JPH08151082A - Preservation of part applied with metal vapor deposition film - Google Patents

Abstract

PURPOSE: To well hold a metal vapor deposition film by preventing the oxidation of the metal film applied to glass, ceramic matter, various metals, plastic, paper or cloth by vapor deposition. CONSTITUTION: A part to which a metal vapor deposition film is applied is hermetically sealed in a gas barrier container along with an oxygen absorbing agent containing a substance based on an unsaturated fatty acid compd. and/or a chain hydrocarbon polymer having an unsaturated group and accelerating oxygen absorption and a dehumidifying agent to be preserved under an atmosphere from which oxygen and moisture are substantially removed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for storing a component having a metal vapor deposition film, for example, glass vapor deposition for welding, Al vapor deposition of a reflective layer of an optical disk, and a substrate for semiconductor components in the electronic industry. And photomask deposition,
Glass, ceramic body, various metals, plastic, paper,
And to prevent oxidation of a vapor deposited metal film deposited on a cloth.

[0002]

2. Description of the Related Art In recent years, surface processing techniques such as vacuum deposition method, ion plating method and laser deposition method have progressed, and it has become possible to deposit a metal very thinly and uniformly. For this reason, it is becoming possible to utilize the characteristics of the metal by using only a small amount of expensive metal. For example, as a mask for welding, Ti on the glass surface
There is a technique of using a vapor-deposited product. In this case, Ti
There is no problem if it is made into laminated glass immediately after vapor deposition of, but if it is stored for a long time after vapor deposition, the surface of the activated vapor deposition film becomes cloudy, and when it is made into laminated glass, the performance as a welding mask It was often not possible to get.

The Al reflection layer of an optical disk such as a compact disk or a video disk is formed by forming a disk using a synthetic resin such as polycarbonate or acrylic, and then depositing Al on the pit transfer surface.
There is a step of providing a transparent resin protective layer to protect the Al reflective layer, but if a protective layer is provided before the protective layer is provided, even if a protective layer is provided later, the Al vapor deposition surface will be There was a case where a good reflective surface could not be obtained due to corrosion.

For the purpose of preventing such a metal vapor deposition film from fogging, even if a desiccant such as silica gel is used to store the vapor deposited metal on glass, ceramics, various metals, plastics, paper, cloth, etc. After vapor deposition, the surface lost its gloss due to oxygen in the system and became cloudy, and often did not function sufficiently as a vapor deposition film. Therefore, for the purpose of deoxidizing oxygen, an attempt was made to store the parts on which a metal vapor deposition film was formed by using an oxygen agent in combination with a desiccant. However, even if a conventionally known deoxidant, for example, an iron powder, sulfite, catechol, or a deoxidant containing ascorbic acid as a main component is used, the oxygen absorption capacity is lowered on the way and the oxygen cannot be sufficiently deoxidized. Even if oxygen was sufficiently removed, the surface was still cloudy and the vapor deposited metal film could not always be held well. As described above, the fact is that there is no simple storage method for a component provided with a metal vapor deposition film so far.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to prevent the active vapor-deposited film from being deteriorated by oxidation after vapor-depositing the metal, and to keep the vapor-deposited surface of the metal well. It is an object of the present invention to provide a method of storing a component having a metal vapor deposition film, which can achieve the above.

[0006]

The inventors of the present invention need to simultaneously cut off both oxygen and moisture in the storage atmosphere in order to prevent the deterioration of the metal vapor deposition film and achieve the above object. The above object is obtained by sealing the metal vapor-deposited component in a gas barrier container together with an oxygen absorbent and a dehumidifying agent whose main component is an unsaturated fatty acid compound and / or a chain hydrocarbon polymer having an unsaturated group. The inventors have found that this can be easily achieved and have reached the present invention.

That is, the method for preserving a component provided with a metal vapor deposition film of the present invention is characterized in that the component provided with a metal vapor deposition film is sealed in a gas barrier container from which oxygen and water have been substantially removed. Is. Further, the method of the present invention is characterized in that in the above method, the inside of the gas barrier container is kept at an oxygen concentration of 5% or less and a relative humidity of 10% or less. Furthermore, the method of the present invention is a method in which a metal vapor-deposited film-containing component is used as a main component of a chain hydrocarbon polymer having an unsaturated fatty acid compound and / or an unsaturated group to promote oxygen absorption. It is characterized in that it is sealed in a gas barrier container together with an oxygen absorbent and a dehumidifying agent. Further, the method of the present invention comprises
In the above method, an acidic gas absorbent is further enclosed in the gas barrier container. The present invention will be described in detail below.

