JPS58185430A - Metallized inorganic film - Google Patents

Abstract

PURPOSE:The titled film having toughness, flexibility, adhesiveness, and improved heat resistance, obained by forming a metallized layer on a film consisting of a mixture of an inorganic layer compound and a proper amount of a polar high polymer compound. CONSTITUTION:A metallized layer is formed on at least one side of a film consisting of a mixture of an inorganic layer compound and 1-30wt% polar high polymer compound based on it, to give a metallized inorganic film having improved characteristics. An inorganic compound such as LiMg2Li(Si4O10)F2, etc. consisting essentially of silicon oxide, having crystal structure of repeating crystal unit in the thickness direction is used as the inorganic layer compound. A high polymer compound such as PVA, etc. having >=about 100 polymerization degree and at least one organic functional group in the repeating unit is used as the polar high polymer compound. Preferably the metallized film consists of a metal such as Al, Zn, Sn, Cu, Ni, Cr, Fe, Ti, etc. or its alloy and has >=about 50Angstrom metallized film thickness.

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, an example of a metallized inorganic film is a film in which a metal is deposited on a film A made of an inorganic layered compound (
For example, British Patent No. 1o163B5) is known. However, such metallized inorganic films have poor flexibility and low strength and elongation.
It did not have enough toughness to withstand practical use, and had drawbacks such as 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 to provide a metallized inorganic film that has excellent toughness, flexibility, and adhesion (vapor deposition strength) as well as excellent heat resistance properties. .

The present invention has the following configuration to achieve the above three objectives.

That is, it is characterized by 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 metallized 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, preferred are:
Main ingredient is silicon oxide.

It is a clay-based mineral and a mica-based mineral represented by the following general formula.

Wow! ~l X2.6=-=3. Q (“4”I
N) Z2 here.

W: A type of ion called an interlayer ion selected from organic ions such as lithium, sodium, potassium, calcium, barium, strontium, lead, and alkylammonium ions.

X: One or two ions selected from magnesium, iron, nickel, manganese, aluminum, and lithium.

Y: silicon, aluminum, germanium.

A type selected from iron and boron. are two types of ions.

0: Oxygen Z: One or two ions selected from fluorine or hydroxyl groups.

Specific examples of inorganic layered compounds represented by the above general formula are shown in the following fl) to kan, and among these, particularly preferred ones are (
1) to (6).

(1) 'LiMg2Li (Si40..)F2N
aMg, Li(Si, Ol,,)F.

KMg, Li (Si40..)F.

(2'Llo, 33Mg2.67L10.55(
S14010) F2Na, 3. li! g2゜67""
0.55 (s14o10)F2KO1AMg2. l
7 ”10.55 (S1401 Q) F2 (3
) ”0.6 yMgz.S&””0.61 (S1
401o) F21' ao, 6q M g 2°,
3Lio. 47 (S'4oLO)F! KO, 6y”gz, 5&”0.67 (S14010)
Fl(1) 1lao, 3. Mgo...A12゜6
7 (s14o,.) (OH)2Ko,s s”a, 5s
A1t, 6y (S140H)) (OH) 2(5
1Ill~ (4) in which interlayer ions are replaced with alkyl ammonium ions.

((Gencho, 11 slope, S (Si40.
. ) F2NaMg2.5 (81401,,) F
2K Mg 2 ,5 (S l 40 ,.)F2(
Power Bao, ssMgo, 5sAlt, 67 (S1
401(3)(OH)2f81 LiMg,,Li
(Si40..) (OH).

Na Mg 2 Li (Sia O1,+)
(OH) 2K Mg2L1(Si40..1) (O
H) 2f91 LIMgs (B 5150..)
F2NaMgs (Bsi, o,,,)F2K Mg
s (B S L s Os.) FQil Li M
g s (B51s○,.) (01() 2NaMg
, (BSi, O,.) (OH) 2K Mg, (
BSi, Ol, ) (OH) 2. What is the polar polymer compound used in the present invention?

It is a compound with a degree of polymerization of 100 or more, and refers to a polymer compound having at least one polar functional group in the repeating unit of the polymer.

Here, a polar functional group is defined as having a bonding moment of o, 7 Deb: i'e or more, preferably 1.
A functional group having at least one bond of ODe bye or more. The coupling moment is Q, 7 Deby
Specific examples of bonds of θ or more include N-H, O-H, H
-F, H01,OF, C-C1,C-Br, C-
I.

