JPH083727A - Vacuum deposition method - Google Patents

Abstract

(57) [Abstract] [Purpose] In a vacuum vapor deposition method for continuously supplying / discharging a mixed raw material of a silicon oxide and an alkali metal or alkaline earth metal fluoride, a vapor deposition film having a composition reflecting the raw material composition is formed. To provide a vacuum vapor deposition method for obtaining. A vacuum deposition method for continuously supplying / discharging a mixed raw material of a silicon oxide and a fluoride of an alkali metal or an alkaline earth metal, a deposition rate of a silicon oxide / an alkali metal or an alkaline earth metal A vacuum vapor deposition method, characterized in that the ratio of the vapor deposition rates of fluorides is 9.5 to 7.5 / 2.5 to 0.5. [Effects] A vapor-deposited film having both barrier properties and dimensional stability dependent on silicon oxide and high transparency dependent on a fluoride of an alkali metal or an alkaline earth metal can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to vacuum deposition of a flexible plastic film having various functions, which can be used in the fields of food packaging, pharmaceutical packaging, electronic device component packaging, tobacco packaging, photoengraving, photosensitive photographic materials and the like. Regarding the method.

[0002]

2. Description of the Related Art In recent years, the surface of a flexible plastic film is coated with a metal or a metal oxide by a vacuum vapor deposition method to improve the decorative property, gas barrier property, chemical resistance, wetting property, magnetic property, electrical conductivity, dimensional stability, etc. With added functionality, it has come to be used in fields such as food packaging, pharmaceutical packaging, electronic device component packaging, tobacco packaging, photoengraving and photosensitive photographic materials. In addition, recently, research and development of silicon oxide vapor deposition film has been actively carried out as a transparent high barrier material with little environmental pollution, and it is expected that it will be widely spread, and the demand for the development of metal oxide vapor deposition technology is increasing day by day. It's getting stronger.

In particular, when vacuum vapor deposition is performed using two or more kinds of raw materials, the characteristics of the mixed raw materials are reflected in the vapor deposition film, and the resultant vapor deposition film has two or more characteristics. For example, when a material obtained by adding a metal fluoride to silicon oxides is vacuum-deposited, a high transparency can be obtained in addition to the barrier property and the dimensional stability. However, in reality, when a mixture of a silicon oxide and a metal fluoride is vacuum-deposited, the reaction sublimation point, the sublimation point, etc. are different from each other. When the vapor deposition film composition does not reflect the raw material composition, the expected physical properties were not obtained as a result.

[0004]

An object of the present invention is to reflect a raw material composition in a vacuum deposition method for continuously supplying / discharging a mixed raw material of a silicon oxide and a fluoride of an alkali metal or an alkaline earth metal. It is to provide a vacuum vapor deposition method for obtaining a vapor deposited film having the above composition.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a vacuum vapor deposition method for continuously supplying / discharging a mixed raw material of a silicon oxide and a fluoride of an alkali metal or an alkaline earth metal. The ratio of the rate / vapor deposition rate of the alkali metal or alkaline earth metal fluoride is 9.5 to
It is achieved by a vacuum vapor deposition method characterized in that it is 7.5 / 2.5 to 0.5.

Examples of silicon oxides include one or more silicon oxides selected from silicon, silicon dioxide, silicon monoxide, and SiO _x (X = 1 to 2).
Silicon is not particularly limited as long as it has a purity of 97% or more and is in powder form. Further, silicon oxides are silicon monoxide (SiO).
And SiO _x containing silicon dioxide (SiO ₂ ) (X = 1 to
It is 2), and it may be powdery with a purity of 97% or more, and the silicon dioxide may be amorphous or crystalline. When silicon / silicon dioxide is used as the silicon oxides, the composition ratio thereof is basically desired to be equimolar, and 40 mol% to
It may be in the range of 60 mol% / 60 mol% to 40 mol%. If it deviates from this range, the reaction is unlikely to occur, so that elution of silicon or silicon dioxide occurs. When silicon monoxide is further mixed with silicon and silicon dioxide, the mixing ratio of silicon monoxide is not particularly limited.

