CN100382212C - Electrolytic condenser - Google Patents
Electrolytic condenser Download PDFInfo
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- CN100382212C CN100382212C CNB021061653A CN02106165A CN100382212C CN 100382212 C CN100382212 C CN 100382212C CN B021061653 A CNB021061653 A CN B021061653A CN 02106165 A CN02106165 A CN 02106165A CN 100382212 C CN100382212 C CN 100382212C
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Abstract
The present invention discloses an electrolytic condenser, which is characterized in that: using conductive macromolecules and organic acid complex salts as electrolyte. The electrolytic condenser has: (1) samll creepage current, improved voltage withstand value; (2) good impedance characteristic; (3) good stability; (4) fabricating under a simple project.
Description
Technical field
The present invention relates to a kind of electrolytic capacitor, especially use the electrolytic capacitor of electroconductive polymer and organic acid complex salt.
Background technology
In recent years, be accompanied by the digitlization of electronic device, it is small-sized to require capacitor to have, big capacity, and have low-impedance characteristic in the high frequency field.The capacitor that uses in the high frequency field mostly was plastic film capacitor, laminated type ceramic capacitor etc. in the past.The common shape of the capacitor of this class is bigger, reach difficulty of big Capacity Ratio.On the other hand,, the dry type aluminium electrolytic capacitor is arranged as large value capacitor, and aluminium or tantalum solid electrolytic capacitor.Such electrolytic capacitor must form anodic oxidation film (dielectric) as the anode surface of valve with metal, simultaneously also within it portion the electrolyte of double as negative electrode is arranged.For example, make anode with etching method on the dry type aluminium electrolytic capacitor, between cathode aluminum foil and anode, place isolated substance and it is curling, isolated substance is fully immersed in and drives in the electrolyte.
But,,, will cause serious problems such as its deterioration in characteristics if situations such as electrolytic liquid leakage or evaporation take place as the dry type aluminium electrolytic capacitor.Therefore liquid electrolyte can cause capacitance loss bigger, problems such as the remarkable deterioration of impedance cycle characteristic because the resistivity of its ionic conduction is bigger.In order to improve the problems referred to above, the aluminium or the tantalum solid electrolytic capacitor that use solid electrolyte have just been produced.Electrolyte as solid electrolytic capacitor has Mn oxide, 7-7-8-8-tetracyano-p-quinodimethane salt (TCNQ), and polypyrrole, polythiophene reaches electroconductive polymer materials such as polyaniline.
Summary of the invention
The technical problem to be solved in the present invention: though with Mn oxide as electrolytical solid electrolytic capacitor, it can improve its temperature characterisitic, the problem that situation such as capacity and capacitance loss constantly changed with service time, but because the resistivity of Mn oxide than higher, has therefore just been had no idea for the raising of impedance cycle characteristic.In addition, with Mn oxide as electrolyte, when causing damage through dielectric oxide film after the thermal decomposition process repeatedly.And use tcnq salt as on the electrolytical solid electrolytic capacitor, when smearing up, TCNQ can cause that resistivity rises, the problem that can cause the contact with Cathode Foil to descend like this.
On the other hand, utilize the pyrroles, monomer such as thiophene or aniline, electroconductive polymer surface by chemical oxidising polymerisation reaction formation, oxidant can influence the dielectric oxide film, make its performance degradation, simultaneously electroconductive polymer does not have chemical synthesis (the damage location repair ability of dielectric oxide film) basically, so the production rated voltage electrolytic capacitor that surpasses 35V is suitable difficulty.The electrolytic capacitor that has this structure in addition is when carrying out burin-in process and high-temperature test, owing to the increase of leakage current causes the phenomenon that is short-circuited between K-A.
The present invention has solved the problems referred to above just, so that impedance operator to be provided, and the leakage current characteristic, all very good high voltage withstanding electrolytic capacitor of stability is a purpose.
Technical scheme of the present invention: the present inventor has carried out special investigation in order to address the above problem, draw as drawing a conclusion: with electroconductive polymer (A) and organic acid complex salt (B) as electrolytical electrolytic capacitor, the impedance operator of its electrolytic capacitor, the leakage current characteristic, stability is all very good, and can realize high voltage withstanding characteristic.
Therefore the present invention mainly describes: use electroconductive polymer (A) and organic acid complex salt (B) electrolyte as electrolytic capacitor; This electrolytical constitute; The organic acid complex salt that uses on this electrolytic capacitor.Wherein, described electroconductive polymer (A) adds the compound that obtains behind the additive for conjugated double bond polymer (A-1) or in this polymer; Described organic acid complex salt (B) is made up of complex cation and organic anion, wherein complex cation is at least a kind of cation selecting from the group of 4 grades of ammoniums, 3 grades of sulfanilamide (SN), 4 grades of phosphorus and 3 grades of hydronium(ion)s, and organic anion is at least a kind of anion that removes deprotonation selecting from organic acid groups such as carboxylic acid, sulfonic acid, phenol monomer or dialkyl phosphate, boron fluor-complex; The weight ratio of described electroconductive polymer (A) and described organic acid complex salt (B) is (A): (B)=1: 0.1～5.
Wherein, the complex cation of described organic acid complex salt (B) is 4 grades of ammonium cations.4 grades of ammonium cations in the described electrolyte are from trimethyl second ammonium, diethyl dimethylammonium, triethyl group first ammonium, 1,2,3,4-tetramethyl imidazoline, 1 is selected at least a kind of formation in 2-dimethyl-3-ethyl imidazol(e) quinoline, 1-ethyl-3-methylimidazole and the 1-methyl-3-ethyl imidazol(e).Wherein, the organic anion of described organic acid complex salt (B) is that the anion of selecting to remove deprotonation from carboxylic acid, aromatic sulphonic acid constitutes.Perhaps, the organic anion of described organic acid complex salt (B) is that the anion of selecting to remove deprotonation from the polycycle aromatic sulphonic acid constitutes.
Wherein, the equivalent proportion of complex cation in the described organic acid complex salt (B) and organic anion is 1: 0.2～3.
Wherein, described conjugated double bond polymer (A-1) is to select at least a kind of formation from the group of polypyrrole, polythiophene, polyethylene dihydroxy thiophene, polyaniline.
Electrolytic capacitor of the present invention can be the electrolytic capacitor with solid forms.
Effect of the present invention: the material of forming jointly with electroconductive polymer (A) and organic acid complex salt (B) described in the present invention is as electrolytical electrolytic capacitor, and it has following effect:
(1) leakage current is little, and the proof voltage value increases,
(2) impedance operator is good,
(3) excellent in stability,
(4) can under simple and easy engineering, make.
The specific embodiment of the present invention
Special feature of the present invention is: electroconductive polymer (A) is, conjugated double bond polymer (A-1), or in this polymer, be mixed into the compound that obtains behind the additive (A-2).
(A-1) be a kind of monomer (a-1) or the polymer more than 2 kinds that forms the conjugated double bond polymer.The process that forms (A) can be added (A-2) after (a-1) polymerization, also can in polymerization reaction, add, but reasonable method is to be added into (A-2) in (a-1) polymerization reaction, make it participate in polymerization process, because when adding (A-2) in the polymerization reaction, it can be used as oxidant (a-2), and (a-2) also plays the effect of composite absorber when participating in polymerization reaction as oxidant like this.
As (a-1), list carbon atom quantity 2～30 or above compound below:
(1) fatty family triple bond polymer: acetylene, 1,6-heptadiyne etc.
(2) aromatic series conjugated compound: benzene, naphthalene, anthracene etc.
(3) contain the conjugated compound of heterochain atom: pyrroles, thiophene, furans, multielement lopps compounds such as ethene dihydroxy thiophene; Aniline, sulfo-aniline, non-multielement lopps compounds such as biphenyl thioether.
(4) alkyl of the carbon number 1～20 of described (1)～(3) displacement compound (for example methyl, ethyl, lauryl, stearyl etc.), aryl displacement compound (phenyl, naphthyl etc.).
Described monomer (a-1) uses can more than a kind or 2 kinds.Reasonable in these materials is the conjugated compound that contains different chain atom of (3), is more preferably multielement lopps compound and aniline, it would be desirable the pyrroles, thiophene, ethene dihydroxy thiophene and aniline.
