JPS637363A - Vacuum deposition method - Google Patents

Abstract

PURPOSE:To form a vapor deposited film having a sharp contour without having the conductive vapor deposition material sticking to a non-vapor deposition part with good productivity by coating a specific masking oil to the non-vapor deposition part at the time of forming the conductive film consisting of various metals or metal oxides, etc., by vapor deposition on a base material for vapor deposition except the non-vapor deposition part. CONSTITUTION:Metals such as Al, Zn, Cu, Au, and Ag or oxides such as SnO2 and In2O3 are deposited by evaporation on the surface of the base material for vapor deposition such as plastic film or glass sheet except the non-vapor deposition part by a vacuum deposition method. The perfluoroalkyl polyether having the repeating units expressed by formulas (I)-(III) and having 1,000-15,000 average mol.wt. is coated as the masking oil on the non-vapor deposition part of the base material for vapor deposition in this case; thereafter, the above-mentioned metals and oxides, etc., are deposited on the base material by the vacuum deposition method. The patterned vapor deposition having the sharp contour of the non-vapor deposition part is easily executed without sticking of the vapor deposition material to the non-vapor deposition part.

Description

Detailed Description of the Invention [Technical Field] The present invention applies masking oil to a vapor deposition base material to provide a non-evaporated area while depositing metal or gold Ii? The present invention relates to a vacuum deposition method using an oil mask method for depositing a film such as an immide conductor.

[Background Art] Conventionally, A is deposited on a deposition substrate such as a plastic film or a glass sheet, leaving a non-deposited area, that is, in a pattern.
1. Vacuum deposition methods are widely used to form metal films such as Zn, Au, and Ag, or metal oxide conductor films such as tin oxide, indium oxide, or mixtures thereof (ITO). A variety of steam products are manufactured for commercial and electrical purposes. Examples of vapor-deposited products having such a pattern-like vapor-deposited film include capacitor films in which a metal vapor-deposited film is formed leaving a margin part (non-deposited part), and electrode substrates in which a transparent electrode film such as ITO is formed. This is a typical example.

In order to form the above-mentioned patterned vapor deposition film on a vapor deposition substrate, there is a method of forming a margin part at the same time as vapor deposition using tape or an oil coating film as a masking material, or a method of forming a margin part at the same time as the vapor deposition, or using a conductive film like that described above. A known method is to form a margin portion by selectively removing the conductor film by dry or wet etching.

However, among the various methods mentioned above, in the tape mask method, which generally uses an endless tape as a masking material, (I) the tape is repeatedly exposed to metal vapor; Dimensional changes occur during work, and the margin part is easily disturbed in the width direction as it shifts from the tape guide roll. (11) The metal deposited and laminated on the tape peels off and scatters in the form of particles, causing foreign matter on the metallized film being manufactured. (III) Therefore, even endless tapes cannot be used for long periods of time, which limits the length of film that can be deposited, and the tape must be replaced after each operation. be.

Furthermore, the etching method requires a complicated etching process and has the drawback of increasing manufacturing costs.

On the other hand, the oil mask method uses a simple method of applying masking oil to the position corresponding to the margin of the vapor deposition base material by jetting steam from a nozzle or transferring it from a roll, just before the vapor deposition process. Therefore, it is expected to improve the quality of the wood over the drawbacks of the tape mask method or etching method. As the masking oil, electrically insulating silicone oil (Vacuum, Vol. 7, No. 12, p. 392), liquid paraffin, and the like have been used.

However, with the conventional oil mask method, depending on the evaporation material, a small amount of conductor adheres to the area where the oil is applied, making it difficult to form a clear margin area, and the boundary between the evaporation area and the margin area. 1. For example, when a metallized film for capacitors obtained by vapor deposition of AI is rolled up to create small precision capacitors, which have been in high demand in recent years, the insulation resistance of the room will be low due to imperfections in the margins. etc., sufficient electrical characteristics cannot be obtained.

In order to solve these problems, an average molecular weight of 230
~680, and the vapor pressure at 200°C is 0
．． A method in which oils of 1 to 20 Torr are used alone or in combination (Japanese Patent Publication No. 55-47113). After the oil is deposited, the film and the deposited oil are cooled by a cooling roll, and the evaporation of the oil is suppressed to within the limit. , a method in which oil remains on the film even after metal vapor deposition (Japanese Patent Application Laid-open No. 151011/1983) has been proposed.

