JPH10128908A - Metal vapor-deposition film, its production method, and capacitor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the anti-moisture property without deteriorating the press molding property or the laminating property, and prevent deterioration of the insulating resistance by providing a metal deposition layer on at least one side of a metal vapor-deposition film substrate, and providing an organic compound layer with a certain thickness on the metal vapor-deposition layer. SOLUTION: A metal vapor-deposition film 1 is formed by laminating a metal vapor-deposition film 3, an organic compound layer 4, and an insulating part (margin) 5, which is an insulating layer with out a metal deposition layer, or for maintaining the insulation between the metal metal-deposition layer and the opposite electrode when an insulating layer formed with metal oxide with a margin oil 6 on a film substrate 2. The organic compound layer thickness should be 1 to 1000Å. As the organic compound, a crosslinked silicone resin containing dimethyl polysiloxane or methyl phenyl silicone oil, having a di-, tri- or tetra-functional siloxane bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-deposited film suitable for use in a capacitor or packaging, and particularly to a metal-deposited film most suitable for a capacitor and a method for producing the metal-deposited film. It relates to a capacitor.

[0002]

2. Description of the Related Art A capacitor using a metal-deposited film has a self-healing property (self-healing property).
In particular, it accounts for about 80% of the film capacitors using an organic polymer film as a dielectric. However, since these metal-deposited films are composed of ultra-thin metal-deposited layers of 100 to 500 angstroms, all the layers are not in a sufficiently crystalline state, and easily become oxides by humid air,
It includes the danger of dielectric breakdown due to thermal bombardment due to a decrease in capacity and an increase in tan δ due to insulation. Especially Z
This tendency is strong in metal-deposited films on which metals such as n and Sn are deposited.

In addition, with the improvement of high temperature and humidity resistance of semiconductors, electric circuit elements have been used even under high temperature and high humidity, and capacitors using metal vapor deposited films, especially metal vapor deposited films on which Al is vapor deposited, have been developed. Also the conventional 40 ℃ ×
85% RH to 60 ° C x 95% RH or 85 ° C x 8
It has been required to have a moisture resistance of 5% RH. In recent years, several improvement proposals have been made in response to improvement of these drawbacks or new requirements.

First, as an improvement of a Zn-deposited metal film, Japanese Patent Application Laid-Open No. 57-206031 proposes to provide an Al-deposited layer on a Zn-deposited layer to improve the moisture resistance. Although it is improved compared to, it is still not enough. Further, Kokoku 5-63092, JP Sho 60-224211 issue in Japanese Zn or inorganic Si on the Al deposited metal, or SiO ₂ is deposited inorganic oxide, to improve the moisture resistance Proposed. Although it is recognized that the moisture resistance of the metal-deposited film produced by this method is clearly improved, there is a disadvantage that the moisture resistance varies, and furthermore, the deposition rate of Si or SiO ₂ is extremely low, so that Zn or Al There is too much difference in the deposition rate between the above and production difficulties are involved. In addition,
It is considered that the variation in the moisture resistance performance is caused by the fact that the evaporation amount of Si or SiO ₂ is very small when the deposition rate of Zn or Al is made to follow, so that a uniform layer cannot be formed.

[0005] Further, as a method actually used at present, Japanese Patent Application Laid-Open No. Sho 59-227115 and Japanese Patent Publication No.
No. 15737 (US Pat. No. 4,785,374),
Japanese Patent Application Laid-Open No. 3-143629 proposes a method of depositing silicone oil or the like on a metal deposition layer in a vacuum vapor.

Although such a method certainly improves the moisture resistance, the performance is insufficient for recent severe demands, and furthermore, the press-moldability for forming a flat capacitor or a multilayer capacitor requires a metal-deposited film. There is a disadvantage that adhesion between layers is poor. In recent years, as the element molding speed has increased, such inconvenience has been highlighted as an important problem.