Examples of functional groups having at least one of these bonds include hydroxyl group, amine group, carbonyl group, ether group, nitrile group, carboxyl group, and amide group. , imide group.

Examples include, but are not limited to, pyrrolidone groups.

Note that the bond moment refers to the dipole moment that acts between two bonded atoms, and its numerical value can be found in "Chemistry Handbook" Basic Edition If, P. 1406. Table 11173 (19
75) The values shown in '(Maruzen) were adopted. The binding moment unit Dθbyθ is 1o-IllCg
(4” O+i u @).

Furthermore, particularly preferred among the polar polymer compounds used in the + invention are polar linear polymer compounds.

What is the linear polymer compound referred to here?

Polymers are polymerized in a nearly linear manner with some branching, or are polymerized in a linear manner and then cross-linked between the linear polymer chains.

Specific examples of preferable polar polymer compounds used in the present invention are shown in (1) to Ql below, and among these, particularly preferable ones are (1) to (katana).

(1) Polyvinyl alcohol (2) Polyacrylamide (3) Polyethylene oxide (4) Polyacrylic nitrile (5) Polyvinylpyrrolidone (6) Polymer of boric acid (salt) (7) Polymer of phosphoric acid (salt) (8) ) Aromatic polyimide (and derivatives thereof) (9
) Aromatic polyester (and derivatives thereof) Ql
Aromatic polyamide (and derivatives thereof) In the present invention, the content of the polar polymer compound contained in the inorganic layered compound is 1 to 30% by weight based on the inorganic layered compound.
, preferably 3 to 25% by weight, more preferably 7 to 2% by weight
If it is not 0% by weight, a metallized inorganic film having excellent toughness, flexibility, vapor deposition strength, and heat resistance properties cannot be obtained.

The metal of the vapor-deposited metal layer in the present invention is a metal selected from group mA, group IVA, group VA, group VIA, group II, group IB, group IIB, group IB, and group IVB of the periodic table of one element. and their alloys are desirable, among which aluminum, zinc, and tin are particularly preferred.

Mainly made of copper, nickel, chromium, iron, titanium, or alloys thereof.

In addition, the thickness of the inorganic film of the substrate in the present invention is
It varies depending on the application and is not particularly limited, but the bf length is 21J D Bm or less, and the particularly good width is 100μ.
The flexibility of the metallized inorganic film is particularly good when the temperature is m or less.

9 The thickness of the vapor-deposited metal layer in the present invention is 5QA or more.
-9 preferably 100/r or more, more preferably 20
If it is above OS, it is preferable because the electric conductivity inherent in metal can be obtained, and if it is below I5ooo'A, preferably 3G]
If it is 0 or less, more preferably 1ooo''A or less, the vapor deposition strength will be higher, which is preferable.

Next, an example of the method for manufacturing the film of the present invention will be explained. Swellability 1 For example, a water-swellable inorganic layered compound is swollen with a suitable solvent 1 such as water to form a suspension, and the concentration is 1 to 2.
It is adjusted to 0% by weight, preferably 2 to 10% 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 7 to 20% by weight. This mixed suspension is further stirred to form a homogeneous suspension. The concentration of the inorganic layered compound in this suspension is within the above concentration range (1 to 20% by weight, preferably 2 to 20% by weight).
(10% by weight), it is adjusted again to fall within this range.

The suspension obtained in this way is poured onto a releasable substrate such as a metal plate, glass plate, or polyethylene plate coated with silicone resin, using a casting method or a spraying method, so that the suspension has a uniform thickness. expand so that it becomes This is dried at a temperature of room temperature to 250'Q 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.

Also, if you want to make films continuously.

A rotating drum or an endless belt tracker can also be used as the substrate. Needless to say, other known solution casting methods and wet casting methods can be used to form a film. Also, thus obtained J and fill l,
Appropriate temperature as required.

Heat treatment can also be performed over time.

The above description includes polar polymer compounds from the beginning.
Although the case has been described above, a polymerizable 1i matrix may first be incorporated into an inorganic layered compound, and then this may be polymerized to form a polymer compound.

The above description deals with the case where the polar polymer compound is contained in the inorganic layered compound before film formation, that is, at the stage of suspension.

10 You can make a film of only the inorganic layered compound and impregnate this film with a polar polymer compound, or you can impregnate it with a polymerizable monomer and then polymerize it to form a polymer. It may also be used as a compound.

