JPH0226578B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metallized inorganic film, which is formed by providing a metal vapor-deposited layer on a film mainly made of an inorganic layered compound. Conventionally, as an example of a metallized inorganic film, there is a film in which a metal is deposited on a film made of an inorganic layered compound (for example, British Patent No. 1016385).
It has been known. However, such metallized inorganic films have poor flexibility;
It had drawbacks such as low strength and elongation, not having enough toughness to withstand practical use, and poor adhesion (deposition strength) between the base film and the deposited metal layer. An object of the present invention is to eliminate the above-mentioned drawbacks and provide a metallized inorganic film that has excellent toughness, flexibility, and adhesion (vapor deposition strength) as well as excellent heat resistance properties. . In order to achieve the above object, the present invention has the following configuration:
That is, it is characterized by a metallized inorganic film comprising a mixture of an inorganic layered compound and a polar polymer compound in an amount of 1 to 30% by weight based on the inorganic layered compound, and a metal vapor-deposited layer provided on at least one side of the film. It is something. The inorganic layered compound used in the present invention is an inorganic compound having a crystal structure in which the crystal unit cell is repeated in the thickness direction. Among the inorganic layered compounds, preferable ones include silicon oxide as a main component,
It is a clay-based mineral and a mica-based mineral represented by the following general formula. _{W 0.3 ~ 1 _} A type of ion selected from among them. X: One or two ions selected from magnesium, iron, nickel, manganese, aluminum, and lithium. Y: One or two ions selected from ion, aluminum, germanium, iron, and boron. O: Oxygen Z: One or two ions selected from fluorine or hydroxyl groups. Specific examples of the inorganic layered compound represented by the above general formula are shown in the following (1) to (10), among which particularly preferred are (1) to (6). (1) LiMg ₂ Li (Si ₄ O ₁₀ ) F ₂ NaMg ₂ Li (Si ₄ O ₁₀ ) F ₂ KMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (2) Li _0.33 Mg _2.67 Li _0.33 (Si ₄ O ₁₀ )F ₂ Na _0.33 Mg _2.67 Li _0.33 (Si ₄ O ₁₀ ) F ₂ K _0.33 Mg _2.67 Li _0.33 (Si ₄ O ₁₀ ) F ₂ (3) Li _0.67 Mg _2.33 Li _0.67 (Si ₄ O ₁₀ ) F ₂ Na _0.67 Mg _2.33 Li _0.67 (Si ₄ O ₁₀ ) F ₂ K _0.67 Mg _2.33 Li _0.67 (Si ₄ O ₁₀ ) F ₂ (4) Na _0.33 Mg _0.33 Al _2.67 (Si ₄ O ₁₀ ) (OH) ₂ K _0.33 Mg _0.33 Al _2.67 (Si ₄ O ₁₀ ) (OH) ₂ (5) Interlayer ions in (1) to (4) are replaced with alkylammonium ions. (6) LiMg _2.5 (Si ₄ O ₁₀ ) F ₂ NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ KMg _2.5 (Si ₄ O ₁₀ ) F ₂ (7) Ba _0.33 Mg _3.33 Al _2.67 (Si ₄ O ₁₀ ) (OH ) ₂ (8) LiMg ₂ Li (Si ₄ O ₁₀ ) (OH) ₂ NaMg ₂ Li (Si ₄ O ₁₀ ) (OH) ₂ KMg ₂ Li (Si ₄ O ₁₀ ) (OH) ₂ (9) LiMg ₃ ( BSi ₃ O ₁₀ ) F ₂ NaMg ₃ (BSi ₃ O ₁₀ ) F ₂ KMg ₃ (BSi ₃ O ₁₀ ) F ₂ (10) LiMg ₃ (BSi ₃ O ₁₀ ) (OH) ₂ NaMg ₃ (BSi ₃ O ₁₀ ) (OH) ₂ KMg ₃ (BSi ₃ O ₁₀ ) (OH) ₂ The polar polymer compound used in the present invention is a compound with a degree of polymerization of 100 or more, and has at least one repeating unit in the polymer. A polymer compound with polar functional groups. Here, a polar functional group is a functional group with a bonding moment of 0.7 Debye or more, preferably
A functional group with at least one bond of 1.0 Debye or more. Coupling moment is 0.7Debye
Specific examples of the above bonds include N-H, O-H,
H-F, H-Cl, C-F, C-Cl, C-Br, C
-I, C-O, C=O, C≡F, etc. Examples of functional groups having at least one of these bonds include hydroxyl group, amino group, carbonyl group, ether group, nitrile group, carboxyl group, Examples include, but are not limited to, an amide group, an imide group, a pyrrolidone group, and the like. The bond moment is the dipole moment that acts between two bonded atoms, and the numerical values are shown in "Chemistry Handbook" Basic Edition, P. 1406, Table 11173 (1975) (Maruzen). The value was adopted. Debye, the unit of bonding moment, is 10 ^-18 cgs・