On the other hand, JP-A-2-218716 and JP-A-4-245414 disclose an Al-deposited metal film.
JP, JP-A-5-275276, JP-A-6-1
As disclosed in Japanese Patent No. 40281, a method is proposed in which a thin layer of an organic polymer is provided on a substrate, and Al is vapor-deposited on the thin layer. However, the effect of improving the moisture resistance of the method is insufficient with respect to a target level. Tan which seems to be due to interfacial polarization
There is a disadvantage that δ rises, and a product that can meet the demand has not yet been developed.

Further, D. SHAW et al.
3000 fluorinated bifunctional acrylates (fluor
Inert diacrylate is deposited to a thickness of 4000 angstroms on the Zn deposition layer and then cross-linked with an electron beam to improve the moisture resistance of Zn (16th Capacitor and Re).
Sistor Technology Symposi
m, 1996), this method has the disadvantages that the pressability is poor, that charging is considered to be caused by an electron beam, that the slipperiness between the metallized films is poor, and that the element winding characteristics of the capacitor are deteriorated.

[0009]

SUMMARY OF THE INVENTION The present invention has been accomplished to improve moisture resistance without impairing press formability or laminability. In addition, the present inventor has also found that as a concomitant effect of the present invention, the problem that the IR (insulation resistance) of the Al vapor-deposited film has been reduced in winter can be improved.

[0010]

According to the present invention, there is provided a metal-deposited film according to the present invention which has the above-mentioned object and has a metal-deposited layer on at least one surface of a substrate, and has a thickness of 1 angstrom or more on the vapor-deposited layer. A metal-deposited film having an organic compound layer of Å or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a metal-deposited film of the present invention, a method for producing the metal-deposited film, and a capacitor using the film will be described in more detail.

FIG. 1 is a schematic view of a metal-deposited film according to an embodiment of the present invention.

The present invention is not limited to the embodiment.

In FIG. 1, reference numeral 1 denotes a metal-deposited film of the present invention, 2 denotes a substrate, 3 denotes a metal-deposited layer, 4 denotes an organic compound layer, 5 denotes whether a metal-deposited layer is not formed, or Insulating part (referred to as "ear width" or "margin", hereinafter referred to as "margin") for maintaining insulation between the metal-deposited layer and the counter electrode when the capacitor is formed by an insulating layer formed from an object or the like. It is. Reference numeral 6 denotes a margin oil for forming a margin.

In FIG. 1, the metal deposition layer 3, the organic compound layer 4, and the margin 5 are provided only on one side of the substrate 2, but they may be provided on both sides of the substrate 2. The margin 5 is provided at one end of the metallized layer 3 in the width direction of the metallized film 1. However, as described in Japanese Patent Publication No. 1-30285, a series capacitor is provided on both sides, or at the center, and in the case of Japanese Patent Publication No. As described in Japanese Patent No. 225508 (US Pat. No. 5,136,462), in a capacitor with a security mechanism, a margin 5 having various patterns can be provided in the metal deposition layer 3.

The thickness of the organic compound layer is preferably 1 angstrom or more and less than 1000 angstrom. 1000
Above Angstroms, interfacial polarization occurs and ta
nδ increases. More preferably, it is not less than 5 Å and not more than 500 Å, more preferably not less than 10 Å and not more than 100 Å. If it is 10 Å or more, a sufficient moisture resistance effect is recognized, and if it is 100 Å or less, the pressability is extremely good.

The organic compound layer is obtained by observing the cross section of the metal-deposited film with an electron microscope or by performing Auger electron spectroscopy (AES) while performing ion etching with Ar ions to determine the atomic weight of the organic compound such as carbon atoms. It can be quantified by measuring and calculating the thickness of the organic compound layer from the etching time from the surface of the organic compound to the metal deposition layer using a known etching rate of the organic compound.