Examples of alkali metal fluorides include sodium fluoride, potassium fluoride, lithium fluoride and cesium fluoride. Examples of the alkaline earth metal fluoride include magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride and the like.
Particularly, magnesium fluoride and calcium fluoride are excellent. The average particle size of the silicon oxide and the alkali metal or alkaline earth metal fluoride is preferably 0.5 to 40 μm, more preferably 0.8 to 20 μm. Further, it is preferable that the average particle diameters of the respective particles are relatively the same, and the difference between the average particle diameters of the respective particles is preferably within ± 15 μm. Further, the composition ratio of silicon oxides / fluoride of alkali metal or alkaline earth metal is from 64 mol% to 98 mol% / 2 mol%.
36 mol% is preferable.

In the present invention, the vacuum vapor deposition method for continuously supplying / discharging the raw material is basically not limited as long as it is the vacuum vapor deposition method for continuously supplying / discharging the raw material, but JP-A-1-252786. Japanese Patent Laid-Open No. 2-277774
The vapor deposition method described in the publication is desirable. The heating method is also not limited, and any known method such as resistance heating method, high frequency induction heating method, or electron beam heating method can be selected without particular limitation. As a method for controlling the vapor deposition rate (evaporation amount per unit time), a temperature-based control method can be mentioned. Here, the temperature control is the temperature control of the evaporation source. As a method of measuring the vapor deposition rate (evaporation amount per unit time), a method of using a quartz-type film thickness monitor or the light transmittance of the vapor deposition film obtained from the correlation between the light transmittance of the vapor deposition film and the geometrical film thickness is used. There is a method of using.

In the present invention, the vapor deposition rates at the respective temperatures of silicon oxides and alkali metal or alkaline earth metal fluorides are measured, and the vapor deposition rate ratio is 9.5.
The vapor deposition temperature is determined so as to be ~ 7.5 / 2.5-0.5. By performing vacuum vapor deposition at a vapor deposition temperature that is a ratio of this vapor deposition rate, the composition ratio of the raw material can be reflected in the composition ratio of the vapor deposition film, and the barrier property dependent on silicon oxide, humidity dimensional stability, etc. and alkali metal or It is possible to achieve both high transparency depending on the fluoride of the alkaline earth metal. If you want to achieve both high barrier properties and high transparency, use a mixed raw material of silicon oxide and fluorides of alkaline earth metals, and if you want to achieve both low barrier properties and high transparency, use silicon oxide. A mixed raw material of alkali metal fluoride is used.

When the ratio of the deposition rate of silicon oxides exceeds 9.5 (the ratio of the deposition rate of fluorides of alkali metal or alkaline earth metal is less than 0.5), the dependence of the alkaline earth metal fluoride depends. Is inferior in transparency, and if it is less than 7.5 (ratio of deposition rate of fluoride of alkali metal or alkaline earth metal exceeds 2.5), problems such as barrier property and dimensional stability dependent on silicon oxide occur. Occurs.

[0011]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples as long as the gist thereof is not exceeded. The test method in the examples is as follows. Water vapor barrier property: In accordance with ASTM F 1249,
PERMATRAN-W of Modern Controls, Inc.
-The water vapor transmission rate was measured using TWIN. transparency:
The transmittance at 350 nm was measured using a spectrophotometer (U-best30 manufactured by JASCO Corporation) with air as a reference.

