JPH04368114A - Electrolytic capacitor for acoustic use - Google Patents

Abstract

PURPOSE:To improve impregnation of electrolyte for driving, and enhance developing of capacitance, by setting the intervals of adjacent titanium columns of a titanium evaporation foil to be 50Angstrom . CONSTITUTION:On a flat aluminum substratum 1, a titanium evaporation coating film of 0.1mum in thickness wherein the intervals T of adjacent columns 2 are 50Angstrom is formed and turned into a cathode foil. Said foil is wound, via a separator, together with an anode foil of 90mum in thickness wherein an anode oxide coating film is formed, and a capacitor element is formed. The said element is impregnated with electrolyte for driving composed of 12wt.% water content, 74wt.% ethylene glycol, and 14wt.% ammonium adipate, and an electrolytic capacitor for coupling is formed. Thereby acoustic characteristics are improved and the superior regeneration of an audio signal is realized.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acoustic electrolytic capacitor using an electrode foil for electrolytic capacitors having a vapor-deposited film formed on the surface of the substrate.

0002

[Prior Art] Electrolytic capacitors are made by winding an anode foil and a cathode foil made of a valve metal such as aluminum with a separator interposed between them to form a capacitor element.Generally, the capacitor element is impregnated with a driving electrolyte, and The capacitor element is housed in a case made of synthetic resin or synthetic resin, and has a sealed structure.

[0003] Conventionally, the driving electrolyte for such an electrolytic capacitor uses an organic polar solvent such as ethylene glycol or γ-butyrolactone alone or a mixture thereof as a main solvent, and a carboxylic acid or its salt as a solute. An electrolytic solution in which sugars, water, phosphoric acid, etc. are dissolved as additives is generally used.

[0004] Furthermore, in order to increase the capacitance of electrolytic capacitors, the surface area of aluminum foil, which is the base material of the electrode material, is enlarged by chemical or electrochemical etching. There is a limit to increasing the capacitance of the electrode material by etching technology, because if it becomes excessive, the surface of the aluminum foil will simultaneously melt, which will actually hinder the increase in the area enlargement ratio. In order to solve these problems, we used aluminum foil, which is a valve metal, as a base material, roughened the surface of the base material, and then used a vapor-deposited film on the surface of this base material as a cathode material. It can also be used as JP-A-61-180
No. 420, JP-A-61-214420, JP-A-62-
No. 58609, JP-A-62-15813, JP-A-64
-33918, JP-A-63-100711, and JP-A-1-304720.

[0005] When fine irregularities are formed physically, chemically, or electrochemically on the surface of the base material in advance, the effect of increasing the capacitance of the vapor-deposited foil may be observed. It significantly impairs the strength and elongation of the material, and also requires a roughening process, forcing a disadvantageous choice in terms of cost.

[0006] Furthermore, various proposals regarding vapor deposition methods are known from Japanese Patent Laid-Open Nos. 56-29669, 64-33915, and 64-33918. That is, it is known that titanium is formed into columnar shapes by adjusting the deposition angle or by depositing titanium while cooling the base material, thereby achieving the expression of capacitance.

[0007]

[Problem to be Solved by the Invention] When titanium is formed in columnar form by vapor deposition on a substantially smooth base material of aluminum foil, that is, as shown in FIG. If the distance T between the titanium pillars (hereinafter referred to as columns) 2 formed on 1 and the other columns 2 is close, the above-mentioned driving electrolyte will be sufficiently impregnated between the adjacent columns 2 and 2. There has been a problem in that the development of capacitance is reduced without being absorbed.

[0008]

[Means for Solving the Problems] In order to solve these problems, the present inventors conducted various experiments and studies, and found that the spacing (gap) between adjacent columns is less than 50 angstroms. , the impregnating property of the driving electrolyte is poor,
It was found that the ability to express capacitance was poor. Also, the spacing (gap) between adjacent columns is 50 angstroms.
It has been found that when it is more than 0.0 mm, the impregnating property of the driving electrolyte is improved and the ability to develop capacitance is improved. In particular, a range of 50 to 500 angstroms is very good.