The substance constituting the organic compound layer is not particularly limited as long as it is an organic compound, but is preferably a crosslinked organic polymer layer. If such a cross-linked organic polymer layer is used, the cross-linked film is deformed without causing cracks or the like due to deformation due to press working when forming a capacitor, shrinkage due to heat treatment, etc. It is less likely to cause deterioration. According to the findings of the present inventors, among them, a crosslinked silicone resin is preferable, and in particular, a bifunctional siloxane bond of the following formula 1, a trifunctional siloxane bond of the formula 2,

Embedded image

Embedded image And / or a tetrafunctional siloxane bond of the following formula 3:

Embedded image Is particularly excellent in the moisture resistance and the pressability is also good. This is due to trifunctional siloxane bonds,
Further, it is considered that the tetrafunctional siloxane bond improves the moisture resistance performance and the pressability, and the bifunctional siloxane bond portion corresponds to the deformation stress caused by press working, heat treatment, and the like.

Among them, according to the findings of the present inventors, a crosslinked silicone resin composed of dimethylpolysiloxane or methylphenylsilicone oil and having a di-, tri-, or tetra-functional siloxane bond as described above may be used. More preferred.

According to the findings of the present inventors, it is effective for the pressability that the surface tension of the surface of the organic compound layer is 38 dyne / cm or more. Among them, silicone having a di-, tri-, or tetra-functional siloxane bond is preferred. It is most preferable that the resin is a crosslinked silicone resin layer having a surface tension of 38 dyne / cm or more in terms of moisture resistance and pressability.

The material constituting the substrate 2 is not particularly limited, but paper, an organic polymer film and the like can be preferably used. In particular, an organic polymer film is more preferable because of its excellent flexibility and electric insulation.

The organic polymer film referred to in the present invention is a film obtained by molding a natural, semi-synthetic, or synthetic polymer resin into a film. Among them, an organic polymer film made of a synthetic polymer resin has heat resistance, mechanical properties, and electrical properties. It is more preferable in terms of characteristics and physicochemical characteristics.

Preferred polymer resins include polyolefin resins, polyester resins, polyamide resins, polyimide resins, polyamide imide resins, polycarbonate resins, polysulfone resins, polyphenylene resins, polyarylate resins, fluororesins, polystyrene resins, and polyarylene resins. Can be used. In particular, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polycarbonate, and polystyrene are more preferable in terms of mechanical properties and electrical properties. Among them, polypropylene, polyethylene terephthalate, and polyethylene naphthalate are preferable because of their high AC withstand voltage (AC withstand voltage).

For DC applications, polyethylene naphthalate, polyethylene terephthalate, and polyphenylene sulfide are particularly preferred.

Further, it is more preferable to increase the surface tension of the surface of the organic polymer film to 38 dyne / cm or more, since it is possible to increase the adhesion of the vapor-deposited metal or the impregnation with the impregnating agent.

The metal of the metal deposition layer 3 is Al, Zn, C
Any material having conductivity such as u, Ag, Au, Su, Fe, or an alloy thereof can be used without any particular limitation. However, Al, Zn, Cu, Su, and the like have corona deterioration resistance. Less preferred. Among them, Al-Zn alloys are more preferable in terms of moisture resistance performance, corona deterioration resistance and self-recovery characteristics, and among them, the Al content ratio in the deposited alloy film 膜 (Al content × 100) / (Al content + Zn content) ｝ Is the metal deposition layer surface C ₁ , the metal deposition layer center C ₂ ,
When C ₃ in the polymeric film interface, C ₂ as in FIG. 2
A metal vapor-deposited layer continuously changing as <C ₁ and C ₂ <C ₃ is preferable. Further, a metal vapor deposition layer made of an Al—Zn alloy in which the Al content ratio of the entire metal vapor deposition layer is 0.5 to 15 wt%, more preferably 8 to 12 wt% is particularly preferable. Among them, an Al—Zn alloy having a distribution of Al content ratio C ₂ <C ₁ ≦ C ₃ is more preferable because the self-healing property is not deteriorated.