The parts provided with the metal vapor deposition film in the present invention include glass, ceramics, various metals, plastics,
It means one having a metal vapor deposition film deposited on the surface of paper, cloth and the like. The metal vapor deposition film is made of Cu, Ag, Au, Ni, P.
d, Pt, Co, Rh, Ru, Ti, Zr, Hf, V,
A thin film of a metal such as Cr, Mn, Al, Pb, or Bi is formed by a vapor deposition method such as a vacuum vapor deposition method, an ion plating method, or a laser vapor deposition method.

In the method of the present invention, it is necessary that the metal vapor-deposited film-coated component is hermetically sealed in a gas barrier container from which oxygen and water have been substantially removed. Here, the state in which oxygen is substantially removed means an oxygen concentration of 5% or less, preferably 1% or less, and more preferably 0.1% or less.
In addition, the state in which water is substantially removed means that the relative humidity is 1
0% or less, preferably 5% or less, more preferably 1%
Says: In the method of the present invention, an atmosphere in which only one of oxygen and water is removed is insufficient, and it is essential to create a state of substantially oxygen-free and low humidity in the system at the same time. When either the oxygen concentration or the relative humidity is high, oxidation of the metal vapor deposition film progresses and clouding may occur on the vapor deposition surface.

In the present invention, the above atmosphere can be created by sealing the metal vapor-deposited film part together with the oxygen absorbent and the dehumidifying agent in the gas barrier container, and the oxygen absorbent can be used even under low humidity. It must be able to absorb oxygen. Further, since the deterioration of the vapor deposition surface is further promoted in the presence of the acidic gas, the combined use with the acidic gas absorbent is also effective. By the way, conventionally, for example, an oxygen absorbent containing iron powder, sulfite, catechol, ascorbic acid and / or a salt thereof as a main ingredient is well known.
These oxygen absorbents require moisture in order to absorb oxygen, and those in which moisture coexists are used in the dry system. However, such an oxygen absorbent that requires water for absorbing oxygen cannot be used in the present invention.

The oxygen absorbent used in the present invention contains an unsaturated fatty acid compound which is a main component and / or a chain hydrocarbon polymer having an unsaturated group, and a substance which promotes oxygen absorption, and is usually It further comprises a carrier material.

The unsaturated fatty acid compound used herein is an unsaturated fatty acid having 10 or more carbon atoms and a double bond between carbons, or a salt or ester of the unsaturated fatty acid. The unsaturated fatty acid and its fatty acid salt or ester may have a substituent such as a hydroxyl group and a formyl group. Further, the unsaturated fatty acid compound does not necessarily have to be a pure substance.

Examples of unsaturated fatty acid compounds include unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, parinaric acid dimer acid, ritinoleic acid and ricinoleic acid, and fats and oils containing these esters. , And metal salts. Further, as the unsaturated fatty acid, vegetable oil, fatty acid obtained from animal oil, that is, linseed oil fatty acid, soybean oil fatty acid, tung oil fatty acid, bran oil fatty acid, sesame oil fatty acid, cottonseed oil fatty acid rapeseed oil fatty acid, tall oil fatty acid and the like are also used.

The chain hydrocarbon polymer having an unsaturated group is a polymer having 10 or more carbon atoms and one or more double bonds between carbon atoms and its derivatives. The derivative may have, for example, a hydroxyl group, an amino group, a formyl group or a carboxyl group as a substituent. Examples of chain hydrocarbon polymers having unsaturated groups include oligomers and polymers such as butadiene, isoprene and 1,3 pentadiene. The chain hydrocarbon polymer having an unsaturated group does not necessarily have to be a pure substance, and a small amount of impurities such as a solvent mixed in at the time of its production is allowed within a common sense range.