[0009] In the present invention, aluminum foil is suitably used as the base material, and it is possible to use an aluminum foil base material having minute irregularities as described above or a substantially smooth aluminum foil base material. You can. By using smooth aluminum foil as the base material, it is possible to reduce the thickness of the base material without compromising tensile strength or elongation, and also because there is no need for a process to roughen the surface in terms of cost. It is advantageous for Although such a substrate can also be used as an anode foil for a capacitor element, it is more preferable to use it as a cathode foil.

On the other hand, as the cathode foil of the capacitor element used in the present invention, a substantially smooth aluminum foil with a thickness of 5 to 100 μm is used as a base material.
~60 μm is preferably used. Examples of methods for depositing titanium on the aluminum base material include vacuum evaporation, sputtering, ion plating, and CVD. Also, in vacuum or oxygen gas,
50 in an atmosphere of inert gas such as nitrogen or argon
Preferably, the deposit is formed to a thickness of .about.3000 angstroms. In particular, if the deposition conditions are selected in nitrogen gas, a titanium nitride deposited film can be formed. The titanium nitride deposited film also includes a partially nitrided titanium thin film represented by TiNx (0<x≦4/3). Further, the titanium nitride deposited film also includes a mixed film of titanium nitride and titanium oxide.

[0011] Furthermore, the cathode foil on which the vapor deposited film was formed and the aluminum anode foil on which the oxide film was formed were wound together with a separator in between, and impregnated with an electrolytic solution. When an aluminum electrolytic capacitor consisting of a capacitor element is applied as a coupling capacitor in an amplifier circuit, as a smoothing capacitor in a power supply circuit, or as a capacitor for a speaker network, it provides an extremely excellent acoustic electrolytic capacitor. Therefore, it was possible to reproduce a good audio signal.

As the organic polar solvent of the driving electrolyte used in the present invention, any organic polar solvent commonly used in electrolytic capacitors can be used. Preferred solvents include amides, lactones, glycols,
Sulfur compounds, ketones, ethers or carbonates can be used. Preferred specific examples include propylene carbonate, N,N-dimethylformamide, N-methylformamide, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, ethylene cyanohydrin, ethylene glycol, ethylene glycol mono- or dialkyl ether, 3-alkyl-1,3-oxazolidine-
2-on etc. can be used. Particularly preferably, lactones, ethylene glycols, etc. are used.

As the solute of the driving electrolyte used in the present invention, any solute that is commonly used in electrolytic capacitors can be used.

Preferred solutes include inorganic acids or salts thereof such as boric acid and phosphoric acid, heteropolyacids such as tungstic acid or salts thereof, organic acids having a phenolic hydroxyl group or salts thereof, and organic acids having a sulfonic acid group. Organic acids or their salts, chain monocarboxylic acids or their salts such as formic acid and dodecylic acid, aromatic monocarboxylic acids or their salts such as benzoic acid and salicylic acid, and chains such as adipic acid and sebacic acid. dicarboxylic acids or their salts, unsaturated dicarboxylic acids or their salts such as maleic acid or citraconic acid, cyclic dicarboxylic acids or their salts consisting of phthalic acid, nitrophthalic acid or tetrahydrophthalic acid, tricarboxylic acids such as citric acid or The salt thereof can be exemplified. Particularly preferred are quaternary alkyl ammonium salts of aromatic carboxylic acids or unsaturated dicarboxylic acids, and ammonium salts of aromatic carboxylic acids.

[0015] As the salt, ammonium salt,
Examples include tertiary amine salts and quaternary ammonium salts. In addition, water is added to increase conductivity, but 15% water is added to prevent changes in capacitor characteristics over time.
% or less, preferably 8% or less, particularly preferably 5% or less.

[0016]

【Example】

<Example 1> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 50 angstroms between adjacent columns, and this was used as a cathode foil.
A capacitor element is manufactured by winding the film together with a 90 μm anode foil having an anodic oxide film formed thereon through a separator, and this capacitor element is coated with a mixture containing 12 wt% of water, 74 wt% of ethylene glycol, and 14 wt% of ammonium adipate. Impregnated with driving electrolyte, rated at 50V47μF,
A JIS 04 type coupling electrolytic capacitor with an outer diameter of 8 mm and a length of 11.5 mm was manufactured.