Below cited in (1)～(7) be as (a-2) oxidant:
(1) transform slaine:
Inorganic acid salt: ferric sulfate, ferric nitrate, iron chloride is crossed ferric chlorate, ferric phosphate, ferric bromide, iron hydroxide, copper nitrate, copper sulphate, copper chloride etc.,
Acylate: oxalates (ferric oxalate, cupric oxalate etc.), the aliphatic category sulfonic acid iron of carbon number 1～30 (methanesulfonic acid iron, propane sulfonic acid iron etc.), the aromatic sulphonic acid iron of carbon number 7～30 (benzene sulfonic acid iron, p-toluenesulfonic acid iron etc.), the aliphatic category sulfonic acid copper of carbon number 1～30 (copper methane sulfonate, propane sulfonic acid copper etc.), the aromatic sulphonic acid copper of carbon number 7～30 (benzoic acid copper, phthalic acid copper etc.)
Complex salt: nickel sodium chromate, nickel potassium chromate, nickel ammonium chromate, sodium permanganate, potassinm permanganate, molybdenum phosphate sodium etc.
(2) Bronsted acid and protonated salt thereof [removing the conversion slaine in (1)]: hydrochloric acid, sulfuric acid, nitric acid, fluorosulfuric acid, sulfuric chlorohydrin, hydrofluoric acid, phosphorus is fluoridized hydracid etc., and the alkali metal salt (sodium of above-mentioned Bronsted acid, potassium etc.), ammonium salt, the organic amine salt of carbon several 3～10 (Trimethylamine, triethylamine etc.).
(3) the different amine salt of diazonium: hydrosulphuric acid benzene diazonium drone salt, hydrosulphuric acid o-toluene diazonium drone salt etc.
(4) halogen and halide thereof: bromine, iodine, IBr, arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminium chloride, aluminium bromide etc.
(5) peracid and its esters: cross hydrogen-oxygen acid, cross inorganic acid (crossing chloric acid, periodic acid etc.), cross organic acid (peracetic acid, and the alkali metal salt of above-mentioned peracid (sodium, potassium etc.) perbenzoic acid etc.),, ammonium salt, the organic amine salt of carbon number 3～10 (Trimethylamine, triethylamine etc.).
(6) quinones: benzoquinones, naphthoquinones etc.
(7) other oxidants: sulfur trioxide, nitrogen dioxide, ozone etc.
More satisfactory in these oxidants is to transform slaine, Bronsted acid and its esters, and more better is that sulfonic acid transforms slaine, iron chloride, hydrochloric acid, sulfuric acid, optimal oxidant are the aliphatic sulfonic iron of carbon number 1～30, the aromatic sulphonic acid iron of carbon number 7～30, iron chloride, sulfuric acid.
In addition, (a-2) can use a kind also can use more than 2 kinds.
(A) or formation method (A-1), be according to cited method in following (I)～(III), in (a-1), add comparatively ideal (a-2) and react:
(I) liquid chemical polymerization reaction method:
When carrying out this polymerization reaction, at first capacitor core is immersed in the solution that contains (a-1), make it carry out oxidative polymerization.It is relatively good to add oxidant (a-2) in this polymerization process.Also can in this reaction, add solvent in order to adjust solution viscosity and concentration.The polymerization solvent that uses in this polymerization reaction is generally the relatively good of called optical imaging, for example: water, absolute alcohol (methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc.), ethylene glycol (ethylene glycol, divinyl ethylene glycol, trietbhlene glycol, three propyleneglycoles etc.), absolute ether (Propylene Glycol ether, ethohexadiol ether, methyl carbitol, ethyl carbitol, butyl carbitol, the trietbhlene glycol monomethyl ether, trietbhlene glycol monobutyl ether, propyleneglycoles monomethyl ether, propyleneglycoles list propyl ether, two propyleneglycoles monomethyl ethers, tetrahydrofuran etc.), diethyl ether (ethylene glycol dimethyl ether, the ethylene glycol diethyl ether, diethylene glycol (DEG) ethyl methyl ether, diglyceride, trichlorine cycloalkane, tetrem allyl diglycol dimethyl ether, 1,3-two chalk alkane etc.), nitrile (acetonitrile, benzene nitrile etc.), ketone (acetone, methyl ethyl ketone etc.), acid amides (dimethyl formamide, dimethylacetylamide etc.), carbonic ester (vinyl carbonate, propylene carbonate etc.), ester (ethyl acetate, diethyl maleate etc.), lactone (gamma-butyrolacton, δ-valerolactam ester etc.), sulfur-bearing iodine solution (dimethyl sulfoxide (DMSO) amine, sulfonyl lanthanum etc.), halogenated alkane (chloroform, carrene etc.), alkane (hexane, toluene etc.).Here relatively more commonly used is water, absolute alcohol, absolute ether.These solvents also can use more than 2 kinds usually.
The comparatively ideal molar concentration of monomer in the described mixed solution (a-1) is 0.01～10mol/l (mol), optimal proportion is 0.05～5mol/l, the optimum range of oxidant (a-2) is that 0.0001～10mol/l is more satisfactory, and optimum range is 0.001～5mol/l.The optimum range of viscosity (temperature 25 ℃ time) is 0.1～10,000mPas, and the optimum viscosity scope is 0.1～500mPas.
Polymeric reaction condition is relatively good under the condition that everybody knows usually, and suitable temperature range is between-100 ℃～200 ℃, and the reaction time is between 1 minute～48 hours.Optimum reaction condition is 0 ℃～150 ℃ of temperature ranges, 1～60 minute reaction time.This polymerization reaction is carried out on capacitor core by the combinations thereof mode, also can carry out repeatedly polymerization reaction repeatedly.
(II) gaseous chemical polymerization reaction method
This kind reactive mode is actually the oxidative polymerization in (I) is carried out in gaseous state, in advance capacitor core is immersed in the solution that contains (a-2), and the capacitor core that will soak is placed on and carries out oxidative polymerization in the gas that contains (a-1) then.
(a-1), (a-2) with solvent etc. can use with (I) in cited identical material, preferably use and (I) listed identical material.The more satisfactory molar concentration of described oxidizing agent solution (a-2) is 0.0001～10mol/l, and the optium concentration ratio is 0.001～5mol/l.
Polymeric reaction condition is relatively good under the condition that everybody knows usually, and the preference temperature scope is between-60 ℃～200 ℃, and the reaction time is between 1 minute～48 hours.Optimum reaction condition is, temperature range-15 ℃～25 ℃, 1～60 minute reaction time.This polymerization reaction is carried out on capacitor core by the combinations thereof mode, can carry out repeatedly polymerization reaction repeatedly.
(III) electrolysis polymerization reaction method
This kind polymerization reaction is, with (a-1) and capacitor core be immersed in the solution that contains (a-2) that (a-1) is complementary in, make it energising simultaneously and carry out polymerization reaction.(I) and polymerization (II) be chemical oxidising polymerisation reaction, (III) be the electrolysis polymerization reaction.
(a-1), (a-2) can use and above-mentioned (I), (II) cited identical material with solvent, desirable material (a-1) is the material identical with (I).(a-2) desirable material is Bronsted acid and its esters, peracid and its esters, and optimisation substance is the aromatic azochlorosulfonate acid sodium of carbon number 7～30, the aromatic sulphonic acid ammonium of carbon number 7～30, ammonium perchlorate.
The concentration of monomer in the described solution (a-1) is between 0.01～10mol/l, and suitable concentration range is 0.05～5mol/l.The optimum range of oxidant (a-2) is 0.00001～10mol/l, and optimum concentration range is 0.0001～5mol/l.The condition that polymeric reaction condition uses usually everybody to know is relatively good, and the preference temperature scope is between-100 ℃～200 ℃, and the energising reaction time is 1 minute～48 hours, and the reaction optimum temperature range is 10 ℃～100 ℃, and the reaction time is 1～60 minute.
This polymerization reaction is carried out on capacitor core by the combinations thereof mode, preferably uses and decides potentiometry or decide current method, utilizes the Current Decomposition effect to make and forms a polymer layer on the capacitor core.The ideal potential scope of deciding potentiometry is 0.1～5VvsSCE (saturated calomel electrode), and the ideal current density of deciding current method is 0.01～100mA/cm
2But polymerization reaction with this understanding also repeated multiple times is carried out.