The method for producing the metal-deposited film of the present invention is not particularly limited. However, after depositing a metal on a substrate in a vacuum deposition machine, an organic compound is then deposited on the deposited metal layer.
Further, by performing glow discharge treatment on the surface of the organic compound, the moisture resistance can be remarkably improved, and the pressability can be further improved.

For example, after vapor-depositing Al on a polyethylene terephthalate film to a thickness of 2 Ω / □, a silicone oil (SH7 manufactured by Dow Corning Toray Silicone Co., Ltd.) is produced by the method of Japanese Patent Publication No. 63-15737.
02), the moisture resistance is improved. However, when the glow discharge treatment using oxygen gas is performed after the silicone oil deposition, the deposition is performed even at 130 ° C. × 90% RH (in an autoclave). It is a surprising finding that the moisture resistance is remarkably improved as the film disappears and the increase in the deposited film resistance is also within 50%.

Conventionally, in general, an Al vapor-deposited film on which silicone oil is not vapor-deposited or an Al vapor-deposited film on which only silicone vapor is vapor-deposited has a temperature of 130.degree.
When left in an atmosphere of 90% RH, the deposited film disappeared within 1 hour (the deposited film became transparent), but it was surprising that the deposited film did not disappear as described above. .

Further, the pressability deteriorates with a vapor-deposited film in which only silicone oil is vapor-deposited, and it is necessary to press at a higher temperature for a long time as compared with a metal-deposited film in which only aluminum is vapor-deposited. X-ray photoelectron spectroscopy (XP)
S, or ESCA), the surface is analyzed. In addition to the bifunctional siloxane bond inherent in the silicone oil, tri- and tetrafunctional siloxane bond components are formed, and the silicone oil is cross-linked. (It is considered that some siloxane bonds chemically react with the Al deposited film.) This is considered to significantly improve the moisture resistance performance. Further, after the silicone oil is deposited, the surface tension of the metal-deposited film subjected to the glow discharge treatment is 38 dyne / cm or more.
It is considered that this significantly improved the pressability.

The thickness of the organic compound deposited on the metal deposition layer is preferably less than 1000 Å,
When angstrom is exceeded, the tan of the metallized film
δ rises, and the lower layer of the organic compound does not crosslink,
Further, the effect of improving pressability is small.

Glow discharge (low temperature plasma) in the present invention
Is a discharge that is started and sustained by applying an electromagnetic field in a vacuum, and can be formed by applying a DC voltage, a low, a medium, a high frequency voltage, and a microwave to a discharge starting or / and a discharge sustaining gas in a vacuum. Further, by applying a magnetic field together, the discharge can be further stabilized at a lower voltage.

The type of gas used in the present invention is not limited, but a gas containing an oxygen atom is more preferable. For example, O
₂ , CO, CO ₂ , or a mixed gas of these and other gases can be preferably used.

In a metal-deposited film for a capacitor, a margin is usually formed. There are two methods for forming the margin: a tape margin method using tape and an oil margin method made by evaporating oil.The metal deposited film made by the oil margin method has a higher withstand voltage, but the pressability is reduced. There is. However, as in the method of the present invention, a metal-deposited film that has been subjected to a glow discharge treatment after an organic compound has been deposited on a metal-deposited layer has the feature that pressability is not reduced even if a margin is formed by an oil margin method. In the method of the present invention, it is particularly preferable to use silicone oil as an oil for forming a margin (margin oil). Among them, the weight average molecular weight MW is 300 ≦ MW ≦ 8
A dimethylpolysiloxane oil of 00 or a methylphenylsilicone oil is preferred, and a methylphenylsilicone oil having a ratio to the number average molecular weight MN of 1.0 ≦ MW / MN ≦ 1.1 is particularly preferred. Further, this silicone oil can be preferably used also as an organic compound deposited on the metal deposition layer.

When the surface opposite to the surface on which the metal vapor-deposited layer is provided is subjected to corona discharge treatment or glow discharge treatment and the surface tension of the surface is set to 38 dyne / cm or more, the pressability is further improved, and when the capacitor is impregnated. This is preferable because the impregnating property of the impregnating agent is improved.