However, these methods are still far from satisfactory.
For example, most of the reprinted AI-deposited metallized films for capacitors are based on the tape mask method, despite the process problems mentioned above.

[Object of the Invention] In view of the above-mentioned circumstances, an object of the present invention is to provide a vacuum evaporation method capable of forming a 'lIi kimono, particularly a clear margin portion free from adhesion of conductive vapor deposits.

Another object of the present invention is to provide a vacuum evaporation method capable of producing a evaporation product without disturbances in the margins and without defects due to entrapped foreign matter. Still another object is to provide an oil mask type vacuum deposition method that has high productivity and enables the deposition of long films.

[Summary of the Invention] The vacuum evaporation method of the present invention was developed to achieve the above-mentioned object, and more specifically, the vacuum evaporation method of the present invention is a method for vapor deposition while providing a non-base portion on a evaporation substrate using an oil mask method. It is characterized in that perfluoroalkyl polyether is used as a masking oil when forming a film.

The perfluorofurkyl polyether has an average molecular weight range of 1000 to 15000, particularly 1500 to 10
000 is preferably used.

Although it is not necessarily clear why the use of perfluoroalkyl polyether as a masking oil in the present invention achieves the desired effect, especially during vapor deposition, no adhesion of reeds and clear margins are formed. , the following can be considered.

In general, in the oil mask vacuum evaporation method, the reason why the applied oil exhibits a certain masking effect is as follows.
1) The effect of blocking vapor deposits due to oil molecule vapors that evaporate or re-evaporate due to vacuum or heat of vapor vapors, 2) The physical shielding effect of the film itself, and 3) The effect of inhibiting the formation of vapor deposits due to oil. However, the perfluoroalkyl polyether used in the present invention has a particularly preferable molecular weight range of 1500 to 100.
00, the vapor pressure at 200°C is about to'
~10-' Torr.

This cannot be explained solely by the conventional thinking that 1) above is the main factor.On the other hand, as mentioned above, perfluoroalkyl polyether has a molecular weight of 1000 to 15000, which is considerably higher than that of conventional masking oils. Although the molecular weight is 1, the surface tension is approximately 20 dyne/cm
It has an extremely low surface tension of less than 1,000 yen, and also has excellent mold releasability. Therefore, even if perfluoroalkyl polyether evaporates to some extent under the vapor deposition conditions, or even if it remains as an oil film, its large molecules exert a masking effect on the adhesion of vapor deposit particles, and its high The chemical inertness and excellent mold releasability also contribute to preventing the formation of vapor deposits. Furthermore, since the surface tension is extremely low, even if the amount of residual oil decreases due to evaporation or collision of deposited particles, reduction in the coated shape due to aggregation is prevented.

Due to these factors, perfluoroalkyl polyether is considered to have an excellent effect of preventing the adhesion of vapor deposits and an effect of forming a sharp edge margin.

[Example] Hereinafter, a method for manufacturing a metallized film for a capacitor as an example of the vacuum deposition method of the present invention will be specifically described with reference to the drawings. FIG. 1 is an internal front view of a semi-continuous manufacturing apparatus for metallized films for capacitors by oil mask vacuum deposition, and FIG. 2 is a partial plan view of the metallized film for capacitors obtained by the above method.

Referring to FIG. 1, in a vacuum chamber A, a raw film unwound from a raw film roll 1 made of PET (polyethylene terephthalate) or the like is wound onto a winding roll 4 via a cooling can 3. It will be done. During this time film 2
, vapor deposition is performed from a metal evaporation source 5 such as A1 located below the cooling can 3, and perfluoroalkyl polyether is applied in stripes from an oil supply device 6 (transfer roll in this example). A non-deposited part is formed. After vapor deposition, the film 7 that is wound up consists of a vapor deposition part 8 and a margin part 9, as shown in plan view in FIG. A film capacitor is formed by winding and laminating.

The perfluoroalkyl polyether used in the present invention preferably has F-1CF3-1CF30 at both ends.
- t f = If C2F a -te is stabilized, and the repeating unit is the following formula (1) to (m) formula (I) (C! F
a O)n Formula (II) '(Ci Fs O)n (CF20h
m formula (IIri +C2F40)n (CF20), (
Here, n and m represent the average number of repeating units that give an average molecular weight of 1,000 to 15,000 as a whole of the per-70-roalkyl polyether. Used as a mixture. Note that n:m in formulas (II) and (m) is,
The former is usually much larger, for example about 30 to 40:1. The repeating unit (CiFsO) n may be either directly owned.