The polymer (A-1) that obtains and capacitor core carry out after the polymerization reaction attached on the capacitor core from (I)～(III) reaction, and in fact polymerization reaction is an introduction of substances rather than remove material on capacitor element.
The polymer of polymerization formation is conjugated double bond polymer (A-1) in this way, also can sneak into additive (A-2) again in this polymer.Mix (perhaps mixing up) can cause (A-1) with (A-2) between electric charge move, thereby make the conductivity rising of (A-1).Additive is to provide the conductivity electronics to (A-1), that is to say that it is the reagent with electron donability.Both contained in the oxidant (a-2) and have electronics and be subjected to the composition of capacitive also to contain the composition with electron donability, it plays the effect of additive when carrying out polymerization reaction, therefore in above-mentioned polymerization reaction method, also has to mix in polymerization and adds.For example, when using oxidant to generate to transform slaine, accept electronics its oxidizability is reduced thereby transform the metal monomer, equilibrium ion then provides electric conductivity to the polymer with electron donability.
As (A-2) the concrete material that uses, as following cited:
(1) Bronsted acid:
Inorganic proton acid: hydrochloric acid, sulfuric acid, nitric acid, fluorosulfuric acid, sulfuric chlorohydrin, phosphoric acid, hydrofluoric acid, phosphorus is fluoridized hydracid etc.;
Molecular weight is lower than 1,000 low molecular organic acids: tropolones (phenol, naphthols etc.), the aliphatic carboxylic acid of carbon number 1～30 (acetic acid, Bronsted acid etc.), aromatic carboxylic acid (the benzoic acid of carbon number 7～30, phthalic acid etc.), the aliphatic sulfonic of carbon number 1～30 (methanesulfonic acid, propane sulfonic acid etc.), the aromatic sulphonic acid of carbon number 7～30 (benzene sulfonic acid, p-toluenesulfonic acid etc.);
Weight average molecular weight 1,000～1,000,000 polymeric organic acid (polystyrolsulfon acid, polyvinyl sulfonic acid etc.).
(2) halogen and halide thereof: bromine, iodine, IBr, arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminium chloride, aluminium bromide, iron chloride, copper chloride etc.
More satisfactory in these materials is Bronsted acid, more better is hydrochloric acid, sulfuric acid, the aliphatic carboxylic acid of carbon number 1～30, the aromatic carboxylic acid of carbon number 7～30, the fats sulfonic acid of carbon number 1～30, the aromatic sulphonic acid of carbon number 7～30, wherein best is the fats carboxylic acid of carbon number 1～30, the aromatic carboxylic acid of carbon number 7～30, the fats sulfonic acid of carbon number 1～30, the aromatic sulphonic acid of carbon number 7～30.
In addition, the additive among the present invention (A-2) can use a kind also can use more than 2 kinds.
In case after adding (A-2) and forming (A-1), just can react according to common chemical method or electron chemistry method that everybody knows, as preceding note, optimal method is to use oxidant, i.e. additive package in the time of polymerization when carrying out polymerization reaction.Gaseous state or liquid state (A-2) are mixed mutually with (A-1) reacts, in the electrolytics reaction method, (A-1) is immersed in the solution that is dissolved with (A-2), with (A-1) as electrifying electrodes, carry out the electrolytics reaction and mix stirring, on capacitor core, form (A).The forming process of Here it is electroconductive polymer (A), its perfect conductivity scope is 10
-5～10
5S/cm, best conduction scope is 10
-2～10
5Between the S/cm.
By the invention describes, organic acid network and salt (B) are formed by network and cation and organic anion reaction.That is to say that (B) is network and cationic acylate, concrete molecular structure is that network and cation are from 4 grades of ammoniums, 3 grades of sulfones, 4 grades of phosphorus are selected cation more than a kind or 2 kinds in the cation group of 3 grades of water and hydrogen, organic anion is from carboxylic acid, sulfonic acid, tropolones monomer or dialkyl phosphate are in the organic acids such as boron fluor-complex, remove the anion of selecting in the anion group of deprotonation more than a kind, form organic acid network and salt jointly.
The instantiation that contains (B) of complex cation is listed below:
(I) about 4 grades of ammonium cations, as cited in following (I-1)～(I-10):
(I-1) carbon number 4～30 or more than, contain 4 grades of ammoniums of fatty family of alkyl and/or alkynyl:
Tetramethyl-ammonium, ethyl trimethylammonium, diethyl dimethylammonium, triethyl group first ammonium, trimethyl second ammonium, tetraethyl ammonium, trimethyl third ammonium, dimethyl dipropyl ammonium, ethyl dipropyl ammonium, butyl trimethylammonium, dimethyl two fourth ammoniums, TBuA, tetrahexyl ammonium, trimethyl ammonium in the last of the ten Heavenly stems etc.
(I-2) 4 grades of ammoniums of carbon number 6～30 or above aromatic series:
The trimethyl puratized agricultural spray, dimethyl ethyl puratized agricultural spray, triethyl group puratized agricultural spray etc.
(I-3) carbon number 3～30 or more than, 4 grades of ammoniums of ring type fats:
N, N-dimethyl dinitro benzene, N-ethyl-N-methylpyrimidine, N, N-diethyl pyrroles, N, N-thebaine, N-ethyl-N-methylmorpholine, N, N-diethyl morpholine, N, N-lupetazin, N, N-diethyl piperazine etc.
(1-4) carbon number 3～30 or above imidazoline:
1,2,3-tri-methylimidazolium quinoline; 1; 2,3,4-tetramethyl imidazoline; 1; 3,4-trimethyl-2-ethyl imidazol(e) quinoline; 1,3-dimethyl-2; 4-diethyl imidazoline; 1,2-dimethyl-3,4-diethyl imidazoline; 1; 2-dimethyl-3-ethyl imidazol(e) quinoline; 1,2,3; 4-tetraethyl imidazoline; 1,2,3-triethyl group imidazoline; 4-cyano group-1; 2,3-tri-methylimidazolium quinoline; 2-cyanogen methyl isophthalic acid, 3-methylimidazole quinoline; 4-acetyl group-1; 2,3-tri-methylimidazolium quinoline; 3-acetonyl-1,2-methylimidazole quinoline; 4-methyl methoxy carboxyl-1; 2,3-tri-methylimidazolium quinoline; 3-methoxyl methyl-1,2-methylimidazole quinoline; 4-formoxyl-1; 2; 3-tri-methylimidazolium quinoline; 3-formyl methyl isophthalic acid, 2-methylimidazole quinoline; 3-ethoxy-1,2-methylimidazole quinoline; 4-methylol-1; 2,3-tri-methylimidazolium quinoline etc.
(I-5) carbon number 3～30 or above imidazoles:
1, the 3-methylimidazole; 1-ethyl-3-methylimidazole; 1-methyl-3-ethyl imidazol(e); 1,2; the 3-tri-methylimidazolium; 1,3-dimethyl-2-ethyl imidazol(e); 1,2-dimethyl-3-ethyl imidazol(e); 1; 2,3-triethyl group imidazoles; 1,2; 3,4-tetraethyl imidazoles; 1,3-dimethyl-2-phenylimidazole; 1; 3-dimethyl-2-benzyl imidazole; 1-benzyl-2; the 3-methylimidazole; 4-cyano group-1,2, the 3-tri-methylimidazolium; 3-cyanogen methyl isophthalic acid; the 2-methylimidazole; 4-acetyl group-1; 2, the 3-tri-methylimidazolium; 3-acetonyl-1, the 2-methylimidazole; 4-methyl methoxy carboxyl-1; 2; the 3-tri-methylimidazolium; 3-methyl methoxy carboxyl-1, the 2-methylimidazole; 4-methoxyl group-1,2; the 3-tri-methylimidazolium; 4-formoxyl-1; 2, the 3-tri-methylimidazolium; 3-formyl methyl isophthalic acid, the 2-methylimidazole; 3-ethoxy-1; the 2-methylimidazole; 2-ethoxy-1; the 3-methylimidazole; N, N '-dimethyl benzene imidazoles; N, N '-diethylbenzene imidazoles; N-methyl-N '-ethylo benzene imidazoles etc.