The metallized film of the present invention is laminated or wound, or further pressed and, if necessary, impregnated.
A good capacitor can be made by packaging. The impregnating agent for the capacitor using the metal-deposited film of the present invention is not particularly limited, but an epoxy resin, a urethane resin, a silicone resin or the like can be preferably used.

The use of the metallized film of the present invention is not limited to a capacitor.

[0038]

[Measurement and evaluation methods of physical properties]

(1) Composition analysis of Al—Zn alloy A 9 cm ² metal-deposited film sample was dissolved in diluted nitric acid, and then dissolved in 20 ml. The constant solution was quantified for Al and Zn by ICP emission spectroscopy. ICP emission spectrometer is SPS1200VR manufactured by Seiko Electronic Industry Co., Ltd.
A mold was used.

(2) Composition distribution of Al and Zn Quantitative analysis of Al and Zn was performed by using a JAMP-10S type Auger electron spectrometer manufactured by JEOL while etching the surface of the deposition layer with Ar ions.

Ar ion etching conditions Acceleration voltage: 3 kV Sample current: 1 × 10 ⁻⁶ A Etching rate: 190 Å / min in terms of SiO ₂ Measurement conditions Acceleration voltage: 3 kV : 5 Sample current: 8 × 10 ^-8 A Sample tilt angle: 72 degrees Beam diameter: 10 μm In addition, Al content increases from the film interface to the film interface from the center of the vapor-deposited film, and decreases after reaching the maximum. The position of the maximum point is the film interface, and the content ratio of the maximum point is C ₃ .

(3) Presence or absence of an organic compound on the deposited film The presence of the organic compound can be confirmed by observing the surface of the deposited film by XPS (ESCA).

Apparatus: SSX-100-206 manufactured by SSI Excitation X destination: monochromated Al K
α1.2 line (1486.6 ev) Photoelectron escape angle (θ): 35 degrees Energy correction: The binding energy value of the C _1S main peak was adjusted to 284.6 ev.

Since XPS has good sensitivity, it sometimes detects organic matter due to contamination. However, the signal from the crosslinked organic compound formed on the vapor deposition surface is extremely high, and can be distinguished from contaminated organic matter.

(4) Measurement of Molecular Weight Distribution of Silicone Oil Gel Permeation Chromatograph GPC-244 (WATER
S), detector: differential refractive index detector R-401 (WATE)
RS), and molecular weight calibration was performed with polystyrene.

In the case of methylphenyl silicone oil, the column is TSK-gel-G3000HXL.
(1) G2500HXL (1) (Tosoh Corporation) was used. (5) Moisture resistance Performance Press Cook TP manufactured by Tabai Co., Ltd.
Put the metal deposition film in C-211 and 130 ℃ × 90
% RH for 1 hour or 3 hours in high-temperature and high-pressure steam, and the resistance change of the deposited film before and after the standing or the disappearance of the deposited film was visually determined.

(6) Surface tension According to JIS K 6768-1971, a wettability test method for polyethylene and polypropylene films.

(7) Evaluation of pressability Two metal vapor-deposited films were superposed and wound, and a load was applied to the press-formed element with tensilon, and the load when the core was opened (molding collapsed) was read. . The greater the load, the better the pressability.

[0048]

【Example】

Example 1, Comparative Example 1, Comparative Example 2 A 5 μm thick polyethylene terephthalate film
1 was vapor-deposited to prepare a vapor-deposited film for a capacitor having a margin 5 width of 2 mm and a metal vapor-deposited layer having a resistance of 2Ω / □.

In Example 1, Al was deposited in a vacuum deposition machine, and then phenyl methyl dimethyl polysiloxane oil (Toray Dow Corning Silicone Co., Ltd.)
SH702) is heated and vapor-deposited on Al, and the surface thereof is glow-discharged using O ₂ gas under the conditions of a primary side voltage of 280 V, a current of 1.1 A, a secondary side frequency of 15 kHz and an output of 0.32 kW. Was wound up. In Comparative Example 1, after depositing Al, silicone oil was similarly deposited. In Comparative Example 2, only the conventional method of depositing Al was used.