<Example 2> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 50 angstroms between adjacent columns, and this was used as a cathode foil.
A capacitor element is manufactured by winding it together with a 90 μm anode foil having an anodic oxide film formed thereon via a separator, and this capacitor element is coated with 1 wt% moisture, 74 wt% γ-butyrolactone, and 25 wt% tetramethylammonium o-phthalate. Impregnated with driving electrolyte consisting of 50%
V47μF, outer diameter 8mm, length 11.5mm JIS0
We manufactured a type 4 electrolytic capacitor for coupling.

<Example 3> Thickness: 40 μm, tensile strength: 4.
A vapor-deposited film of titanium nitride with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 50 angstroms between adjacent columns, and this was used as a cathode foil to form an anodized film. A capacitor element is manufactured by winding the formed 90 μm anode foil through a separator, and this capacitor element is coated with a driving electrolyte consisting of 1 wt% moisture, 74 wt% γ-butyrolactone, and 25 wt% tetraethylammonium maleate. Impregnated with rated 5
0V47μF, outer diameter 8mm, length 11.5mm JIS
We manufactured a 04 type electrolytic capacitor for coupling.

<Comparative Example 1> Thickness: 40 μm, tensile strength: 4.
A vapor-deposited film of titanium nitride with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 10 angstroms between adjacent columns, and this was used as a cathode foil to form an anodized film. A capacitor element was manufactured by winding the anode foil with a thickness of 90 μm through a separator, and this capacitor element was coated with 12 wt% moisture, 74 wt% ethylene glycol, and 14 wt% ammonium adipate.
Impregnated with driving electrolyte consisting of %, rated 50V47μ
A JIS04 type coupling electrolytic capacitor with an F outer diameter of 8 mm and a length of 11.5 mm was manufactured.

<Example 4> Thickness: 40 μm, tensile strength: 4.
A vapor-deposited film of titanium nitride with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 70 angstroms between adjacent columns, and this was used as a cathode foil to form an anodized film. A capacitor element was manufactured by winding the formed 90 μm anode foil through a separator, and this capacitor element was coated with a driving material consisting of 1 wt% moisture, 74 wt% γ-butyrolactone, and 25 wt% tetraethylammonium o-phthalate. Impregnated with electrolyte, rated 80V 12000μF, outer diameter 51mm, length 120mm
, manufactured a JIS62 type electrolytic capacitor for power supply.

<Example 5> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 70 angstroms between adjacent columns, and this was used as a cathode foil.
A capacitor element is manufactured by winding it together with a 90 μm anode foil having an anodic oxide film formed thereon via a separator, and this capacitor element is coated with 1 wt% moisture, 74 wt% γ-butyrolactone, and 25 wt% tetramethylammonium o-phthalate. Impregnated with driving electrolyte consisting of 80%
V12000μF outer diameter 51mm, length 120mm, J
We manufactured an IS62 type electrolytic capacitor for power supply.

<Example 6> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 70 angstroms between adjacent columns, and this was used as a cathode foil.
A capacitor element is manufactured by winding the anode foil with an anodized film of 90 μm through a separator, and this capacitor element contains 1 wt% of water, 74 wt% of γ-butyrolactone, and 2 wt% of tetraethylammonium maleate.
Impregnated with driving electrolyte consisting of 5wt%, rated at 80V
12000μF outer diameter 51mm, length 120mm, JI
We manufactured an S62 type electrolytic capacitor for power supply.

<Comparative Example 2> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 20 angstroms between adjacent columns, and this was used as a cathode foil.
A capacitor element is manufactured by winding the anode foil with a 90 μm thick anode film formed with an anodized film through a separator, and this capacitor element is coated with 1 wt% moisture, 74 wt% γ-butyrolactone, and 25 wt% tetraethylammonium o-phthalate salt. Impregnated with driving electrolyte consisting of 8%
0V12000μF outer diameter 51mm, length 120mm,
We manufactured a JIS62 type electrolytic capacitor for power supply.

<Example 7> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 100 angstroms between adjacent columns, and this was used as a cathode foil to form an anodic oxide film. A capacitor element was manufactured by winding the 90 μm anode foil with a separator in between.
This capacitor element contains 12 wt% moisture, 74 wt% ethylene glycol, and 14 wt% ammonium adipate.
Impregnated with driving electrolyte consisting of, rated at 50V8.2μ
We manufactured a JIS04 type electrolytic capacitor for speaker networks.