(I-6) carbon number 4～30 or above tetrahydro pyrimidine:
1,3-dimethyl tetrahydro pyrimidine; 1,2; 3-trimethyl tetrahydro pyrimidine; 1,2,3; 4-tetramethyl tetrahydro pyrimidine; the 8-methyl isophthalic acid, the different amine [5,4 of 8-diazonium; 0]-the 7-endecatylene; the 5-methyl isophthalic acid; the different amine of 5-diazonium [4,3,0]-5-nonane; 4-cyano group-1; 2; 3-trimethyl tetrahydro pyrimidine; 3-cyanogen methyl isophthalic acid, 2-dimethyl tetrahydro pyrimidine; 4-acetyl group-1,2; 3-trimethyl tetrahydro pyrimidine; 3-acetonyl-1; 2-dimethyl tetrahydro pyrimidine; 4-methyl methoxy carboxyl-1,2,3-trimethyl tetrahydro pyrimidine; 4-methoxyl group-1; 2; 3-trimethyl tetrahydro pyrimidine; 3-methoxyl methyl-1,2-dimethyl tetrahydro pyrimidine; 4-methylol-1,2; 3-trimethyl tetrahydro pyrimidine; 2-ethoxy-1,3-dimethyl tetrahydro pyrimidine etc.
(I-7) carbon number 4～30 or above dihydro-pyrimidin:
1,3-dimethyl-2,4-or-2, the 6-dihydro-pyrimidin is [at this with 1; 3-dimethyl-2,4 (6)-dihydro-pyrimidin represents that following method for expressing is identical]; 1; 2,3-trimethyl-2,4 (6)-dihydro-pyrimidin; 1; 2,3,4-tetramethyl-2; 4 (6) dihydro-pyrimidins; 1,2,3; 5-tetramethyl-2,4 (6)-dihydro-pyrimidin; the 8-methyl isophthalic acid, the different amine [5 of 8-diazonium; 4,0] (10)-endecatylene-7,9; the 5-methyl isophthalic acid; the different amine of 5-diazonium [4,3,0]-5; 7 (8)-nonanes; 2-cyanogen methyl isophthalic acid, 3-dimethyl-2,4 (6)-dihydro-pyrimidin; 3-acetonyl-1; 2-dimethyl-2,4 (6)-dihydro-pyrimidin; 4-methyl methoxy carboxyl-1,2; 3-trimethyl-2,4 (6)-dihydro-pyrimidin; 4-methoxyl group-1,2; 3-trimethyl-2,4 (6)-dihydro-pyrimidin; 4-formoxyl-1,2; 3-trimethyl-2,4 (6)-dihydro-pyrimidin; 3-ethoxy-1,2-dimethyl-2; 4 (6)-dihydro-pyrimidins; 2-ethoxy-1,3-dimethyl-2,4 (6)-dihydro-pyrimidin etc.
(I-8) carbon number 3～30 or more than contain the guanidine of imidazoline structure:
2-dimethylamino-1; 3; 4-tri-methylimidazolium quinoline; the 2-diethyl is for amino-1; 3; 4-tri-methylimidazolium quinoline; the 2-diethyl is for amino-1; 3-dimethyl-4-ethyl imidazol(e) quinoline; 2-dimethylamino-1-methyl-3; 4-diethyl imidazoline; the 2-diethyl is for amino-1; 3; 4-tetraethyl imidazoline; 2-dimethylamino-1; 3-methylimidazole quinoline; the 2-diethyl is for amino-1; 3-methylimidazole quinoline; the 2-diethyl is for amido-1; 3-diethyl imidazoline; 1; 5; 6; 7-tetraethyl-1; 2-dimethyl-2H-imines [1; 2a] imidazoline; 1; 5; 6; 7-tetrahydrochysene base-1; 2-dimethyl-2H-metadiazine [1,2a] imidazoline; 1,5-dihydro base-1; 2-dimethyl-2H-metadiazine [1; 2a] imidazoline; 2-dimethylamino-3-cyanogen methyl isophthalic acid-methylimidazole quinoline; 2-dimethylamino-4-acetyl group-1,3-methylimidazole quinoline; 2-dimethylamino-4-methyl methoxy carboxyl-1,3-methylimidazole quinoline; 2-dimethylamino-3-methyl methoxy carboxyl-1-methylimidazole quinoline; 2-dimethylamino-3-methoxyl methyl-1-methylimidazole quinoline; 2-dimethylamino-4-formoxyl-1; 3-methylimidazole quinoline; the 2-diformazan is for amido-3-ethoxy-1-methylimidazole quinoline; 2-dimethylamino-4-methylol-1,3-methylimidazole quinoline etc.
(I-9) carbon number 3～30 or the above guanidine that contains glyoxaline structure:
2-dimethylamino-1; 3; the 4-tri-methylimidazolium; the 2-diethyl is for amino-1; 3; the 4-tri-methylimidazolium; the 2-diethyl is for amino-1; 3-dimethyl-4-ethyl imidazol(e); the 2-diethyl is for amino-1-methyl-3; 4-diethyl imidazoles; the 2-diethyl is for amino-1; 3; 4-tetraethyl imidazoles; 2-dimethylamino-1; the 3-methylimidazole; 2-dimethylamino-1-ethyl-3-methylimidazole; the 2-diethyl is for amino-1; 3-diethyl imidazoles; 1; 5; 6; 7-tetrahydrochysene base-1,2-dimethyl-2H-sulfilimine [1,2a] imidazoles; 1; 5; 6,7-tetrahydrochysene base-1,2-dimethyl-2H-pyrimidine [1; 2a] imidazoles; 1; 5-dihydro base-1,2-dimethyl-2H-metadiazine [1,2a] imidazoles; 2-dimethylamino-3-cyanogen methyl isophthalic acid-methylimidazole; 2-dimethylamino-4-acetyl group-1; the 3-methylimidazole; 2-dimethylamino-4-methyl methoxy carboxyl-1; the 3-methylimidazole; 2-dimethylamino-4-methoxyl group-1, the 3-methylimidazole; 2-dimethylamino-3-methoxyl methyl-1-methylimidazole; 2-dimethylamino-3-formyl methyl isophthalic acid-methylimidazole; 2-dimethylamino-4-methylol-1,3-methylimidazole etc.
(I-10) carbon number 4～30 or the above guanidine that contains the tetrahydro pyrimidine:
2-dimethylamino-1; 3; 4-trimethyl tetrahydro pyrimidine; the 2-diethyl is for amino-1; 3; 4-trimethyl tetrahydro pyrimidine; the 2-diethyl is for amino-1; 3-dimethyl-4-ethyl tetrahydro pyrimidine; the 2-diethyl is for amino-1-methyl-3; 4-diethyl tetrahydro pyrimidine; 2-dimethylamino-1; 3-dimethyl tetrahydro pyrimidine; the 2-diethyl is for amino-1; 3-dimethyl tetrahydro pyrimidine; the 2-diethyl is for amino-1; 3-diethyl tetrahydro pyrimidine; 1; 3; 4; 6; 7; 8-own hydroxyl-1; 2-dimethyl-2H-sulfilimine [1; 2a] pyrimidine; 1,3,4; 6; 7,8-own hydroxyl-1,2-dimethyl-2H-pyrimidine [1; 2a] pyrimidine; 2; 3,4,6-tetrahydroxy-1; 2-dimethyl-2H-pyrimidine [1; 2a] pyrimidine; 2-dimethylamino-3-cyanogen methyl isophthalic acid-methyltetrahydro pyrimidine; 2-dimethylamino-4-acetyl-1,3-dimethyl tetrahydro pyrimidine; 2-dimethylamino-4-methyl methoxy carboxyl-1,3-dimethyl tetrahydro pyrimidine; 2-dimethylamino-3-methyl methoxy carboxyl-1-methyltetrahydro pyrimidine; 2-dimethylamino-3-methoxyl methyl-1-methyltetrahydro pyrimidine; 2-dimethylamino-4-formoxyl-1; 3-dimethyl tetrahydro pyrimidine; 2-dimethylamino-3-ethoxy-1-methyltetrahydro pyrimidine; 2-dimethylamino-4-methylol-1,3-dimethyl tetrahydro pyrimidine etc.