It refers to esu・cm. Also, particularly preferred among the polar polymer compounds used in the present invention are polar linear polymer compounds. The linear polymer compound referred to here is one in which the monomer is polymerized almost linearly with some branching, or one in which the monomer is polymerized in a linear manner and then the linear polymer chain is polymerized. refers to something that is cross-linked. Specific examples of preferable polar polymer compounds used in the present invention are shown in the following (1) to (10), among which particularly preferable ones are (1) to (7). (1) Polyvinyl alcohol (2) Polyacrylamide (3) Polyethylene oxide (4) Polyacrylonitrile (5) Polyvinylpyrrolidone (6) Polymer of boric acid (salt) (7) Polymer of phosphoric acid (salt) (8) Aromatic polyimide (and its derivative) (9) Aromatic polyester (and its derivative) (10) Aromatic polyamide (and its derivative) In the present invention, the content of the polar polymer compound contained in the inorganic layered compound is , based on the inorganic layered compound, 1 to 30% by weight, preferably 3 to 25% by weight, more preferably 7 to 20% by weight,
It is not possible to obtain a metallized inorganic film that has excellent toughness, flexibility, vapor deposition strength, and heat resistance properties. The metal of the vapor-deposited metal layer in the present invention refers to Group A, Group A, Group VA, Group A of the periodic table of elements,
Metals selected from Group I, Group B, Group B, Group B, and alloys thereof are preferred, and particularly preferred among these are aluminum, zinc, tin,
Mainly made of copper, nickel, chromium, iron, titanium, or alloys thereof. Further, the thickness of the inorganic film of the substrate in the present invention varies depending on the use and is not particularly limited, but is preferably 200 μm or less, particularly preferably
The flexibility of the metallized inorganic film is particularly good when the thickness is 100 μm or less. Further, the thickness of the vapor-deposited metal layer in the present invention is 50
Å or more, preferably 100 Å or more, more preferably 200 Å or more, the electric conductivity inherent to the metal can be obtained, and 5000 Å or less, preferably 3000 Å or less, and even more preferably 1000 Å or less, the deposition strength can be improved. It is preferable that the size becomes larger. Next, an example of the method for manufacturing the film of the present invention will be explained. A swellable, for example, hydration-swellable inorganic layered compound is swollen with a suitable solvent, such as water, to form a suspension, and the concentration is 1 to 20% by weight, preferably 2 to 10% by weight.
Adjust to % by weight. A polar polymer compound (or its solution) is gradually added to this suspension, and the polar polymer compound is 1 to 30% by weight, preferably 3 to 25% by weight, based on the inorganic layered compound. More preferably, it is adjusted to 7 to 20% by weight. This mixed suspension is further stirred to form a homogeneous suspension. If the concentration of the inorganic layered compound in this suspension deviates from the above concentration range (1 to 20% by weight, preferably 2 to 10% by weight), it is adjusted again to fall within this range. The suspension thus obtained is spread uniformly onto a releasable substrate such as a metal plate, glass plate, or polyethylene plate coated with silicone resin by a casting method or a spraying method. Roll it out until it is thick. This is dried at a temperature of room temperature to 250°C to form a film, and then the film is peeled off from the substrate to obtain a single inorganic film. In this case, in order to shorten the drying time, an infrared heater or the like may be used in combination, excess solvent may be removed using centrifugation, or vacuum drying may be used. Further, if continuous film formation is desired, a rotating drum or an endless belt may be used as the substrate. Needless to say, other known solution casting methods and wet casting methods can be used to form a film. Further, the film thus obtained can be heat-treated at an appropriate temperature and time, if necessary. The above description deals with the case where a polar polymer compound is contained from the beginning, but a polymerizable monomer may first be contained in an inorganic layered compound, and then this may be polymerized to form a polymer compound. The above description deals with the case where a polar polymer compound is contained in an inorganic layered compound before film formation, that is, at the stage of suspension.