The film thus obtained is set in a vapor deposition apparatus, and 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 blating 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 it is desired to impart water resistance to this metallized inorganic film, the dried film may be treated with potassium chloride, calcium chloride, or barium nitrate.

It is immersed in a saturated solution of salt containing metal ions, such as lead acetate, which have lower water utilization energy than lithium ions and sodium ions, for at least 1 hour, preferably for at least 6 hours, and then dried again to form interlayer ions of lithium and sodium ions. can be made into a metallized inorganic film in which the salt is exchanged with the metal ion of the above salt. If the film thus obtained is desired to be a metallized inorganic film that has a high affinity for contact with water, it can also be made into a metallized inorganic film with organic ions interlayered in A/A/ by the same method. .

In addition, after one or more descriptions are metalized inorganic films,
That is, although the case has been described in which interlayer ions are exchanged after metal is vapor-deposited on a film, interlayer ions may be exchanged before metal is vapor-deposited on a film, or,
A metallized inorganic film may be obtained by forming a film using an inorganic layered compound in which the interlayer ions of the inorganic layered compound are exchanged with desired metal ions or organic ions in advance, and then depositing a metal onto this film.

Further, by incorporating a fibrous substance into the inorganic layered compound layer of such a metalized inorganic film, a metalized inorganic film with even greater strength can be obtained. In this case, the fibrous material may include organic fibers such as pulp and synthetic fibers.

Even inorganic fibers such as glass fiber and asbestos.

Alternatively, metal fibers may be used. In addition, the form of the fiber is
It is suitable that the length is 1 to 100 mm, preferably 5 to 50 plates, and the diameter is 1 to 25 μm, preferably 5 to 15 μm. In addition, the content is 1 to 1 to
40% by weight, preferably 5 to 60% by weight.

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.

In addition, 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, as long as it does not impede the purpose of the present invention. .

Also, by pressurizing the film of the present invention.

The effects of the present invention cannot be further enhanced.

In this case, the pressure step is performed before the metal is deposited on the film.
In other words, in the inorganic film manufacturing process, before drying,
This may be carried out during or after drying, or may be carried out after the metal is vapor-deposited on the film. In any of these cases, if pressure is applied on 9 sides, 100 w/a
n' or more, 100y/- in case of roll rolling etc.
It is preferable to carry out the reaction at a pressure higher than that.

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 rough characteristic values according to the present invention will be explained.

(11 Strength and elongation The strength and elongation used in the present invention refer to breaking strength and elongation at break when tensile, according to the method specified in J Engineering 5-Z-1702.

Measurements were made using an Instron type tensile testing machine.

(2) Toughness P To quantitatively express toughness, it is defined by the formula below. In the case of , it was determined that the toughness was poor.

P to -X (AXB) where A is the strength of the film (kg/dish 1) and B is the elongation (%χ).

(3) Flexibility After repeating the operation of bending 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 flexibility is good.

If the film cracked or broke at the bent part, it was determined that the film had poor flexibility.

(4) Heat resistance properties The dielectric breakdown voltage of the film was measured at 25°C and 500°C, and the value at 300°C was 80% of the value at 25°C.
A value of 80 cm or more was determined to have good heat resistance properties, and a value of less than 80 cm was determined to be poor heat resistance properties. Note that the dielectric breakdown voltage is measured using J
The measurement was carried out according to the method specified in IS-0-2530, and the average value of 50 measurements was taken.

(5) Attach cellophane tape to the vapor-deposited surface of the inorganic film classified into 9th category of vapor-deposition strength, and rapidly peel it off.

As a result of this operation, if the rate of peeling of the vapor-deposited metal layer is less than 5% of the total area of the cellophane tape, the vapor deposition strength is good; if the peeling is equivalent to 5 to 50% of the total area of the cellophane tape, the vapor deposition strength is unsatisfactory and the peeling is poor. If the portion exceeds 30 inches, it was determined that the deposition strength was 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, for magnetic tape, and for electrical insulation for capacitors and the like.

It can be used for building materials such as decorative board 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. , it was possible to obtain excellent effects such as the 9th order due to the unique interaction between the three metals. Namely.

(1) Excellent toughness, flexibility, and vapor deposition strength;
Furthermore, the heat resistance properties are not limited to those of the contained polymer compound, and the metallized inorganic film exhibits heat resistance properties as an inorganic material and can be used even under severe thermal conditions.