(I-11) carbon number 4～30 or more than, contain the guanidine of dihydroxy pyrimidine structure:
2-dimethylamino-1; 3; 4-trimethyl-2; 4 (6)-dihydroxy pyrimidines; the 2-diethyl is for amino-1; 3; 4-trimethyl-2; 4 (6)-dihydroxy pyrimidines; 2-dimethylamino-1-methyl-3; 4-diethyl-2; 4 (6)-dihydroxy pyrimidines; the 2-diethyl is for amino-1-methyl-3; 4-diethyl-2; 4 (6)-dihydroxy pyrimidines; the 2-diethyl is for amino-1; 3; 4-tetraethyl-2; 4 (6)-dihydroxy pyrimidines; the 2-diethyl is for amino-1; 3-dimethyl-2,4 (6)-dihydroxy pyrimidine; 2-dimethylamino-1-ethyl-3-methyl-2,4 (6)-dihydroxy pyrimidine; 1; 6; 7,8-tetrahydroxy-1,2-dimethyl-2H-sulfilimine [1; 2a] pyrimidine; 1; 6-dihydroxy-1,2-dimethyl-2H-sulfilimine [1,2a] pyrimidine; 1; 6-dihydroxy-1; 2-dimethyl-2H-sulfilimine [1,2a] pyrimidine; 2-dimethylamino-4-cyano group-1,3-dimethyl-2; 4 (6) dihydroxy pyrimidines; 2-dimethylamino-4-acetyl group-1; 3-dimethyl-2,4 (6) dihydroxy pyrimidines; 2-dimethylamino-3-acetonyl-1-methyl-2,4 (6) dihydroxy pyrimidines; 2-dimethylamino-3-methyl methoxy carboxyl-1-methyl-2; 4 (6) dihydroxy pyrimidines; 2-dimethylamino-4-methoxyl group-1; 3-dimethyl-2,4 (6) dihydroxy pyrimidines; 2-dimethylamino-4-formoxyl-1,3-dimethyl dihydroxy pyrimidine; 2-dimethylamino-3-formyl methyl isophthalic acid-methyl dihydroxy pyrimidine; 2-dimethylamino-4-methylol-1; 3-dimethyl-2,4 (6)-dihydroxy pyrimidine etc.
(II) contain 3 grades of cationic materials of sulfanilamide (SN), cited in the row specific as follows (II-1)～(II-3):
(II-1) carbon number 1～30 or more than, contain 3 grades of sulfanilamide (SN) of fatty family of alkyl and/or alkynyl:
Trimethyl sulfanilamide (SN), triethyl group sulfanilamide (SN), ethyl dimethyl sulfanilamide (SN), diethylmethyl sulfanilamide (SN) etc.
(II-2) carbon number 6～30 or above 3 grades of sulfanilamide (SN) of aromatic series:
Xyxylene sulfanilamide (SN), phenethyl first sulfanilamide (SN), benzyl benzylsulfamide etc.
(II-3) carbon number 3～30 or above 3 grades of sulfanilamide (SN) of ring type fats:
The methyl thiamines, phenyl thiamines, methyl thiazine etc.
(III) about 4 grades of phosphorus cations, as cited in following (III-1)～(III-3):
(III-1) carbon number 1～30 or more than, contain 4 grades of phosphorus of fatty family of alkyl and/or alkynyl:
Tetramethyl phosphorus, tetraethyl phosphorus, tetrapropyl phosphorus, tetrabutyl phosphorus, methyl triethyl phosphine, methyl tripropyl phosphorus, methyl tributyl phosphorus, dimethyl diethyl phosphorus, trimethyl ethyl phosphorus, trimethyl propyl group phosphorus, ethyl tripropyl phosphorus, ethyl tributyl phosphorus, diethyl tributyl phosphorus, triethyl group tributyl phosphorus, propyl group tributyl phosphorus, dipropyl dibutyl phosphorus, tripropyl tributyl phosphorus etc.
(III-2) carbon number 6～30 or more than, 4 grades of phosphorus of aromatic series:
Trimethylbenzene methyl phosphorus, dimethylbenzene dimethyl phosphorus, trimethylbenzene benzyl phosphorus etc.
(III-3) carbon number 3～30 or more than, 4 grades of phosphorus of ring type fats:
1,1-solutions of dimethyl phosphoryl amine, 1-methyl isophthalic acid-ethyl phosphamide, 1,1-diethyl phosphamide, 1,1-dimethyl phosphoric acid acetamide, 1-methyl isophthalic acid-ethyl phosphonic acid acetamide, 1,1-diethyl phosphoric acid acetamide, 1,1-pentamethylene base phosphoric acid acetamide etc.
(IV) for 3 grades of hydronium(ion) cations, as cited in following (IV-1)～(IV-3):
(IV-1) carbon number 1～30 or more than, contain 3 grades of oxygen drone ions of fats of alkyl and/or alkynyl:
Trimethyl oxygen drone, triethyl group oxygen drone, the ethyl dimethyl oxygen drone, diethylmethyl oxygen drone etc.
(IV-2) carbon number 6～30 or more than, 3 grades of oxygen drone ions of fragrant family:
Xyxylene oxygen drone, phenethyl methyl oxygen drone, benzyl benzyl oxygen drone etc.
(IV-3) carbon number 3～30 or more than, 3 grades of oxygen drone ions of ring type fats:
The first oxyquinoline, benzene oxyquinoline, tolyl chalk piperazine ketone etc.
Comparatively ideal in these ions is 4 grades of ammonium cations, and more better is carbon number 4～30 or above fats ammonium, carbon number 3～30 or above imidazoline, carbon number 3～30 or above imidazoles it would be desirable the trimethyl ethyl ammonium, the dimethyl diethyl ammonium, the triethyl group ammonium methyl, 1,2,3,4-tetramethyl imidazoline, 1,2-dimethyl-3-ethyl imidazol(e) quinoline, 1-ethyl-3-methylimidazole, 1-methyl-3-ethyl imidazol(e).These complex cations can use a kind also can use more than 2 kinds.
Provide anionic organic acid with described (B) is corresponding, instantiation is listed below:
What (I) following (I-1)～(I-4) was cited is carboxylic acid:
(I-1) carbon number 1～30 or above saturated and unsaturated fat class carboxylic acid:
(I-1-1) the fats carboxylic acid of 1 valency: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, capric acid, di-n-octyl formic acid, laurate, myristic acid, hard ester acid, saturated carboxylic acids such as Yu Shu acid, acrylic acid, methacrylate, unsaturated carboxylic acids such as oleic acid etc.
(I-1-2) the above fats carboxylic acid of divalent:
The sweet acid of nitre, malonic acid, butanedioic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, 1,10-decyl dicarboxylic acids, 1,12-decyl dicarboxylic acids, positive ten acid, 1, straight chain saturated carboxylic acids such as the positive pentane dicarboxylic acid of 15-, methylmalonic acid, ethyl malonic acid, the butyl propionic acid, 3-methyl adipic acid, 1,6-decyl dicarboxylic acids, diethyl malonic acid, 2,2-or 2,3-dimethyl succinate, 2-ethyl-3-methylsuccinic acid, 2,2-or 2,3-or 2,4-or 3,3-dimethylated pentanedioic acid, 3-ethyl-3 methylvaleric acid, 2-butyl octane diacid, 5, branch chain saturated carboxylic acids such as 6-decane dicarboxylic acid, the acid of formyl triamido, 1,6,11-or 1,10,11-or 5,6, the positive penta decyl tricarboxylic acids of 11-, 1,2,34-butane group tetrabasic carboxylic acid, maleic acid (maleic acid), fumaric acid, unsaturated dicarboxylics such as paddy ancient unit of weight, equal to one fourth of a liang acid etc.
(I-1-3) hydroxy aliphatic class carboxylic acid: two alkyd, lactic acid, tartaric acid etc.
(I-1-4) fats thiocarboxylic acid: sulfo-two propionitrile acid etc.
(I-2) carbon number 7～30 or above aromatic carboxylic acid:
(I-2-1) 1 valency aromatic carboxylic acid: benzoic acid, the acid of cassia tree skin, naphthoic acid etc.
(I-2-2) the above aromatic carboxylic acid of divalent: phthalic acid, terephthalic acid (TPA), phthalic acid connects phthalic acid etc. partially.
(I-2-3) aromatic hydroxyl carboxylic acid: salicylic acid, mandelic acid etc.
(I-3) carbon number 3～30 or above ring type fats carboxylic acid:
Cyclobutane base-1,2-dicarboxylic acids, cyclopentanol base-1,2-dicarboxylic acids, 1,2-or 1,4-cyclohexyl dicarboxylic acids, 2-or 3-methyl isophthalic acid, 4-cyclohexane dicarboxylic acid, furyl-2,3-dicarboxylic acids, two rings [2,2,1] heptenyl-2-alkene-2,3-dicarboxylic acids, two rings [2,2,1] heptenyl-2,5-alkadienes-2,3-dicarboxylic acids etc.