After slitting these metal-deposited films to a width of 30 mm, the films were placed in a pressure cooker at 130 ° C. and 90% RH for 3 hours to evaluate the moisture resistance. Table 1 shows the results.

As shown in Table 1, in the metal-deposited film of the present invention of Example 1, the resistance value increased by only about 14% even though the deposited metal disappeared (cleared) until the film resistance could not be measured. And showed good moisture resistance.

Next, these two deposited films were stacked and wound, and pressed at 125 ° C. and a pressure of 30 kgf / cm ² for 5 minutes to form a 1.6 μF capacitor element. The pressability of this capacitor element was evaluated.

Table 1 shows the results of the pressability evaluation. As shown in Table 1, it can be seen that the metal vapor-deposited film of the present invention shows the same good pressability as the conventional vapor-deposited film (Comparative Example 2).

[0054]

[Table 1] Example 2, Comparative Example 3, Comparative Example 4 A 4 μm thick polyphenylene sulfide film
1 was deposited to produce a metal-deposited film shown in FIG. The margin width (after the slit) was 0.4 mm, and the resistance of the metal deposition layer was 2Ω / □.

In the second embodiment, phenyl methyl dimethyl polysiloxane oil having a MW of 520 and a MW / MN of 1.0 (SH702 manufactured by Dow Corning Toray Silicone Co., Ltd.) after Al deposition in a vacuum vapor deposition machine.
Is heated to a thickness of about 70 angstroms on the Al deposited film, and further subjected to glow discharge using a mixed gas of Ar and O ₂ (40:60 v%) at 13.56 MHz and 500 W. Wound up. When the surface of the metal-deposited film was observed by XPS, a large amount of trifunctional siloxane bonds and tetrafunctional siloxane bonds was observed in addition to the bifunctional siloxane bonds. The surface tension is 56 dyne / c
m or more.

For comparison, a metal-deposited film in which phenyl-methyl-dimethyl-polysiloxane oil was similarly deposited after Al deposition (Comparative Example 3) and a conventional metal-deposited film in which only Al was deposited (Comparative Example 4) were implemented. Prepared under the same conditions as in Example 2.

These metal-deposited films were slit to a width of 4 mm, and two sheets of each film were laminated and laminated to form a 0.01 μF capacitor. Note that an epoxy resin was used as the impregnating agent.

Each capacitor is placed in a high-temperature, humidity atmosphere of 85 ° C. and 85% RH, and a voltage change of 100 VDC is applied, and the capacitance change after 1000 hours (△ C = ｛(C ₁₀₀₀ -C ₀ ))
/ C ₀ ｝ × 100 (%)). The results are shown in Table 2. As shown in Table 2, it can be seen that the capacitor using the metal-deposited film of the present invention according to Example 2 has the least change in capacitance and shows good moisture resistance.

[0059]

[Table 2] Example 3, Comparative Example 5, Comparative Example 6 Al was vapor-deposited on a 12 μm-thick polyethylene terephthalate film, and immediately Zn was vapor-deposited, and the average Al content was 8 wt%, C ₁ = 16 wt%, and C ₂ = 0.5wt%,
An Al—Zn alloy deposited film of C ₃ = 25 wt% was prepared. Note that a margin (after the slit) having a width of 2 mm was formed with silicone oil. The metal deposition layer was a heavy edge type, and each film resistance value was 3Ω / □ in the heavy edge portion and 9Ω / □ in the high film resistance portion.

In the third embodiment, after Al deposition in a vacuum deposition machine, dimethylpolysiloxane oil (SH200 10 manufactured by Dow Corning Toray Silicone Co., Ltd.) was used.
cst) is heated so that the pressure in the evaporator is constant,
Evaporation was performed to a thickness of about 10 angstroms on the Al—Zn vapor-deposited film, and then glow discharge was started and sustained by microwave using a mixed gas of Ar and O ₂ , and processed by microwave plasma.

