JP3094702B2 - Silicon oxide-based deposited film and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is excellent in gas barrier properties of oxygen gas and carbon dioxide gas, water vapor barrier properties, water resistance and chemical resistance, and has stable performance even under various severe environments. In addition, the present invention relates to a vapor-deposited film useful in applications requiring almost colorless transparency in the field of packaging materials such as food and drink, pharmaceuticals, the field of electronics such as electric insulating or conductive materials, and the field of medical materials.

[0002]

2. Description of the Related Art Conventionally, a film obtained by depositing aluminum on a plastic film has been widely used as a material for food packaging. These aluminum deposited films are excellent in flexibility, gas barrier properties and water vapor barrier properties, but are inferior in acid resistance, chemical resistance such as alkali resistance, water resistance, transparency, etc. ,
When it comes into contact with an alkali or the like, a part of the vapor-deposited layer is peeled off, and the gas barrier property and the water vapor barrier property are considerably reduced.

On the other hand, a plastic film disclosed in JP-A-49-41469 has SixOy (x = 1,2, y = 1,2,3).
A deposited film provided with a deposited thin film layer having a composition of, although having high chemical resistance, exhibits a slight yellow tint, and particularly when directly printed on the deposition surface side, a large adverse effect is exhibited by the yellow tint, In terms of design or use, for example, electroluminescent constituent materials have been a major obstacle to performance. In addition, a method of reducing the thickness of a vapor-deposited film to reduce yellow tint has been proposed,
There is also an adverse effect that the oxygen gas barrier property and the water vapor barrier property are inferior. In addition, a film provided with a vapor-deposited thin film containing Si and other elements is also known, but a particularly effective means for making the film transparent is almost unknown.

[0004]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned drawbacks. As a result, a vapor-deposited film formed by coating an organic metal compound on a vapor-deposited surface to form a vitreous film is obtained. , Gas barrier properties, water vapor barrier properties,
Not only excellent in chemical resistance and water resistance, it is not necessary to reduce the thickness of the deposited film to reduce the yellow tint, without peeling or cracking even when subjected to boiling sterilization treatment,
Further, they have found that they are almost colorless and transparent without deteriorating the gas barrier properties and water vapor barrier properties, and have reached the present invention.

[0005]

That is, the present invention provides a plastic film comprising, on at least one side of a plastic film, a silicon oxide or a vapor-deposited thin film layer containing a silicon oxide as a main component, and one or more kinds of organometallic compounds. Provided is a vapor-deposited film formed by sequentially laminating a glassy coating formed from a sol solution that has been hydrolyzed and partially condensed. The present invention also provides a method for forming one or two types of organometallic compounds on at least one surface of a plastic film after forming a silicon oxide or a deposited thin film layer containing silicon oxide as a main component on the deposited thin film layer. Provided is a method for producing a vapor-deposited film that forms a vitreous film by coating a sol solution obtained by dissolving a solution obtained by mixing the above or a mixed solution in an organic solvent such as alcohol and hydrolyzing and partially condensing the solution, and performing a heat treatment. .

[0006] The plastic film is not particularly limited. Polyester such as polyethylene terephthalate and polybutylene terephthalate, polyamide, polyvinyl chloride, polyacrylonitrile, polycarbonate, polystyrene, polypropylene, saponified ethylene-vinyl acetate copolymer, aromatic polyamide , A film made of a fluororesin or the like, or a film obtained by laminating two or more of these materials is used, and printing, silane coupling agent, application of a primer, etc., corona discharge treatment,
It may have been subjected to surface treatment such as low-temperature plasma treatment, or may be uniaxially stretched or biaxially stretched. For general packaging applications, biaxially stretched polypropylene films, polyester films and the like are preferably used in terms of gloss and strength.

A vapor deposition layer is provided on one or both sides of these plastic films, and a silicon oxide SiOx (x = 1,2)
Thin film, or magnesium with silicon oxide as a main component,
1 shows a thin film containing at least one compound containing at least one element selected from the group consisting of aluminum, zirconium, titanium, iron, calcium, boron, nickel, and chromium.

[0008] The above-mentioned deposition surface has two or more alkoxyl groups having 1 to 4 carbon atoms in the molecule, and is composed of Si, Ti, Al, B, Zr, W, and Ta.
An organometallic compound containing one kind of metal element selected from
A solution obtained by dissolving one or two or more kinds of mixed solutions, or a mixed solution thereof in an alcohol such as ethanol, and adding a hydrochloric acid and water as needed, hydrolyzing and partially condensing a sol solution, and performing a heat treatment on the glass. A porous coating is formed.

As the organometallic compound, for example, silicon tetramethoxide, silicon tetrapropoxide, titanium tetraethoxide, titanium tetrabutoxide, aluminum trimethoxide, aluminum triethoxide,
Tantalum pentapropoxide, tantalum pentabutoxide, boron trimethoxide, boron tributoxide, zirconium tetraethoxide, zirconium tetrapropoxide, tungsten hexamethoxide, tungsten hexaethoxide, silicon diethoxide, silicon triethoxide, silicon phenyl Trimethoxide, silicon diethoxydimethyl, silicon 3-aminopropyl triethoxide, silicon benzyl triethoxide, silicon 3-chloropropyl dimethoxide, silicon diethoxy dichloride, titanium dimethoxide, titanium diethoxydimethyl, titanium diethoxy diphenyl , Titanium dichlorodiethoxide, aluminum dimethoxide, aluminum diethoxyethyl, aluminum diethoxyphenyl, tantalum Liethoxide, tantalum diethoxy trimethyl, boron dimethoxide, boron diethoxymethyl, boron chlorodiethoxide, zirconium diethoxide, zirconium triethoxide, zirconium phenyl trimethoxide, zirconium diethoxydimethyl, zirconium diethoxy dichloride, tungsten trimethoxy , Tungsten triethoxytrimethyl, tungsten dichlorotetraethoxide, tungsten diphenyltetraethoxide and the like.