(I-4) contain the homopolymers and the copolymer of carboxylic formyl:
Homopolymers (partially) acrylic acid that contains the carboxylic formyl, the acid of cassia tree skin, vinylbenzoic acid etc., and the carboxylic acid that contains the carbon number 3～30 of polymerisable double bond has been enumerated out.Polymerizing condition is advisable with the common method that everybody knows, and the optimum range of the degree of polymerization is: 16～10,000, and optimum range is between 20～1000.
Optimal acid is in the above-mentioned carboxylic acid: adipic acid, 1,6-decyl dicarboxylic acids, phthalic acid, benzoic acid.
(II), cited in (II-1)～(II-3) specific as follows about sulfonic acid:
(II-1) carbon number 1～30 or above saturated and unsaturated fat class sulfonic acid:
(II-1-1) 1 valency fats sulfonic acid:
Methanesulfonic acid, ethyl sulfonic acid, propane sulfonic acid, different propane sulfonic acid, fourth sulfonic acid, isobutyl sulfonic acid, t-fourth sulfonic acid, penta sulfonic acid, isoamyl sulfonic acid, own sulfonic acid, the ninth of the ten Heavenly Stems sulfonic acid, the last of the ten Heavenly stems sulfonic acid, 11 charcoal sulfonic acid, 12 charcoal sulfonic acid, three the last of the ten Heavenly stems sulfonic acid, four the last of the ten Heavenly stems unsaturated sulfonic acid such as sulfonic acid, hot sulfonic acid, bay sulfonic acid, 16 charcoal sulfonic acid, vinyl sulfonic acid, 1-propylene-1-sulfonic acid, benzylalcohol sulfonic acid, benzene ethyl sulfonic acid etc.
(II-1-2) the above fats sulfonic acid of divalent:
Methane-disulfonic acid, 1,1-ethionic acid, 1,2-ethionic acid, 1,1-propane sulfonic acid, 1,3-N-morpholinopropanesulfonic acid, polyvinyl sulfonic acid etc.
(II-1-3) hydroxy aliphatic class sulfonic acid:
Isohexadecane acid, 3-hydroxyl-propane sulfonic acid etc.
(II-1-4) thio group fats carboxylic acid:
Thioacetic acid, sulfo-butanedioic acid etc.
(II-2) carbon number 6～30 or above aromatic sulphonic acid:
(II-2-1) 1 valency monocyclic aromatic sulphonic acid:
Benzene sulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, o-dimethylbenzene-4-sulfonic acid, m-dimethylbenzene-4-sulfonic acid, 4-bay benzene sulfonic acid, 4-octane benzene sulfonic acid, 2-methyl-5-cumene sulfonic acid etc.
(II-2-2) 1 valency polycycle aromatic sulphonic acid:
Naphthalene sulfonic acids, three different third naphthalene sulfonic acids, etc. alkyl naphthalene sulfonic acid, rylnthracene sulfonin, luxuriant and rich with fragrance sulfonic acid etc.
(II-2-3) the above aromatic sulphonic acid of divalent:
M-benzenedisulfonic acid, 1,4-naphthalene sulfonic acids, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, sulfonated polystyrene etc.
(II-2-4) aromatic hydroxyl sulfonic acid:
Carbolic acid base-2-sulfonic acid, carbolic acid base-3-sulfonic acid, carbolic acid base-4-sulfonic acid, isomery-o-sulfonic acid, isomery-m-sulfonic acid, carbolic acid base-o-sulfonic acid, phenoxy group-m-sulfonic acid, carbolic acid base-2, the 4-disulfonic acid, carbolic acid base-2,4, the 6-trisulfonic acid, isomery-2, the 4-disulfonic acid, phenoxy group-2, the 5-disulfonic acid, 2-hydroxyl triolefin alkyl-4-sulfonic acid, catechol base-4-sulfonic acid, ortho-xylene base-4-sulfonic acid, resorcinol group-4-sulfonic acid, 2-hydroxyl-1-anisyl-4-sulfonic acid, 1,2-dihydroxy phenyl-3, the 5-disulfonic acid, resorcinol group-4, the 6-disulfonic acid, hydroquinone sulfonic acid, quinhydrones base-2, the 5-disulfonic acid, 1,2,3-trihydroxy phenyl-4-sulfonic acid etc.
(II-2-5) aromatic hydroxyl sulfonic acid:
O-sulfo-benzoic acid, m-sulfo-benzoic acid, p-sulfo-benzoic acid, 2,4-two sulfo-benzoic acids, 3-sulfo-phthalic acid, 3,5-two sulfo-phthalic acids, the different phthalic acid of 4-sulfo-, 2-sulfo-terephthalic acid (TPA), 2-methyl-4-sulfo-benzoic acid, 2-methyl-3,5-two sulfo-benzoic acids, 4-propyl group-3-sulfo-benzoic acid, 2,4,6-trimethyl-3-sulfo-benzoic acid, 2-methyl-5-sulfo-terephthalic acid (TPA), 5-thiosalicylic acid, 3-hydroxyl-4-sulfo-benzoic acid etc.
(II-2-6) aromatic hydroxyl sulfonic acid:
Sulfo-carbolic acid base sulfonic acid, sulfo-isomery-4-sulfonic acid, sulfo-phenoxy group-4-sulfonic acid etc.
(II-2-7) have the aromatic sulphonic acid of other functional groups:
Benzoyl group-o-sulfonic acid, benzoyl group-2; 4-disulfonic acid, acetyl phenyl-o-sulfonic acid, acetyl phenyl-2; 4-disulfonic acid, benzophenone phenolic group-o-sulfonic acid, benzophenone phenolic group-3; 3 '-disulfonic acid, 4-aminobenzene phenolic group-3-sulfonic acid, anthraquinonyl-1-sulfonic acid, anthraquinonyl-1; 5-disulfonic acid, anthraquinonyl-1; 8-disulfonic acid, anthraquinonyl-2,6-disulfonic acid, 2-methylanthraquinone base-1-sulfonic acid etc.
(II-3) carbon number 3～30 or above ring type fats carboxylic acid:
Pentamethylene base sulfonic acid, cyclohexyl sulfonic acid etc.
In above-mentioned sulfonic acid, more satisfactory acid is p-toluenesulfonic acid, triisopropyl naphthalene sulfonic acids, naphthalene sulfonic acids, phenylol-4-sulfonic acid.
(III) cited in (III-1) below is phenol.
(III-1) carbon number 6～30 or above displacement or non-displacement phenol:
(III-1-1) 1 bivalent phenol:
Phenol, naphthols, cyclohexylphenol, cresols, xylenols, ethyl-phenol, n and isopropyl-phenol, n and isoamyl alkylphenol, isononane base phenol, different lauryl phenol, eugenol, adjacent phenoxy phenyl etc.
(III-1-2) the above phenol of divalent:
Catechol, resorcinol, 1,2,3,-thrihydroxy-benzene and fluorine asccharin etc.
(IV), cited in following (IV-1)～(IV-2) about the instantiation of monomer alkyl phosphate:
(IV-1) carbon number 1～30 or above monomer alkyl phosphate:
Methyl phosphorodithioate, isopropyl phosphoric acid ester, butyl phosphoric acid ester, 2-ethyl hexane base phosphate, isodecyl alkyl phosphate etc.
(IV-2) carbon number 2～30 or above dialkyl phosphate:
Dimethyl phosphate, diisopropyl phosphate, O-phthalic acidic group phosphate, (2-ethyl hexane base) bisphosphate, diethyl decene base phosphate etc.
(V), cited in following (V-1)～(V-2) about the instantiation of complexing boron:
(V-1) contain the ethanol hydroxy complex compound of boron:
Boric acid ethylene glycol complex compound, boric acid cyclopropane two alcohol complexs etc.
(V-2) the phosphoric acid complex compound of boric acid and/or phosphate complex compound:
Boric acid methyl acid phosphate fat complex compound, boric acid ethyl phosphonic acid fat complex compound.
Detailed description about boric acid complex can be referring to described content in No. 2966451 communiques of patent.