<Example 8> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film with a thickness of 0.1 μm was formed on a smooth aluminum base material with a width of 0 kg/cm with a spacing of 100 angstroms between adjacent columns, and this was used as a cathode foil to form an anodic oxide film. A capacitor element was manufactured by winding the 90 μm anode foil with a separator in between.
This capacitor element was impregnated with a driving electrolyte consisting of 1 wt% water, 74 wt% γ-butyrolactone, and 25 wt% tetramethylammonium o-phthalate, and
0V8.2μF JIS04 type speaker network
We have manufactured an electrolytic capacitor for

<Comparative Example 3> Thickness: 40 μm, tensile strength: 4.
A titanium vapor-deposited film having a thickness of 0.1 μm with an interval of 30 angstroms between adjacent columns was formed on a smooth aluminum base material with a width of 0 kg/cm, and this was used as a cathode foil.
A capacitor element is manufactured by winding it together with a 90 μm anode foil on which an anodized film is formed through a separator, and this capacitor element contains 12 wt% of moisture, 74 wt% of ethylene glycol, and 14 wt% of ammonium adipate salt.
Impregnated with driving electrolyte consisting of, rated at 50V8.2μ
We manufactured a JIS04 type electrolytic capacitor for speaker networks.

Next, the electrolytic capacitors of Examples 1, 2, and 3 and Comparative Example 1 were respectively connected as coupling capacitors between the preamplifier and the power amplifier, and five people listened to the results for comparison. The following items were evaluated: sense of place, amount of information, frequency range/balance, sense of localization, sense of transparency, graininess, sense of distortion, feel of the mid-range sound, feel of the bass/deep bass sound, and feel of the treble range, and an overall evaluation was made based on these items. The results are shown in Table 1.

[0029]

[Table 1]

As can be seen from Table 1, the product of the present invention obtained higher scores in each evaluation source for vocals, orchestra, jazz, and piano, but especially for orchestra A large difference was seen.

Next, the electrolytic capacitors of Examples 4, 5, and 6 and Comparative Example 2 were used as capacitors in the power supply smoothing circuit of an audio power amplifier, and 5 people listened to them for comparison to determine the sound field. We evaluated the following items: sound, information content, frequency range/balance, localization, clarity, graininess, distortion, midrange texture, bass/heavy bass texture, and treble range texture, and made a comprehensive evaluation based on these. The results are shown in Table 2.

[0032]

[Table 2]

As can be seen from Table 2, the product of the present invention obtained higher scores in each evaluation source for vocals, orchestra, jazz, and piano, but especially for vocals. A large difference was seen.

Next, the electrolytic capacitors of Examples 7 and 8 and Comparative Example 3 were used as filter capacitors for a 12 dB/OCT 2-way speaker network.
Comparatively listen to the sound field, amount of information, frequency range balance, localization, transparency, graininess, distortion, midrange texture, bass/heavy bass texture, and treble texture. A comprehensive evaluation was then made from these. Table 3 shows the results.
Shown below.

[0035]

[Table 3]

As can be seen from Table 3, the product of the present invention obtained higher scores in each of the evaluation sources for vocals, orchestra, jazz, and piano, but in particular, it received a high score for piano. I saw a difference.

[0037]

Effects of the Invention As described above, in the present invention, the interval between adjacent titanium columns of titanium-deposited foil is set to 50 angstroms.
By adjusting the time, it is possible to obtain good reproduced sound.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a titanium-deposited foil film structure.

[Explanation of sign]

1 Aluminum base material 2 Column

Claims (2)

[Claims] [Claim 1] A titanium thin film and/or a titanium thin film on an aluminum foil base material with an interval of 50 angstroms or more between adjacent columns.
Alternatively, an electrode foil on which a titanium nitride thin film is formed is used as a cathode foil,
This cathode foil and anode foil are wound through a separator,
An acoustic electrolytic capacitor consisting of a capacitor element impregnated with electrolyte. 2. The electrolytic capacitor according to claim 1, wherein a substantially smooth aluminum foil is used as the base material.