Examples of the substance that promotes oxygen absorption include metal salts and radical initiators that promote autoxidation of organic compounds. Here, the metal is a transition metal, and preferably Cu, Fe, Co, Ni, Cr, Mn and the like can be mentioned. As the transition metal salt, for example, unsaturated fatty acid transition metal salt can be preferably used.

The dehumidifying agent used in the present invention includes paper made of natural pulp and synthetic pulp, synthetic paper, silica gel,
Alumina, activated carbon, zeolite, perlite, activated clay, quicklime, barium oxide, calcium chloride, barium bromide, calcium hydride, calcium sulfate, magnesium chloride, magnesium oxide, magnesium sulfate, aluminum sulfate, sodium sulfate, sodium carbonate, potassium carbonate , Zinc chloride and the like.

These dehumidifying agents can function as dehumidifying agents and can be used as a carrier substance by impregnating or mixing the main ingredient with an oxygen absorption promoting substance as one component of the oxygen absorbing agent. It is desirable that the liquid substance is supported by the adsorptive substance. In the present invention, using a dehumidifying agent as a carrier is a practical use.

In the present invention, it is preferable to further use an acid gas absorbent in combination with the dehumidifying agent. The acidic gas absorbent may be any substance capable of absorbing or adsorbing an acidic substance contained in the atmosphere to be stored or an acidic substance generated by the reaction of the main agent and oxygen, and if the object to achieve this purpose is acidic gas The absorbent is not particularly limited. Preferable examples of the acidic gas absorbent include oxides, hydroxides, carbonates, organic acid salts and organic amines of alkali metals or alkaline earth metals. In the present invention, the dehumidifying agent can function as an acidic gas absorbing agent by selecting a dehumidifying agent having an acid gas absorbing ability.

In the oxygen absorbent used in the present invention, the range of 0.01 to 10 parts by weight is usually preferable for 100 parts by weight of the main agent. Further, the dehumidifying agent is 1 to 100 with respect to 100 parts by weight of the main component of the oxygen absorbent.
The range of 0 parts by weight is preferable, and the acid gas absorbent is 1
A range of up to 1000 parts by weight is preferred.

In the present invention, the oxygen absorbent, the dehumidifying agent, and the acidic gas absorbent may be mixed and used. These mixtures as a composition, as appropriate,
It is used in the form of powder, granules, tablets and the like. The oxygen absorbent composition containing a dehumidifying agent and further an acidic gas absorbent is not preferable to directly touch the article to be stored, and is packaged in a breathable packaging material to be used as a package. Further, the dehumidifying agent and the acidic gas absorbent may be partly or wholly used as a package different from the oxygen absorbent package.
The form of the package is not necessarily limited, for example, a pouch shape,
Examples include a sheet form or a blister package. The packaging material and configuration of the package are not particularly limited, but for example, a pouch obtained by laminating a plastic film having paper or nonwoven fabric as a base material and having holes formed therein may be filled with the above composition and heat-sealed to form a package. it can.

The gas barrier container used in the present invention is
As gas barrier property, oxygen permeability at 25 ° C., 60% RH is 10 ml / m ² · Day · atm or less, and
Water vapor permeability at 40 ° C, 90% RH is 1g / m ² ·
It is preferably Day or less. The barrier container is selected according to the storage of its parts, and it may be a plastic container made of gas barrier material, a film bag or a metal container. It is set in terms of time, and it is also advantageous in terms of cost to choose not to cause excessive performance depending on the purpose.

[0022]

EXAMPLES Examples of the present invention will be shown below and will be described more specifically. The present invention is not limited to these examples.