(2) The electrical properties of the film 9, for example, corona resistance, are not limited to the electrical properties of the polymer compound contained, but can be 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 [indicative formula""io-g5'g2
．． 47L1o, 3. (S140..) An inorganic layered compound represented by F2.

When the powder (manufactured by Dobby L Co., Ltd.) is immersed in a beaker containing distilled water and stirred, a suspension of fine crystals, coarse particles,
Produces precipitation of impurities. A suspension of lithium hectorite from which this precipitate was removed was prepared to have a concentration of 6 ilj (this suspension is referred to as liquid A).

Polyvinyl alcohol powder (Gosenol AL-06, manufactured by Nippon Gosei Kagaku ■) was dissolved in distilled water to prepare a 15% by weight aqueous polyvinyl alcohol solution (this solution was 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.

After stirring this mixture further to make a homogeneous suspension, this suspension was cast onto a glass plate and spread to a uniform thickness of 2 mm. in,
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 set in an electrothermal heating melting vacuum evaporation device, and 55% of aluminum was applied at a vacuum degree of 10 Torr.
A metallized inorganic film was obtained by vapor deposition to a thickness of 0OA.

The strength of this film was 14 kg/mm'', the elongation was 2.5 inches, and the 1 strength toughness P was 1Z5, indicating sufficient toughness.Furthermore, the film had good flexibility.

The film was strong and flexible and had 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 9 is a metallized inorganic film with excellent toughness, flexibility, heat resistance, and vapor deposition strength.

Example 2 Montmorillonite [Symbolic formula: Nao, , AI□, 6
7 pulls. ,,5(S140..)(OH)2 Inorganic layered compound. A powder of "Kunivia" G manufactured by Kunimine Industries Ltd. was immersed in distilled water and purified in the same manner as in Example 1, and the concentration of "Kunivia" G manufactured by Kunimine Kogyo was adjusted to 4% by weight. Let the cloudy liquid be called liquid C).

c 8v i- Cast on a glass plate and spread it out so that the thickness becomes two plates evenly, and then open the gear.

It was dried at 70"0 for 2 hours and at 120°C for 1 hour. The film formed on the glass plate was peeled off from the glass plate.
A film with a thickness of about 40 μm was obtained. This film was immersed in a solution of polyamic acid (Trenice No. 3000 manufactured by Toshi Corporation) to impregnate the polyamic acid so that the solid content of the polyamic acid was 25% by weight of the montmorillonite. This film was heated at 70°C for 2 hours and at 120°C for 1 hour with the gear open.
After drying for an additional 30 minutes at 200°C,
Heat treatment was performed continuously at 00°C for 50 minutes and at 375°C for 30 minutes.

This film was set in an electrically heated melting vacuum evaporation device, and aluminum was deposited at a vacuum level of 10 T-rr for 30 minutes.
The film was deposited to a thickness of 00A to obtain a metallized inorganic film.

The strength of this film was 15 kg/mm'', the elongation was 23 inches, and the 0 strength toughness P was 1Z, indicating sufficient toughness.It also had good 7 flexibility, and had good heat resistance and vapor deposition strength. 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 6 Montmorillonite used in Example 2! ! ! While stirring the cloudy liquid (liquid C), gradually add polyacrylamide (1 Acofloc manufactured by Mikata Cyanamid Co., Ltd.) to liquid C until the solid content of the polyacrylamide becomes 15% by weight of the solid content of montmorillonite. This mixed suspension was further stirred to obtain a homogeneous suspension.

This suspension was cast onto a glass plate to a uniform thickness of 2fl.
[Spread it out so that it becomes 70 mm with the gear open.
It was dried at 120°C for 2 hours and 1 hour at 120°C.

The film formed on the glass plate was peeled from the glass plate to obtain a film with a thickness of about 40 μm. This fill,
was immersed in a saturated aqueous solution of potassium chloride for 96 hours.Next, the film was washed under running water for 20 minutes, and then heated at 70°C for 2 hours in an open gear.

It was dried for 1 hour at 120' (!).
After pressing at a pressure of /an'', heat treatment was performed at 220°0 for 3 hours.

This film was set in an electrically heated melting vacuum deposition apparatus, and aluminum was deposited to a thickness of 300A at a vacuum degree of 10''' Torr 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 the IE content thereof were different from Comparative Examples 1 to 4 in Table 1. When doing so, the object of the present invention could not be achieved as shown in the same 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.