Examples of commercially available products include the product name Demnum (manufactured by Daikin Industries, Ltd., linear structure of formula CI), the product name Talytox (manufactured by DuPont, branched structure of formula (I)), and the product name 7Onpurin (manufactured by Montegisson). , the branched structure of formula (II) and the formula (
■))).

As mentioned earlier, perfluoroalkyl polyether has an average molecular weight of 1000-15000, especially 1500-15000.
Those with a molecular weight in the range of 10,000 are preferably used. Those with a molecular weight of less than 1,000 have a high vapor pressure and a large evaporation loss during vacuum deposition, and the perfluoroalkyl polyether must have a viscosity suitable for coating. 15000
It is not preferable that the amount exceeds the above range because it requires heating to a high temperature for application and causes deformation of the film when applied to a film base material.

In the above, a typical embodiment of the vacuum evaporation method of the present invention has been described. However, it is easy to understand that various modifications can be made within the scope of the present invention. For example,
In addition to PET mentioned above, plastic films such as polyimide, polycarbonate, polyacetate, polypropylene, polyphenylene sulfide, paper, glass substrates, etc. can be used as vapor deposition substrates, and as long as vapor deposition is possible, especially the material There is no above restriction. In addition to Al, Zn, Cu, Nf, Ag, and Au can be used as evaporation sources.
In addition to metals such as or oxide conductors such as ITO, 5
Although V5 electric materials such as tO1Si02 and various vapor-depositable dyes and pigments are also used, various conductive materials are preferably used. Further, as the oil supply device, in addition to the above-mentioned transfer roll, a spray coating device is suitably used, and various printing devices can also be used within the range permitted by device constraints. Furthermore, the vapor deposition can also be carried out by a batch method using a Pelger. Vapor deposition methods include vacuum evaporation in a narrow sense,
Various types of sputtering are possible, and the degree of vacuum can be selected from a wide range of, for example, 10-'' to 10-6 Torr.

Furthermore, it goes without saying that the vapor deposition on the film or sheet-like substrate is not limited to one side, but may be performed on both sides.

The present invention will be explained in more detail below using typical examples and comparative examples.

As the oil supply bag M6, an oil mask type semi-continuous vapor deposition machine as shown in FIG. .

Vapor deposition was performed using different types of oil. As the base film 2, a polyethylene terephthalate film (thickness 2 mm, width 500 mm, length 20000 m) was used, and one side of the film was wound at a winding speed of 240 m/m i.
nTeA I was deposited. The degree of vacuum at the oil supply device installation part within the evaporation mA was approximately 10-2 Torr, and the degree of vacuum near where AI was deposited was 1 to 5XIO-'Torr.

The oil was spouted as vapor onto the film surface in a width of 1 mm at intervals of 8 mm. Furthermore, the surface resistance of the A1 vapor deposited area is 1.
The resistance was set to 7Ω/mouth (approximately 400 people as film thickness).

Regarding the metallized film for capacitors obtained using different oils, the amount of metal deposited and the blurring of the boundary between the vapor deposited part and the margin part of the metallized film were determined by The results of visual observation were as shown in Table 1.

Furthermore, when the margin area was wiped with methanol-impregnated gauze and subjected to luminescence analysis, AI was detected in the samples using liquid paraffin and dimethyl silicone, but not in the samples using perfluoroalkyl polyether. It wasn't done.

As can be seen from Table 1 above, the effectiveness of masking using the oil mask method varies greatly depending on the type of oil, and the specificity of perfluoroalkyl polyether is extremely clear.

Next, an experiment was conducted using a Pelger deposition tester to examine the masking effect of AI deposition on various films of perfluoroalkyl polyether. A cotton swab was impregnated with perfluoroalkyl polyether (average molecular weight: 2500) and applied to various films in a linear shape of about 5 mm in width, and A1 was vapor-deposited on the oil-coated surface of the film. For comparison, a polyethylene terephthalate film coated with liquid paraffin (average molecular weight 310) was also tested.

Table 2 shows the results of observing the state of adhesion of A1 to the oil-applied portion and the disturbance of the outer periphery of the oil-applied portion of the film after vapor deposition.