[Example 1] A vacuum vapor deposition apparatus having a mechanism for continuously supplying / discharging raw materials as described in JP-A-1-252768 was used. The heating method of the evaporation source was a resistance heating method, and the temperature was controlled by a radiation thermometer. silicon/
1 × 10 of an equimolar mixture of silicon dioxide (silicon oxides)
The evaporation rate at ^-3 torr and 1400 ° C was determined by a crystal type film thickness monitor, and it was 0.037 μm ³ / min.
・ It was m ³ . Next, 1 × 10 ^-3 of calcium fluoride
The evaporation rate at 1400 ° C. was determined by a quartz-type film thickness monitor to be 4.1 × 10 ⁻³ μm ³ / mi
It was n · m ³ . The ratio of the evaporation rate of silicon oxides / the evaporation rate of calcium fluoride at 1 × 10 ⁻³ torr and 1400 ° C. was 9.0 / 1.0. Mixture of silicon / silicon dioxide / calcium fluoride (composition ratio is 45 mol% /
45 mol% / 10 mol%) at 1 × 10 ⁻³ torr, 14
It was vacuum-deposited on a polyethylene terephthalate film having a thickness of 12 μm under the condition of 00 ° C.

[Comparative Example 1] Using the vacuum vapor deposition apparatus used in Example 1, vacuum vapor deposition was performed. 1 × 10 ⁻³ torr of silicon / silicon dioxide equimolar mixture (silicon oxides)
When the evaporation rate at 50 ° C. was measured with a quartz-type film thickness monitor, it was 0.12 μm ³ / min · m ³ . Next, 1 × 10 ⁻³ torr of magnesium fluoride, 145
The evaporation rate at 0 ° C. was measured by a crystal type film thickness monitor, and it was 3.1 × 10 ⁻³ μm ³ / min · m ³ . The ratio of the evaporation rate of silicon oxides / the evaporation rate of magnesium fluoride at 1 × 10 ⁻³ torr and 1450 ° C. was 9.75 / 0.25. A mixture of silicon / silicon dioxide / magnesium fluoride (composition ratio: 45 mol% / 45 mol% / 10 mol%) at 1 × 10 ⁻³ torr, 1450 ° C.
Under the above conditions, a 12 μm thick polyethylene terephthalate film was vacuum-deposited.

[Comparative Example 2] Using the vacuum vapor deposition apparatus used in Example 1, vacuum vapor deposition was performed. 1 × 10 ^{-3 of} silicon monoxide
The evaporation rate at 1300 ° C. was determined by a quartz-type film thickness monitor to be 5.1 × 10 ⁻³ μm ³ / mi.
It was n · m ³ . Next, 1 x 1 of magnesium fluoride
The evaporation rate at 0 ^-3 torr and 1300 ° C was determined by a quartz-type film thickness monitor to be 5.1 x 10 ^-3 μm ³ /
It was min · m ³ . 1 × 10 ^-3 torr, 1300
The ratio of the evaporation rate of silicon monoxide / the evaporation rate of magnesium fluoride at 5.0 ° C. was 5.0 / 5.0. Mixture of silicon monoxide / magnesium fluoride (composition ratio is 90 mol% /
10 mol%) was vacuum-deposited on a polyethylene terephthalate film having a thickness of 12 μm under the conditions of 1 × 10 ⁻³ torr and 1300 ° C.

The vapor-deposited films obtained in Examples and Comparative Examples were evaluated for water vapor barrier property and transparency. The results are shown in Table 1.

[Table 1]

[0016]

According to the present invention, it is possible to obtain a vapor-deposited film having both barrier properties and dimensional stability dependent on silicon oxide and high transparency dependent on the fluoride of alkali metal or alkaline earth metal.

Claims (2)

[Claims] 1. A vacuum vapor deposition method in which a mixed raw material of a fluoride of silicon oxides and an alkali metal or an alkaline earth metal is continuously supplied / discharged.
A vacuum vapor deposition method, characterized in that the ratio of vapor deposition rates of alkali metal or alkaline earth metal fluorides is 9.5 to 7.5 / 2.5 to 0.5. 2. The vacuum deposition method according to claim 1, wherein the fluoride of the alkaline earth metal is magnesium fluoride and / or calcium fluoride.