It is also possible to make a film of only an inorganic layered compound in advance and impregnate this film with a polar polymer compound, or to impregnate it with a polymerizable monomer and then polymerize it to form a polymer compound. You can also use it as The film thus obtained is set in a vapor deposition apparatus, and a metal is vapor deposited on the surface of the film to form a metallized inorganic film. In this case, the vapor deposition method includes, but is limited to, electric heating fusion vapor deposition method, ion beam vapor deposition method, sputtering method, ion plating method, or method of casting molten metal onto a film. Do not mean. Although the present invention is characterized by the metallized inorganic film as described above, the interlayer ions of the inorganic layered compound can be freely exchanged depending on the use of the film. A specific example will be explained. A metallized inorganic film produced by the above production method using a hydration-swellable inorganic layered compound having lithium ions, sodium ions, etc. as interlayer ions as a film raw material swells again when it comes into contact with water. If you want to impart water resistance to this metallized inorganic film, once the film has been dried, it can contain metal ions such as potassium chloride, calcium chloride, barium nitrate, and lead acetate, which have lower hydration energy than lithium ions and sodium ions. After being immersed in a saturated salt solution for 1 hour or more, preferably 3 hours or more, it is dried again to obtain a metallized inorganic film in which interlayer ions such as lithium ions and sodium ions are exchanged with the metal ions of the salt. The film thus obtained does not swell again upon contact with water. Furthermore, if a metallized inorganic film having a high affinity with organic substances is desired, a metallized inorganic film with organic substance ions as interlayer ions can be obtained using the same method. The above description is based on the case where interlayer ions are exchanged after forming a metallized inorganic film, that is, after metal is deposited on the film.However, even if interlayer ions are exchanged before metal is deposited on the film, Alternatively, a metallized inorganic film may be obtained by forming a film using an inorganic layered compound in which interlayer ions of the inorganic layered compound are exchanged with desired metal ions or organic ions, and then depositing a metal onto this film. Furthermore, by incorporating a fibrous substance into the inorganic layered compound layer of such a metallized inorganic film, it is possible to obtain a metallized inorganic film with even greater strength. The fibrous material in this case may be organic fibers such as pulp and synthetic fibers, inorganic fibers such as glass fibers and asbestos, or metal fibers. In addition, as for the form of the fiber, the length is 1 to 100 mm, preferably 5 to 50 mm.
mm, diameter of 1 to 25 μm, preferably 3 to 15 μm. The appropriate content thereof is 1 to 40% by weight, preferably 5 to 30% by weight, based on the inorganic layered compound. The fibrous material may be added to a suspension of an inorganic layered compound, or it may be added to a mixed suspension of an inorganic layered compound and a polar polymer compound to form a film. Good too. Furthermore, within the scope that does not impede the purpose of the present invention, there is no problem in mixing organic or inorganic additives for the purpose of improving the fluidity and wettability of the suspension, or increasing the dielectric constant of the film. . Moreover, by pressurizing the film of the present invention,
The effects of the present invention can be further enhanced. In this case, the pressurizing step may be performed before the metal is vapor-deposited on the film, that is, before, during, or after drying in the inorganic film manufacturing process. You can do it later. In any of these cases, it is preferable to use a pressure of 100 Kg/cm ² or more when applying pressure on a surface, and a pressure of 100 Kg/cm ² or more when applying roll rolling. Further, one side of the metallized inorganic film of the present invention,
Alternatively, it may be used as a laminated film in which organic polymer films are laminated on both sides. Lamination methods in this case include, but are not limited to, laminating methods and bonding methods. Next, a method for measuring characteristic values used in the present invention will be explained. (1) Strength and elongation Strength and elongation as used in the present invention refer to breaking strength and elongation when tensile, and are based on JIS-Z-1702.