Example 1 A gas absorbent package containing an oxygen absorbent packaged in a breathable packaging material was manufactured in advance as follows. Soybean oil 1 g and cobalt naphthenate 0.
3.5 g of zeolite was added to 2 g of the mixture, and the mixture was mixed with a blender and allowed to stand at 25 ° C. for 10 minutes to obtain a fluid granular material. 5 g of the obtained powder and granules were mixed with 2.5 g of quick lime, and the mixture was filled in a small paper bag (size: 5 cm × 7.5 cm) laminated with a polyethylene film having an inner surface, and this small bag was heat-sealed. . Next, Ti vapor-deposited glass was obtained by vapor-depositing Ti on the surface of a glass plate (10 mm × 10 mm, thickness 5 mm) to a thickness of 20 Å. Immediately, Ti vapor-deposited glass and the above-prepared gas absorbent package are packed in an aluminum foil laminated material (stretched polypropylene / aluminum foil / polyethylene) packaging bag (size: 220 mm ×).
300mm, hereinafter referred to as "Al bag". ), Air 50
The bag was heat-sealed and sealed with 0 ml (25 ° C., 60% RH). The sealed bag of Ti vapor-deposited glass enclosing the gas absorbent package as described above was stored in an atmosphere of 40 ° C. and 95% RH for 30 days. When the oxygen concentration and the water concentration in this sealed bag were measured by gas chromatography, it was confirmed that the inside of the system was maintained in an atmosphere substantially free of oxygen and water until the 30th day. Further, when the Ti vapor-deposited glass was taken out from the bag and the surface was observed, the Ti vapor deposition surface was not clouded at all, and the surface was the same as that immediately after vapor deposition. The results are shown in Table 1.

Comparative Example 1 Similar to Example 1, Ti vapor-deposited glass immediately after vapor deposition was sealed in an Al bag, and the temperature was 40 ° C. and 95% R.
It was stored under an atmosphere of H 2. Open the bag after 30 days and remove from the bag
When the i-deposited glass was taken out and the surface was observed,
Vague cloudiness was observed on the vapor deposition surface.

Comparative Example 2 As in Example 1, Ti vapor-deposited glass immediately after vapor deposition was enclosed in an Al bag together with four Fuji Silica Gel type A (manufactured by Fuji Davison Chemical Co., 2 g).
It was stored in an atmosphere of 40 ° C. and 95% RH. After 30 days, it was opened and the Ti vapor-deposited glass was taken out from the bag and the surface was observed. As a result, slight fog was observed on the Ti vapor deposition surface.

[Comparative Example 3] Similar to Example 1, Ti vapor-deposited glass immediately after vapor deposition was sealed in an Al bag together with one self-reactive iron powder type oxygen scavenger (Ageless Z-100PK, manufactured by Mitsubishi Gas Chemical Co., Ltd.). It was stored under an atmosphere of 40 ° C. and 95% RH. After 30 days, it was opened and the Ti vapor-deposited glass was taken out from the bag and the surface was observed. As a result, slight fog was observed on the Ti vapor deposition surface.

The results of Example 1 and Comparative Examples 1 to 3 are shown in Table 1.

[Table 1]

[0028]

According to the method of the present invention, oxidation of the metal vapor deposition film is prevented by storing the metal vapor deposition film in a gas barrier container in an atmosphere substantially free of oxygen and water. Can be held satisfactorily and, for example, there will be no fog on the metal vapor deposition surface. Particularly, according to the present invention, a component provided with a metal vapor-deposited film is used as an oxygen absorbent containing an unsaturated fatty acid compound and / or a chain hydrocarbon polymer having an unsaturated group as a main component and a substance that promotes oxygen absorption. By sealing in a gas barrier container together with a dehumidifying agent, it is possible to satisfactorily store a component provided with a metal vapor deposition film by a very simple method.

Claims (4)

[Claims] 1. A method for preserving a component provided with a metal vapor deposition film, which comprises sealing the component provided with a metal vapor deposition film in a gas barrier container from which oxygen and moisture have been substantially removed. 2. The method according to claim 1, wherein the atmosphere in the gas barrier container has an oxygen concentration of 5% or less and a relative humidity of 10% or less. Preservation method. 3. An oxygen absorbent and a dehumidifying agent, which comprises a metal vapor-deposited component as a main component of a chain hydrocarbon polymer having an unsaturated fatty acid compound and / or an unsaturated group, and a substance that promotes oxygen absorption. At the same time, the container is sealed in a gas barrier container, and the method for preserving a component provided with a metal vapor deposition film according to claim 1 or 2. 4. An oxygen absorbent containing a substance having a metal vapor-deposited film, a main component of which is a chain hydrocarbon polymer having an unsaturated fatty acid compound and / or an unsaturated group, and a substance which promotes oxygen absorption, and dehumidification. The method for preserving a component provided with a metal vapor deposition film according to claim 1 or 2, which is sealed in a gas barrier container together with an agent and an acidic gas absorbent.