Comparative Examples 5 and 6 are a metal-deposited film (Comparative Example 5) in which dimethylpolysiloxane oil is similarly deposited after Al-Zn deposition and a metal-deposited film (Comparative Example 6) in which only Al-Zn is deposited. . These metal deposition films were slit to a width of 14 mm. Further, the metal deposited films after each slit were allowed to stand in a high temperature and high steam pressure of 130 ° C. and 90% RH for 3 hours, and the results of measuring the deposited film resistance after standing are shown in Table 3. Further, each metal-deposited film is wound, and a pressure of 25 kgf / cm ² is applied at 120 ° C.
It was pressed for minutes to make a capacitor element. Table 3 shows the results of measuring the pressability of each capacitor element.

As shown in Table 3, the metal-deposited film of the present invention of Example 3 had extremely excellent moisture resistance, and had the same good pressability as Comparative Example 6.

[0063]

[Table 3] Example 4, Comparative Example 7, Comparative Example 8 After both surfaces of a polypropylene film having a thickness of 6 μm were subjected to surface treatment by glow discharge using CO ₂ gas in a vacuum evaporator, Cu was then evaporated as a nucleated metal, followed by Z
n was deposited to form a metal deposited film. The margin width (after the slit) is 3 mm, the metal deposition layer is a heavy edge type, and each film resistance value is 2 Ω / □ in the heavy edge portion,
The high film resistance portion was set to 8Ω / □.

In Example 4, dimethylpolysiloxane oil (SH200 10 cst manufactured by Dow Corning Toray Silicone Co., Ltd.) after Zn deposition in a vacuum vapor deposition machine.
Is heated while controlling the pressure in the evaporator, and is deposited to a thickness of about 50 angstroms on the Zn deposition film.
Glow discharge treatment was performed using a mixed gas of Ar and O ₂ at 0 kHz and 400 W.

The surface tension of the metal-deposited film side surface of the metal-deposited film was 56 dyne / cm or more, and the surface tension of the opposite film surface was 42 dyne / cm.

After slitting these metal-deposited films to a width of 50 mm, they were placed in a pressure cooker at 130 ° C. and 90% RH for 3 hours to evaluate the moisture resistance. Table 4 shows the results.

Further, these metal-deposited films were wound and pressed at 95 ° C. under a pressure of 25 kgf / cm ² for 5 minutes to form a 5 μF capacitor element. Table 4 shows the press characteristics.

Metallicons, heat treatment, lead attachment, epoxy resin vacuum impregnation on these capacitor elements, and potting of urethane resin were performed to prepare capacitors. When the dielectric breakdown voltage and corona starting voltage of these capacitors were measured, the capacitors of the present invention of Example 4 were all 20% higher than those of Comparative Examples.

Further, as shown in Table 4, the metal-deposited film of the present invention of Example 4 was excellent in moisture resistance and pressability was equivalent to that of a conventional Zn-deposited product.

[0070]

[Table 4]

[0071]

According to the present invention, a metal-deposited film has a metal-deposited layer on at least one surface of a substrate, and an organic compound layer having a thickness of 1 Å to 1,000 Å on the vapor-deposited layer. It is intended to improve the moisture resistance without impairing the press formability or the lamination property. Further, as an additional effect of the present invention, the problem that the IR (insulation resistance) of the Al vapor-deposited film is reduced depending on the season is also improved.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a metal-deposited film having a crosslinked organic compound on a metal-deposited layer of the present invention.

FIG. 2 is a schematic diagram showing an example of a composition distribution of Al and Zn in a deposited film of Al and Zn of the deposited film of the present invention.