The above mixed solution is obtained by dissolving 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight of an organometallic compound in 100 parts by weight of a solvent. The mixed solution of the organometallic compound is uniformly applied to the deposition surface by bar coating, gravure coating, or the like, and then heated and dried to form a vitreous film. The film thickness at this time is suitably from 0.1 to 3 μm, and preferably from 0.1 to 0.5 μm. Thickness 0.1μm
If it is less than 3 μm, it is not enough to make the deposited film highly transparent, and if it exceeds 3 μm, the coating will peel off. The vapor-deposited film obtained by forming a glassy film on the vapor-deposited surface obtained according to the present invention, if necessary, is further subjected to printing or coating, or a plastic film laminated with or without an adhesive or a laminating adhesive. You may. And it can be widely used as a packaging material, a gas barrier material, an electrical insulating material or a conductive material in the fields of food and drink, pharmaceuticals, medical care, electronic materials, etc. as a film or processed into a shape such as a bag or a tube. .

[0011]

The present invention will be described in more detail with reference to the following examples. In the examples, OP is the oxygen gas permeability measured by the same pressure method, and its unit is ml / m ² · 24 hours · 1 atm · 25 ° C · 1
00% RH. WVT is the moisture permeability measured by the infrared absorption method, and its unit is ml / m ² · 24 hours · 40 ° C · 90% RH
It is. T% is the transmittance at 400 nm by a spectrophotometer. In addition, the display of those units was all omitted in the example.

Example 1 100 parts of ethanol, 4 parts of tetraethoxysilane, 1 part of trimethoxyborane, 5 parts of water,
A mixed solution comprising 0.3 parts of hydrochloric acid was left for 24 hours to obtain a coating solution.
Silicon oxide vapor deposition film (GT1000 manufactured by Toyo Ink Mfg. Co., Ltd.)
The above coating solution was applied to the deposition surface of N) using a bar coater # 20, dried at 60 ° C. for 1 hour, and T% of the obtained deposition film was measured to evaluate the transparency. Table 1 shows the results. Then, using a polyurethane-based adhesive for lamination (Adcoat # 810, manufactured by Toyo Morton Co., Ltd.), the coated film-deposited film and an unstretched polypropylene film having a thickness of 50 μm were bonded by a conventional method. OP and WTR were measured at 10 points each, and the average of the measured values was calculated. Table 1 shows the results.

[Comparative Example 1] T%, OP, and WTR of an untreated silicon oxide vapor-deposited film (GT1000N manufactured by Toyo Ink Mfg. Co., Ltd.) were measured in the same manner as in Example 1, and the results are shown in Table 1.
Shown in [Example 2] 100 parts of ethanol, tetraethoxysilane
A mixture of 5 parts, 10 parts of water and 0.3 parts of hydrochloric acid was left for 24 hours to obtain a coating liquid. The above coating solution was applied to a deposition surface of a silicon oxide deposition film (GT1000N manufactured by Toyo Ink Mfg. Co., Ltd.) using a bar coater # 20, and dried at 60 ° C. for 1 hour. Unstretched polypropylene of 50 μm was adhered to the deposited film subjected to the coating treatment. The obtained laminate was exposed to steam at 100 ° C. for 3 hours. T%, OP and WVT before and after exposure were measured. Table 1 shows the results.

[0014]

[Table 1]

[0015]

According to the present invention, not only gas barrier properties, water vapor barrier properties, chemical resistance and water resistance are excellent, but also
Even when subjected to boiling sterilization treatment, peeling and cracking did not occur, and gas barrier properties and water vapor barrier properties did not decrease, so that almost colorless and transparent films could be obtained.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C23C 14/00-14/58 B32B 1/00-35/00

Claims (3)

(57) [Claims] A sol solution obtained by hydrolyzing and partially condensing one or more kinds of organometallic compounds with silicon oxide or a vapor-deposited thin film layer containing silicon oxide as a main component on at least one surface of a plastic film. A vapor-deposited film obtained by sequentially laminating a vitreous coating formed by using the method. 2. An organometallic compound having at least two alkoxyl groups having 1 to 4 carbon atoms in a molecule thereof, wherein Si, Ti, Al, B, Zr, W,
The vapor-deposited film according to claim 1, which is a compound containing one kind of metal element selected from Ta. 3. A method according to claim 1, wherein at least one surface of the plastic film is formed with silicon oxide or a vapor-deposited thin film layer containing silicon oxide as a main component, and one or two or more organometallic compounds are formed on the vapor-deposited thin film layer. Or a solution obtained by dissolving this mixed solution in an organic solvent such as alcohol and coating it with a sol solution that has been hydrolyzed and partially condensed, followed by heat treatment to form a glassy film.