JPS58149901A - Production of inorganic film - Google Patents

Abstract

PURPOSE:To obtain a tough, flexible, highly heat-resistant, inorganic film, by forming a composition into a film before or after polymerizing the composition and before impregnating or after mixing an inorganic layered compound with a polar compound having a polymerizable functional group. CONSTITUTION:The titled inorganic film is produced by mixing or impregnating an inorganic layered compound (e.g., sodium tetrasilicic mica, NaMg25(Si4O10)F2 with at least one polar compound having a polymerizable functional group (e.g., acrylamide monomer) under the following conditions. The above conditions include the formation of a film from a composition which is in the state before impregnation with the above monomer or after mixing with the above monomer and before or after polymerizing the above monomer. The titled film thus produced is useful in, for example, packaging food or drug or in magnetic recording or wire insulation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an inorganic film mainly composed of an inorganic layered compound, which is strong, flexible, and has excellent heat resistance.

Conventionally, there is a method for manufacturing such an inorganic film.

A method in which a colloidal solution of an inorganic layered compound is cast onto a substrate with releasable properties, dried, and then peeled off from the substrate to obtain a film (for example, USP-2,266, 636);
Furthermore, a method is known in which a film-like molded product is obtained by blending silicate inorganic fibers into a colloidal solution of an inorganic layered compound (for example, Japanese Patent Publication No. 54-15045). However, these conventional methods have the disadvantage that the obtained films still lack 7 flexibility, and have low strength and elongation, and do not have the toughness to withstand practical use.

An object of the present invention is to provide a method for producing an inorganic film that is strong, flexible, and has excellent heat resistance by overcoming the drawbacks of the prior art described above.

In order to achieve the above object, the present invention provides a first production method, namely, impregnation or Mix and polymerize the (B) to form the (B)
This is a method for producing an inorganic film, which is characterized in that the composition is formed into a film before or after impregnating the odor, or after 4=fik of (B), and before or after polymerizing the odor.

The inorganic layered compound (A) used as a raw material 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 these inorganic layered compounds, preferable ones include silicon oxide as a main component and swell in water or other solvents to form fine scales (one particle size is larger than the wall thickness).

They are so-called swellable inorganic layered compounds, and are clay minerals and mica minerals represented by the first-order general formula.

WOoF-1X2.5-6.0 (F40-)Z2 here.

W: A type of ion called an interlayer ion selected from organic ions such as lithium, sodium, or alkylammonium ions.

X: Magnesium, iron, nickel, manganese, aluminum
One or two types of ions selected from Ni 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 the inorganic layered compound represented by the above general formula are shown in the following (11 to (9)), among which particularly preferred are flI to (6).

(I) LiMg, Li(Si, 0..)F.

NaMg, Li(Si40.,)F.

f2) ”'o, s5Mgz, 1Lio, 55 (S1
aO+,)F2NF'o, ss Mgz, 6y Lio
, 3s (Si40., )F.

(31Llo, 67 Mg2.3s ”'0.47 (
S1401゜) F2N ao, 6y Mg 2.5
B ”lo, 67 (S la Or.) F2
(4) NaO,! 3 Mgo43 A12.67
(S1401°) (OH).

(51 (11-(4) interlayer ions are exchanged with alkyl ammonium ions.

(6i LiMg, (Si40.o)F.

NaMg2.5(si40., )Ft(7) Li
Mg, Li (Si 40..) (OH) tNa
Mg, Li (Si, O,.) (OH).

(8) LiMg1(BSi, 0.3)F.

NaMg, (BSi, 0.0)F.

(91LiMg, (BSi30..) (OH)!
NaMg, (BSi, 0.0) (OH).

The monomer (B) of the polar compound having a polymerizable functional group used in the present invention includes a vinyl group, a carboxyl group, an anhydride carboxyl group, a hydroxyl group, and an epoxy group.

Amine group, imino group, ester group, 7-syl halide group, amide group, sulfone group, sulfonyl halide group, aldehyde group, ditolyl group-acetyl group, thiol group, thiocarboxylic acid group, thioaldehyde group, in It has at least one polymerizable functional group such as a cyanate group and is resistant to heat, radiation, and electron beams.

Give energy such as neutron beams and ultraviolet rays.

It is a compound that causes a polymerization reaction by adding a polymerization initiator, etc., and has at least one polar group (the polymerizable functional group may also serve as a polar group).

゛Here, a polar group is one in which the bonding moment in the polar group is 0.7Dθbye or more, preferably 1.01)e
Refers to a group having at least one bond of bye or more. Specific examples of bonds with a bond moment of 0.7 Dθbyθ or more include N-H, O-H, and H-F.

H-01,O-F, C-(1,Q-Br, O-
I, 0=O, C-○, C:iE-, N, etc. Examples of polar groups having at least one of these bonds include hydroxyl group 1. Amine group, carbonyl group, ether group, nitrile group, carboxyl group, 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 It, p1406. Table 11,175 (197
5) Adopt the values shown in (Maruzen) cgs”esul
Icrn.

Specific examples of preferable monomers (B) of polar composites having polymerizable functional groups used in the present invention are (1) to
Among them, the particularly preferable one is (11
~(8).