It was measured using an Instron type tensile tester according to the method specified in . (2) Toughness P To quantitatively express toughness, it is defined by the following formula. In the case of , it was determined that the toughness was poor. P=1/2×(A×B) Here, A is the strength of the film (Kg/mm ² ), B
is the elongation (%). (3) Flexibility After repeating the operation of folding a film with a length of 150 mm and a width of 10 mm in half along the longitudinal direction 180 degrees 20 times, observe the film. If there is no change, the film has good flexibility. If there is a crack in the part or the part breaks at the bent part, it is judged as having poor flexibility. (4) Heat resistance properties Measure the dielectric breakdown voltage of the film at 25°C and 300°C. If the value at 300°C is 80% or more of the value at 25°C, it has good heat resistance properties, and if it is less than 80%, it is heat resistant. It was determined that the characteristics were poor. The dielectric breakdown voltage was measured in accordance with the method specified in JIS-C-2330, and the average value of 50 measurements was taken. (5) Vapor deposition strength Attach cellophane tape to the vapor deposition surface of the metallized inorganic film and quickly peel it off. As a result of this operation, if the peeling rate of the vapor-deposited metal layer is less than 5% of the total area of the cellophane tape, the vapor deposition strength is good, and if the peeling is equivalent to 5 to 30% of the total area of the cellophane tape, the vapor deposition strength is poor. If unsatisfactory or the peeled portion exceeds 30%, the deposition strength was determined to be poor. The film of the present invention can be used, for example, for packaging such as food, miscellaneous goods, and pharmaceutical packaging, for magnetic recording such as base films for video or audio tapes and magnetic disk bases, for electrical insulation such as capacitors, etc.
It can be used for building materials such as decorative laminate films and wall films. Among these, particularly preferred are those for magnetic recording or capacitors. As described above, the present invention is a metallized inorganic film in which a metal vapor-deposited layer is provided on at least one side of an inorganic layered compound film containing a polar polymer compound. Through the unique interaction between the three metals, we were able to obtain the following excellent effects. In other words, (1) It has excellent toughness, flexibility, and vapor deposition strength, and its heat resistance is not limited to that of the polymer compound it contains, but exhibits heat resistance as an inorganic material, and can withstand harsh thermal conditions. It can also be a metallized inorganic film that can be used. (2) The electrical properties of the film, such as corona resistance, are not limited to the electrical properties of the polymer compound contained therein, and can be made into a metallized inorganic film exhibiting the properties of an inorganic material. Next, embodiments of the present invention will be described based on Examples. Example 1 Lithium hectorite [characteristic formula: Li _0.33 Mg _2.67
An inorganic layered compound represented by Li _0.33 (Si ₄ O ₁₀ ) F ₂ .
When the powder (manufactured by Topy Industries, Ltd.) is immersed in a beaker containing distilled water and stirred, a suspension of fine crystals and a precipitate of coarse particles and impurities are formed. A suspension of lithium hectorite from which this precipitate was removed was prepared to have a concentration of 6% by weight (this suspension was referred to as Liquid A). Polyvinyl alcohol powder (Nippon Gosei Kagaku Co., Ltd.)
"GOHSENOL" AL-06) manufactured by Goshenol, Ltd., was dissolved in distilled water to prepare a 15% by weight aqueous polyvinyl alcohol solution (this solution is referred to as Solution B). While stirring Solution A, Solution B was gradually added to Solution A so that the solid content of polyvinyl alcohol was 20% by weight based on the solid content of lithium hectorite. This mixture was further stirred to make a homogeneous suspension, and then this suspension was cast onto a glass plate to a uniform thickness of 2 mm, and then placed in a gear oven. It was dried at 70°C for 2 hours and at 120°C for 1 hour. The film formed on the glass plate is peeled off from the glass plate to a thickness of approx.
