the result of table 2.
[table 2]
(PEG1000：Polyethylene glycol (mean molecule quantity 1000)
Embodiment 1 ~ 12 improves the polyethylene glycol (mean molecule quantity 1000) of spark discharge voltage with being added be used in the past
Comparative example 13 compare, the ratio resistance of embodiment 1 ~ 12 is low, spark discharge voltage rise, therefore, voltage-resistent characteristic is excellent, confirm
To the effect of the raising voltage-resistent characteristic by being brought using PVA resinoids.
In addition, using sodium content for the embodiment 1 ~ 12 of the PVA resinoids of below 10ppm is high with corresponding use sodium content
The comparative example 1 ~ 12 of PVA resinoids compare, ratio resistance is roughly the same, and observes that spark discharge voltage has inclining of rising
To.
Then, treatment will be etched and the surface of the aluminium foil after making expanded surface area forms electricity by anodic oxidation
The anode foils of amboceptor alumina coating and the Cathode Foil of etching process has been carried out to aluminium foil wound across dividing plate, thus made electric capacity
Device element, makes embodiment 1 ~ 12 and each electrolyte of comparative example 1 ~ 12 be infiltrated up in the capacitor element, by the electric capacity after infiltration
To in metal shell, making rated voltage is 400V, the aluminium electrolutic capacitor that specified static capacity is 200 μ F to device component encapsulation.
For each capacitor for obtaining, static capacity, dielectric loss (tan δ), leakage current are determined, then, at 105 DEG C
Carry out the high temperature load test of the rated voltage 400V of applying 10000 hours.After experiment, static capacity, dielectric are determined again and is damaged
Consumption (tan δ), leakage current.In showing the result in table 3.
[table 3]
As shown in table 3, using the degree of polymerization be 50 ~ 2000, saponification degree be 20.0 ~ 99.5 moles of %, sodium content be 10ppm with
Under PVA resinoids embodiment 1 ~ 12 compared with the comparative example 1 ~ 12 of corresponding use sodium content PVA resinoids high, though
Right static capacity and its rate of change and tan δ do not observe difference, but the leakage current of embodiment is notable compared with the value of comparative example
Reduce, electrode degradation is pressed down in it make use of the capacitor using the electrolyte of the PVA resinoids that sodium content is below 10ppm
System.
Industrial applicability
By using PVA resinoids of the invention, voltage-resistent characteristic can be obtained good and negative in prolonged high temperature
Electrode degradation is also inhibited so as to have good life characteristics at high temperature, particularly mesohigh aluminium electroloysis in lotus experiment
Capacitor drive electrolyte.
Claims (7)
1. a kind of electrolytic capacitor driving electrolytic solution, it is characterised in that contain the solvent with ethylene glycol as main component, carboxylic acid
Or its salt and the degree of polymerization are the polyvinyl alcohol that 50 ~ 2000, saponification degree is 20.0 ~ 99.5 moles of %, sodium content is below 10ppm
Resin.
2. electrolytic capacitor driving electrolytic solution according to claim 1, it is characterised in that the degree of polymerization is 50 ~ 2000, soap
Change degree is 20.0 ~ 99.5 moles of %, sodium content for the polyvinyl alcohol resin of below 10ppm is catalyzed by the saponification without sodium
Compound of being birdsed of the same feather flock together to aliphatic vinyl ester in the presence of agent carries out saponification and obtains.
3. electrolytic capacitor driving electrolytic solution according to claim 2, it is characterised in that the saponification catalyst without sodium
It is phosphazene compound.
4. electrolytic capacitor driving electrolytic solution according to claim 2, it is characterised in that the saponification catalyst without sodium
It is the quaternary phosphonium hydroxides ammonium compounds represented by following formulas (1),
R1R2R3R4N+OH- (1)
In above formula (1), R1~R4It is each independently alkyl, benzyl or the phenyl of carbon number 1 ~ 16.
5. electrolytic capacitor driving electrolytic solution according to claim 2, it is characterised in that the saponification catalyst without sodium
It is guanidine compound or amidine compound.
6. electrolytic capacitor driving electrolytic solution according to claim 2, it is characterised in that the saponification catalyst without sodium
It is sour saponification catalyst.
7. electrolytic capacitor driving electrolytic solution according to claim 6, it is characterised in that sour saponification catalyst be selected from
More than a kind in the group be made up of formic acid, acetic acid, citric acid, lactic acid, butanedioic acid and nitric acid.
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| JP2007048965A (en) * | 2005-08-10 | 2007-02-22 | Kuraray Co Ltd | Electrolyte for aluminum electrolytic capacitors |
| CN101155839A (en) * | 2005-10-28 | 2008-04-02 | Lg化学株式会社 | Method and apparatus for production of polyvinyl alcohol with high degree of polymerization |
| JP2010062223A (en) * | 2008-09-01 | 2010-03-18 | Japan Vam & Poval Co Ltd | Coating liquid for boron diffusion |
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| JP2007048965A (en) * | 2005-08-10 | 2007-02-22 | Kuraray Co Ltd | Electrolyte for aluminum electrolytic capacitors |
| CN101155839A (en) * | 2005-10-28 | 2008-04-02 | Lg化学株式会社 | Method and apparatus for production of polyvinyl alcohol with high degree of polymerization |
| JP2010062223A (en) * | 2008-09-01 | 2010-03-18 | Japan Vam & Poval Co Ltd | Coating liquid for boron diffusion |
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