As can be seen from Table 2, Per70 loalkyl polyether exhibits an excellent masking effect when depositing At on various deposition substrates.

Furthermore, Zn and Cu other than AI are used as vapor deposits.

It was confirmed using a Pelger vacuum evaporation tester that perfluoroalkyl polyether can be suitably used as a masking oil even when metals such as Nt and Cr and oxide conductors such as ITO are deposited.

Furthermore, using a Pelger type vapor deposition tester, the average molecular weight was 3250.
Perfluoroalkyl polyether having an average molecular weight of 14500.5600.8400 was applied in place of the perfluoroalkyl polyether having an average molecular weight of 14500.5600.8400, and AI was deposited on the PET film in the same manner as described above. As a result, the average molecule is 51250
A masking effect equivalent to that of 0 perfluoroalkyl polyether was obtained. On the other hand, poly(trifluoromonochloroethylene) (average molecular weight 500.700.900.1
000.3000), partially fluorinated silicone (aoo
), polybutene (320), dioctyl phthalate (3
90), dodecylbenzene (246), diisopropylnaphthalene (212), and castor oil (432), similar to the liquid paraffin or silicone oil described above, a sufficient masking effect could not be obtained.

[Effects of the Invention] As explained above, according to the present invention, when vacuum deposition is performed while providing non-deposited areas by an oil mask method, par-20 loalkyl polyether is used as a masking oil, thereby eliminating the conventional use. It is much superior to conventional masking oils such as paraffin oil and silicone oil.
Moreover, a masking effect comparable to that of the tape masking method can be obtained, and furthermore, problems in the patterning process caused by the tape masking method or the etching method are eliminated. Therefore, by using a conductor as a vapor deposition material, remarkable effects can be obtained in the production of electrical parts such as metallized films for capacitors, electrode plates, etc., as well as in the production of decorative products, filters, etc. that require patterned vapor deposition films. It can also be suitably used for manufacturing products.

[Brief explanation of the drawing]

FIG. 1 is an internal front view of a semi-continuous manufacturing apparatus for metallized films for capacitors by oil mask vacuum deposition, and FIG. 2 is a partial plan view of the metallized film for capacitors obtained by the above method. l... Original film roll (2... its drawn out state), 3... cooling can, 4... vapor deposited product winding roll, 5... evaporation source, 6... oil supply device, 7...
Vapor deposition amount (metalized film), 8... Vapor deposition part, 9...
Margin section. Next day 13: Figure 1. Shiuni” Procedural Amendment December 17, 1985 Commissioner of the Temple Registration Agency Black 1) Mr. Akio Relationship with Patent applicant Kakogawa Plastics Co., Ltd. 4, agent address 4th floor, Haseyo Building, 3-7-7 Toranomon, Minato-ku, Tokyo 105 105 "Detailed description of the invention" column 6 of the specification, content of amendment The following sections of the specification are amended as follows. Nobuyuki Before correction 'iE #tt-2, 14Zn
% Au, Zn, Cu, Au. 217 is being done, is being done, 31
~2 Capacitor Capacitor 718 Molecular weight range Average molecule 2 ranges from 83 to 4 15.00
0 1500085 Molecular weight Average molecular weight 101 Capacitor Capacitor 12
5 Evaporation source Evaporation material 133 Transfer roll 3 Transfer roll 13 13 1-5
1 to 318 9 Electrode plate Electrode substrate 18 11 Filter Filter or more

Claims (1)

[Claims] 1. A vacuum evaporation method characterized by using perfluoroalkyl polyether as a masking oil when forming a evaporation film on a evaporation substrate while providing non-evaporation areas using an oil mask method. 2. The average molecular weight of perfluoroalkyl polyether is 1
000 to 15,000. The vacuum evaporation method according to claim 1. 3. Perfluoroalkyl polyether has the following formula (I) ~
(III) Formula (I) ■C_3F_6O■_n Formula (III) ■C_3F_6O■_n■CF_2O■_m
Formula (III) ■C_2F_4O■_n■CF_2O■_m
(Here, n and m indicate the average number of repeating units that give an average molecular weight of 1,000 to 15,000 for the perfluoroalkyl polyether as a whole.) The vacuum deposition method according to claim 1, which is a mixture. 4. The vacuum deposition method according to claims 1 to 3, wherein the deposited film is a conductor.