In these materials, more satisfactory is carboxylic acid, sulfonic acid, and even more ideal is carboxylic acid, aromatic sulphonic acid, optimal selection is carboxylic acid, polycycle aromatic sulphonic acid.These organic anions use can more than a kind or 2 kinds.
The manufacture method of being somebody's turn to do (B) is not particularly limited, and such as when making the acylate of 4 grades of ammoniums, after the 3rd level ammonium utilized alkylating agent (alkyl halide, vinic acid etc.) by 4 grades of changes, hydroxide ion reacted with organic acid at once, further generates halide ion.This manufacture method is described in detail in International Patent Publication No. WO No. 95/15572, and is all on the books in No. 2964244 communiques of patent, and concrete manufacture method can be identical therewith.
Generation about 3 grades of thiamines salt is that after thioether utilized alkylating agent (alkyl halide, vinic acid etc.) by 3 grades of changes, hydroxide ion reacted with organic acid at once, further generates halide ion.This manufacture method is described in detail in J.P.Marino, and " Topicsin Sulfur Chemistry ", vol.1,1976, on the books in p.1, manufacture method is identical therewith.
Generation about 4 grades of microcosmic salts is that after 3rd level hydrogen phosphide utilized alkylating agent (alkyl halide, vinic acid etc.) by 4 grades of changes, hydroxyl ion reacted with organic acid at once, further generates halide ion.This manufacture method is described in detail in P.Beck " Organic Phosphorus Compound ", vol.2, and 1972, Chapt.4, on the books in p.189, can use identical therewith manufacture method.
Generation about 3 grades of hydration hydrogen salts is that after ether utilized alkylating agent (alkyl halide, vinic acid etc.) by 3 grades of changes, hydroxyl ion reacted with organic acid at once, further generates halide ion.This manufacture method is described in detail in G, W.Wheland, and " Advanced Organic Chemistry " 1949, on the books in p.38, can use identical therewith manufacture method.
The complex cation among (B) that obtains in this way and the equivalent proportion of organic anion, consider from proof voltage and thermal endurance angle, equivalent proportion is usually at complex cation: more satisfactory between organic anion=1: 0.2～3, optimum range be 1: 0.5～1.5. when organic acid anion 0.2 can be high pressure resistant when above, good in 3 thermal endurances when following.
The electrolyte that electrolytic capacitor described in the present invention uses constitutes jointly by (A) with (B).Here (A) and weight ratio (B) consider that from the angle of conductivity and proof voltage proper weight ratio is (A): (B)=1: 0.1～5.The optimum weight scope is (A): (B)=1: 0.2～2.When (B) raises at 0.1 proof voltage when above, good in 5 conductivity when following.
In the present invention, after this electroconductive polymer (A) formed, the electrolytic capacitor of electrolyte utilize this organic acid complex salt (B) to soak before can using, thereby electroconductive polymer is imported in the middle of the capacitor element.When above-mentioned (A) forms, add above-mentioned (B), it can be imported in the middle of the capacitor element when carrying out polymerization.
Described in the present invention capacitor, in order to improve its sparking voltage, improve chemical synthesis, reduce leakage current, absorb methane gas, prevent that static capacity from changing, prevent short circuit, prevent corrosion, improve anti-detergency, improve characteristics such as flame retardancy, impregnation, in electrolyte, can add additive more than a kind, perhaps add with the form of its salt.Can list as additive: phosphide (phosphoric acid, phosphorous acid, ortho phosphorous acid, phosphoric acid lipid, phosphate etc.); Boron compound (boric acid, boron oxide, boric acid lipid, the complex compound that boric acid and the compound that contains hydroxy and/or carboxyl form etc.); Nitro compound (nitro benzoic acid, nitrophenol, nitro fibric acid, nitro acetophenone, aromatic nitro compound etc.); Sulfur compound (sulfonic acid class, thio-alcohol contain the multielement ring type compound of mercapto etc.); Benzoic acid dielectric (Para Hydroxy Benzoic Acid, tetrahydroxy benzoic acid, benzoic acid fat etc.); Phenol (catechol, nitro-pyrocatechol, 3 bivalent phenols etc.); Oxyacid class (two alkyd, tartaric acid, citric acid etc.); Polyoxyethylene and/or polyoxypropylene dielectric (the adjacent phenetole of polyoxyethylene groups, Emulsifier EL-60 etc.); The compounds (mannitol, hexanoyl alcohol, erythroglucin, sorbierite, poly-glycerine, carbohydrate, cellulose family, starch based etc.) that contains 2 above hydroxys; Macromolecular compound (polyvinyl alcohol class, polyalkamer base glycol, polyalkamer base two alkyd, polyacrylamide, sex change silicone oil etc.); Wolframic acid; Heteropoly acid (silico-tungstic acid, phosphotungstic acid, phosphomolybdic acid etc.); Particulate inorganic compound (silicic acid anhydride, titanium oxide, hydrotalcite etc.); Amino acid etc.The amount of additive considers that from the conductivity angle reasonable ratio is below 10% of electrolyte weight, and optimal proportion is below 5%.
Electrolyte described in the present invention can contain solvent in the scope of occurrence features deterioration not, the molten coal of solid is more satisfactory.
The moisture ratio of this electrolytical ideal is below 1%, and optimal proportion is below 0.3%, and alkali metal ion, the optimum range of corrosive ion content such as halide ion are below 10ppm, and optimum range is below the 1ppm.If water content is 1% when following, electrolytical performance can not descend, when corrosive ion content electrode when 10ppm is following can not be corroded.
Electrolyte described in the present invention uses on the electrolytic capacitor core.Be not particularly limited for above-mentioned electrolytic capacitor core, for example, metal anode foil and Cathode Foil that the valve effect has been arranged on the aluminium electrolytic capacitor of coiled-type, its anode foils surface has formed the dielectric oxide film, the electrolyte that electroconductive polymer (A) and organic anion salt (B) are formed is mediate to be used to separate anode and negative electrode, with above-mentioned capacitor core is example, after having taken in it in bottom tube-like aluminium box, the opening of aluminium box is sealed with sealing compound, so just formed an aluminium electrolytic capacitor.Such electrolytic capacitor, because utilized the high conductivity of electroconductive polymer (A), therefore the electrode resistance of current-carrying part obviously reduces, this electrolytic capacitor is when impedance operator is good like this, owing to also used organic anion salt (B) with dielectric oxide film repair ability, so it is high pressure resistant that such electrolytic capacitor also has concurrently, the characteristic of low leakage electrode stream.
Embodiment
Describe with regard to specific embodiments of the invention below, the invention is not restricted in this scope.
Embodiment 1
Between anode aluminium foil and cathode aluminum foil, between wherein also curling, just obtain a capacitor core with separator.This capacitor core is in the solution 5ml of water that contains ethene dihydroxy thiophene phenol 0.5g and p-toluenesulfonic acid iron 2.0g and ethanol (1: 2), at room temperature soaked 10 minutes, immersion is finished and take out the dry polymerization reaction that carried out 10 minutes the back under 105 ℃, and such reaction repeats 10 times.After forming the electroconductive polymer layer that constitutes by polyethylene dihydroxy thiophene phenol on the electrode foil plate, capacitor element is washed-dry-clean (105 ℃, 10 minutes).Then this capacitor core is immersed in and contains phthalic acid 1,2,3,4-tetramethyl imidazole salts 1g (phthalic acid: 1,2,3, functional group's equivalent proportion of 4-tetramethyl imidazole salts=1: 1) in the solution, so just obtains a rated voltage 50V, the aluminium electrolytic capacitor core of static capacity 220 μ F.This capacitor core is put into the aluminum can, carry out after the insulation processing with the joint filling material sealing, such aluminium electrolytic capacitor has just been made (size: Φ 10mm * L10.2mm).
Example 2～8th replaces electroconductive polymer in the example 1 and organic anion salt with material cited in the table 1.Material beyond electroconductive polymer of being put down in writing in the table 1 and the organic anion salt, using method is identical with example 1.
Comparative example 1
Get involved between anode aluminium foil and the cathode aluminum foil that separator makes it to separate and curl, obtain capacitor core.Then this capacitor core is immersed in the electrolyte 1, so just obtains rated voltage 50V, the aluminium electrolytic capacitor core of static capacity 220 μ F.This capacitor core is put into the aluminum can, with joint filling material sealing, so just produce aluminium electrolytic capacitor (size: Φ 13mm * L10.2mm) after the insulation processing.