[Explanation of symbols]

 1: Metal-deposited film 2: Polymer film 3: Metal-deposited layer 4: Organic compound layer 5: Margin part 6: Margin oil

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01G 4/24 331A

Claims (20)

[Claims] 1. A metal-deposited film having a metal-deposited layer on at least one side of a substrate and an organic compound layer having a thickness of 1 Å to less than 1000 Å on the metal-deposited layer. 2. The metal-deposited film according to claim 1, wherein the thickness of the organic compound layer is not less than 5 angstroms and not more than 500 angstroms. 3. The metallized film according to claim 1, wherein the thickness of the organic compound layer is not less than 10 Å and not more than 100 Å. 4. The metal-deposited film according to claim 1, wherein the organic compound layer is a crosslinked organic polymer layer. 5. The organic polymer constituting the crosslinked organic polymer layer is a silicone resin.
The metallized film as described in the above. 6. The silicone resin according to claim 5, wherein the silicone resin has a bifunctional siloxane bond and a trifunctional siloxane bond and / or a tetrafunctional siloxane bond.
The metallized film as described in the above. 7. The metallized film according to claim 4, wherein the crosslinked organic polymer layer comprises a crosslinked product of dimethylpolysiloxane or methylphenylsilicone oil. 8. The metal-deposited film according to claim 4, wherein the surface of the crosslinked organic compound layer has a surface tension of 38 dyne / cm or more. 9. The method according to claim 1, wherein the substrate comprises an organic polymer film.
The metallized film as described in the above. 10. An organic polymer film having a metal layer on one surface and having a surface tension of 38 dyn on the opposite surface having the metal layer.
The metallized film according to claim 9, wherein the thickness is not less than e / cm. 11. The method according to claim 11, wherein the metal of the metal deposition layer is Al, Zn, C
9. The method according to claim 1, wherein the material is at least one metal selected from u, Sn, An, Ag, and Fe, or an alloy of the at least one metal. 11. The metallized film according to item 9, 9 or 10. 12. The metallized film according to claim 11, wherein the metallized layer is made of Al or an alloy of Al and Zn. 13. The metal deposited layer is made of an alloy of Al and Zn, the Al concentration in the surface layer of the metal layer is C ₁ , the Al concentration in the interface with the base material is C ₃ , the metal in the interface between the metal surface layer and the base material is When the Al concentration at the intermediate position of the vapor deposition layer is C ₂ , the Al concentration in the metal vapor deposition layer changes substantially continuously in the thickness direction,
And _{C 1> C 2, C 3} > metallized film according to claim 12, wherein a relationship of C ₂ is intended to hold. 14. A method according to claim 1, wherein at least one side of the surface of the substrate has a portion (margin portion) without a metal deposition layer formed of silicone oil.
4, 5, 6, 7, 8, 9, 10, 11, 12, or 13
The metallized film as described in the above. 15. A metal is vapor-deposited on a substrate in a vacuum vapor deposition machine, and then an organic compound or an organic polymer having a predetermined thickness is vapor-deposited on the metal vapor-deposited layer. A method for producing a metallized film, characterized by exposing to a glow discharge. 16. The method according to claim 15, wherein the gas for maintaining the glow discharge is a gas containing an oxygen atom or a mixed gas containing a gas containing an oxygen atom. 17. The method for producing a metal-deposited film according to claim 15, wherein an organic polymer film having at least a surface opposite to the surface on which the metal-deposited layer is provided is subjected to a corona discharge treatment. 18. The method for producing a metal-deposited film according to claim 15, wherein the glow discharge treatment is performed in a vacuum deposition machine, and the treatment is performed on at least one surface of the organic polymer film. Method. 19. The method of claim 1, 2, 3, 4, 5, 6, 7,
A capacitor, wherein the metallized film according to 8, 9, 10, 11, 12, 13 or 14 is laminated or wound. 20. The method of claim 1, 2, 3, 4, 5, 6, 7,
The metal deposited film described in 8, 9, 10, 11, 12, 13 or 14 is laminated or wound, and an epoxy resin, a urethane resin or a silicone resin is used as an impregnating agent. And capacitors.