A 40 μm film was obtained. This film was set in an electric heating melting vacuum deposition apparatus, and aluminum was deposited to a thickness of 300 Å at a vacuum degree of 10 ^-5 Torr to obtain a metallized inorganic film. The strength of this film is 14Kg/mm ² and the elongation is 2.5%
The toughness P was 17.5, indicating sufficient toughness. The film also had good flexibility, and was a strong and flexible film that caused no problems in normal handling. Moreover, both heat resistance properties and vapor deposition strength were good. As is clear from the above, the film of the present invention is a metallized inorganic film that is excellent in toughness, flexibility, heat resistance, and vapor deposition strength. Example 2 Montmorillonite [Specific formula: Na _0.33 Al _2.67
An inorganic layered compound represented by Mg _0.33 (Si ₄ O ₁₀ ) (OH) ₂ . A powder of "Kunipia" G manufactured by Kunimine Kogyo Co., Ltd. was immersed in distilled water and purified in the same manner as in Example 1, and the concentration of montmorillonite was adjusted to 4% by weight (this suspension is called liquid C). Cast liquid C onto a glass plate to a uniform thickness of 2 mm.
Spread this in a gear oven,
It was dried at 70°C for 2 hours and at 120°C for 1 hour. The film formed on the glass plate was peeled off from the glass plate to obtain a film with a thickness of about 40 μm. This film was immersed in a polyamic acid solution (Trenice No. 3000 manufactured by Toray Industries, Inc.) to impregnate the polyamic acid so that the solid content was 25% by weight of the montmorillonite. Place this film in a gear oven at 70°C.
After drying at 120°C for 2 hours and 1 hour at 120°C, further heat treatment was performed successively at 200°C for 30 minutes, 300°C for 30 minutes, and 375°C for 30 minutes. This film was set in an electrically heated melting vacuum deposition apparatus, and aluminum was deposited to a thickness of 300 Å at a vacuum degree of 10 ^-5 Torr to form a metallized inorganic film. The strength of this film is 15Kg/mm ² and the elongation is 2.3%.
The toughness P was 17.3, indicating sufficient toughness. The flexibility was also good, and the heat resistance and vapor deposition strength were also good. As is clear from the above, the film of the present invention is a metallized inorganic film that is excellent in toughness, flexibility, heat resistance, and vapor deposition strength. Example 3 While stirring the montmorillonite suspension (liquid C) used in Example 2, polyacrylamide (“Acofloc” manufactured by Mitsui Cyanamid Co., Ltd.) was gradually added to liquid C to reduce the solid content of polyacrylamide. was prepared so that the solid content of montmorillonite was 15% by weight.This mixed suspension was further stirred well to obtain a homogeneous suspension.This suspension was cast onto a glass plate, and a thick The film was spread to a uniform thickness of 2 mm and dried in a gear oven at 70°C for 2 hours and at 120°C for 1 hour.The film formed on the glass plate was peeled off from the glass plate and the thickness was A film with a diameter of approximately 40 μm was obtained. This film was immersed in a saturated aqueous solution of potassium chloride for 96 hours, then washed under running water for 20 minutes, and then heated in a gear oven at 70°C for 2 hours and at 120°C. The film was dried for 1 hour. After being pressed at a pressure of 1 t/cm ² , it was heat treated at 220°C for 3 hours. This film was set in an electrically heated melting vacuum evaporator and heated at a vacuum degree of 10 ^-5 Torr. , aluminum was vapor-deposited to a thickness of 300 Å to form a metallized inorganic film. The properties of this film are shown in Table 1.
Although the metallized inorganic film was excellent in toughness, flexibility, heat resistance, and vapor deposition strength, the additives to be included in the inorganic layered compound and their contents were compared to Comparative Examples 1 to 4 in Table 1. When doing so, as shown in the same table, the object of the present invention could not be achieved. 【table】

Claims (1)

[Claims] 1. A metallized inorganic film comprising a film made of a mixture of an inorganic layered compound and a polar polymer compound in an amount of 1 to 30% by weight based on the inorganic layered compound, and a metal vapor-deposited layer provided on at least one side of the film.