Electrolyte 1: contain phthalic acid 1,2,3,25% gamma-butyrolacton solution of 4-tetramethyl imidazole salts.
Comparative example 2
Compare with the embodiment of the invention 1, except that not soaking in organic anion salt, other are all identical with embodiment 1.
Table 2 is electrolytic capacitors described in embodiment 1～8 and the comparative example 1～2 among the present invention, is used for their initial stage characteristic of comparison [static capacity 120Hz, impedance 100kHz, leakage current value and the short circuit in burin-in process (bad) incidence].Choose 50 trial targets arbitrarily, the initial stage characteristic is got their mean value (except the poor short circuit product).
Can find out obviously that by table 2 aluminium electrolytic capacitor that only uses electrolyte in the comparative example 1 is compared with embodiment 1～8 described in the invention, impedance obviously increases.
In comparative example 2, though impedance operator is better, because the repair ability of oxide film is obviously less, therefore the short circuit incidence in ageing process is than higher.
Table 1
Table 2
| Static capacity (μ F at 120Hz) | Impedance (m Ω at 100kHz) | Leakage current (μ A) | Short circuit incidence (individual) | |
| Embodiment 1 | 221 | 28 | 13 | 0 |
| Embodiment 2 | 219 | 24 | 17 | 0 |
| Embodiment 3 | 222 | 23 | 14 | 0 |
| Embodiment 4 | 225 | 25 | 13 | 0 |
| Embodiment 5 | 223 | 26 | 15 | 0 |
| Embodiment 6 | 221 | 25 | 16 | 0 |
| Embodiment 7 | 225 | 23 | 13 | 0 |
| Embodiment 8 | 220 | 24 | 16 | 0 |
| Comparative example 1 | 218 | 145 | 12 | 0 |
| Comparative example 2 | 207 | 22 | 152 | 23 |
Claims (10)
1. an electrolytic capacitor is characterized in that, described electrolytic capacitor with electroconductive polymer A and organic acid complex salt B as electrolyte; Described electroconductive polymer A is conjugated double bond polymer (A-1) or adds the compound that obtains behind the additive in this polymer; Described organic acid complex salt B is made up of complex cation and organic anion, wherein complex cation is at least a kind of cation selecting from the group of 4 grades of ammoniums, 3 grades of sulfanilamide (SN), 4 grades of phosphorus and 3 grades of hydronium(ion)s, and organic anion is at least a kind of anion that removes deprotonation selecting from organic acid groups such as carboxylic acid, sulfonic acid, phenol monomer or dialkyl phosphate, boron fluor-complex; The weight ratio of described electroconductive polymer A and described organic acid complex salt B is A: B=1: 0.1～5.
2. according to the electrolytic capacitor of claim 1, it is characterized in that the complex cation of described organic acid complex salt B is 4 grades of ammonium cations.
3. according to the electrolytic capacitor of claim 2, it is characterized in that, 4 grades of ammonium cations in the described electrolyte are from trimethyl second ammonium, diethyl dimethylammonium, triethyl group first ammonium, 1,2,3,4-tetramethyl imidazoline, 1 is selected at least a kind of formation in 2-dimethyl-3-ethyl imidazol(e) quinoline, 1-ethyl-3-methylimidazole and the 1-methyl-3-ethyl imidazol(e).
4. according to the electrolytic capacitor of claim 1, it is characterized in that the organic anion of described organic acid complex salt B is that the anion of selecting to remove deprotonation constitutes from carboxylic acid, aromatic sulphonic acid.
5. according to the electrolytic capacitor of claim 1, it is characterized in that the organic anion of described organic acid complex salt B is that the anion of selecting to remove deprotonation constitutes from the polycycle aromatic sulphonic acid.
6. according to the electrolytic capacitor of claim 1, it is characterized in that the complex cation among the described organic acid complex salt B and the equivalent proportion of organic anion are 1: 0.2～3.
7. according to the electrolytic capacitor of claim 1, it is characterized in that described conjugated double bond polymer (A-1) is to select at least a kind of formation from the group of polypyrrole, polythiophene, polyethylene dihydroxy thiophene, polyaniline.
8. according to electrolytic capacitor any in the claim 1～7, it is characterized in that described capacitor is the electrolytic capacitor with solid forms.
9. an electrolytic capacitor electrolyte constituent is characterized in that, the compounding substances that described constituent is made of jointly single polymers with described electroconductive polymer A structure and described organic acid complex salt B; Described electroconductive polymer A is conjugated double bond polymer (A-1) or adds the compound that obtains behind the additive in this polymer; Described organic acid complex salt B is made up of complex cation and organic anion, wherein complex cation is at least a kind of cation selecting from the group of 4 grades of ammoniums, 3 grades of sulfanilamide (SN), 4 grades of phosphorus and 3 grades of hydronium(ion)s, and organic anion is at least a kind of anion that removes deprotonation selecting from organic acid groups such as carboxylic acid, sulfonic acid, phenol monomer or dialkyl phosphate, boron fluor-complex; The weight ratio of described electroconductive polymer A and described organic acid complex salt B is A: B=1: 0.1～5.
10. one kind is used to form electrolytic capacitor with electrolytical organic acid complex salt, it is characterized in that described organic acid complex salt jointly is made up of a kind of complex cation selecting and select a kind organic anion that removes deprotonation at least at least from the organic acid group of carboxylic acid, sulfonic acid, phenol monomer or dihydroxy phosphate, boron fluor-complex from the group of 4 grades of ammoniums, 3 grades of sulfanilamide (SN), 4 grades of phosphorus, 3 grades of hydronium(ion)s.
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| US10262808B2 (en) | 2015-12-24 | 2019-04-16 | Industrial Technology Research Institute | Conductive composite and capacitor utilizing the same |
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| JP5052760B2 (en) * | 2005-04-27 | 2012-10-17 | 株式会社フジクラ | Manufacturing method of conductive material |
| JP2008258526A (en) * | 2007-04-09 | 2008-10-23 | Matsushita Electric Ind Co Ltd | Solid-state electrolytic capacitor, and manufacturing method therefor |
| CN101556867B (en) * | 2009-05-20 | 2011-11-09 | 广东风华高新科技股份有限公司 | Electrolysis solution and preparation method thereof as well as preparation method for obtained aluminum capacitor |
| CN101814374A (en) * | 2010-04-19 | 2010-08-25 | 衡阳县创基电子有限公司 | Electrolyte of wide-temperature aluminium electrolytic capacitor and manufacturing method thereof |
| CN101866751A (en) * | 2010-06-07 | 2010-10-20 | 广东风华高新科技股份有限公司 | Temperature-resistant electrolyte for aluminum electrolysis and application thereof |
| CN107221458B (en) * | 2017-05-25 | 2019-11-15 | 温州大学 | Nickel complex is the carbon dope nickel oxide combination electrode material and preparation method thereof of precursor |
| CN107481858A (en) * | 2017-07-27 | 2017-12-15 | 李勇 | A kind of resistant to elevated temperatures electrolyte |
| CN107680811A (en) * | 2017-11-18 | 2018-02-09 | 陈馨雅 | A kind of electrolyte for aluminum electrolytic capacitor |
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| JP2000095870A (en) * | 1998-09-21 | 2000-04-04 | Japan Science & Technology Corp | Meso-position direct-bonding porphyrin polymer and its production |
| WO2001009972A1 (en) * | 1999-07-29 | 2001-02-08 | Universita' Degli Studi Di Padova | Magnesium-based primary (non-rechargeable) and secondary (rechargeable) batteries |
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| WO2000002949A1 (en) * | 1998-07-09 | 2000-01-20 | Forskarpatent I Linköping Ab | Polymer gel electrode |
| JP2000095870A (en) * | 1998-09-21 | 2000-04-04 | Japan Science & Technology Corp | Meso-position direct-bonding porphyrin polymer and its production |
| WO2001009972A1 (en) * | 1999-07-29 | 2001-02-08 | Universita' Degli Studi Di Padova | Magnesium-based primary (non-rechargeable) and secondary (rechargeable) batteries |
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| US10262808B2 (en) | 2015-12-24 | 2019-04-16 | Industrial Technology Research Institute | Conductive composite and capacitor utilizing the same |
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