(1) Acrylamide (2j 4-vinylpyridine (3) Acrylonitrile (4) Pyromellitic dianhydride +51 4.4'-diaminodiphenyl ether (6)
Boric acid or boric acid salt (caric acid or phosphate salt 8) Titanic acid or titanate salt (9) Vinylpyrrolidone aI ε-Caglolactam Ill Terephthalic acid 03 Ethylene glycol, Col Q31 Hexamethylene diamine 04) Adipic acid 051 Acetic acid Vinyl Qf9 Ethylene glycol diglycidi, etc. ether In the present invention, 9 is a polarized mixture with a polymerizable functional group.
The following three methods are desirable for polymerization, but particularly preferred are (11) and (3'rc ammo (11) in which the inorganic layered compound (A) is a monomer of a polar compound having a polymerizable functional group). After mixing (B) and forming a film, (B)
A method of superimposing.

A method of mixing polar compound monomers (B), polymerizing (B), and then forming a film.

(3) Make a film made of the inorganic layered compound (A).

A method in which this film is impregnated with monomer (B) of a polar compound having a polymerizable functional group, and then polymerized.

Next, the methods fl) to (3) above will be explained in more detail.

Fll's Method First, the powder of the above-mentioned inorganic layered compound (A) is immersed in a suitable solvent to swell it and form a suspension. The concentration of this suspension is adjusted to 1 to 20% by weight, preferably 2 to 10% by weight. Next, the monomer (B) (or its solution) of the polar compound having the polymerizable functional group described above was added to (A
) to make a mixed suspension. In this case, the solid content of (B) is 1 to 5% of the solid content of (A).
If the content is not 0% by weight, preferably 5 to 45% by weight, more preferably 1.0 to 40% by weight, 9 toughness,
It is not possible to produce a film that has excellent flexibility, stability, and heat resistance. Stir this mixed suspension further.

Make a homogeneous suspension. The concentration of the inorganic layered compound in this suspension is within the above-mentioned concentration range (1 to 20% by weight).

If it deviates from the preferred range of 2 to 10% by weight.

Adjust again to fall within this range.

The above description deals with the case where (B) (or its solution) is mixed with the suspension of (A), but (A) (or its suspension °)' is mixed with the solution of (B). Alternatively, a mixture of (A) and (B) may be taken out from this suspension, and this mixture may be swollen again in an appropriate solvent to form a suspension. It may also be used to form a film. Further, a known polymerization initiator or the like may be added to the obtained suspension if necessary.

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. Spread it out to a certain thickness. This is dried at a temperature of room temperature to 250° C. (the drying time varies depending on the thickness of the film) to form a film, and then the film is peeled from the substrate to obtain a single film.

In this case, in order to shorten the drying time, an infrared heater or the like may be used together1, excess solvent may be removed using centrifugation, or vacuum drying may be used. .

Also, if you want to make films continuously.

A mouth plate drum or an endless belt 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.

Polymerization of the monomer (B) of the polar compound having a polymerizable functional group in this film is carried out by a known method until the degree of polymerization reaches 100 or more. The method differs depending on the type of compound, but in addition to thermal polymerization, known methods such as radiation, irradiation with high-energy rays such as electron beams, neutron beams, and ultraviolet rays, and plasma polymerization can be used. Further, the polymerization atmosphere may be in air, vacuum, or inert gas.

Method (2) Inorganic layered compound (A) prepared in the same manner as method (1)
First, a mixed suspension of a monomer (B) of a polar compound having a polymerizable functional group is polymerized. The polymerization is carried out by a known method until the degree of polymerization of (B) becomes 100 or more. The polymerization method varies depending on the type of compound, but in addition to thermal polymerization, radiation, electron beam, and neutron beam are also used.

Known methods such as high-energy ray irradiation such as ultraviolet rays and plasma polymerization can be used.

The mixed suspension in which polymerization has been completed is formed into a film in the same manner as described in method (1).

+3) Method A suspension of the above-mentioned inorganic layered compound (A) is prepared according to method 111, and this suspension is used to form a film in the same manner as described in method (1). A film made of compound (A) is prepared.

This film is immersed in monomer (B) of a polar compound having a polymerizable functional group (or a solution thereof) to uniformly impregnate (B) into the inorganic layered compound film.

In this case, the immersion time, temperature, pressure, concentration of (B), etc. are adjusted so that (]9 is 1 to 50 weights to (A), preferably 5 to 45 weights, more preferably 10 to 40 weights). i
%.

After drying the film thus obtained at a temperature of room temperature to 250'C, (B) is polymerized until the degree of polymerization becomes 100 or more. The method is similar to that described in method (1).

The films obtained by methods 1(1) to (3) below can be further heat treated if necessary, but the temperature condition in this case is preferably 150 to 1.5°C and the atmosphere is air. , in vacuum or in an inert gas.

Note that the present invention is characterized by the method for producing an inorganic film as described above, and one of the inorganic layered compounds (A)
By combining the methods of freely exchanging interstitial ions, it is possible to create a manufacturing method that can produce excellent films such as those shown in the paper. For example, a film made from a hydration-swellable inorganic layered compound containing lithium ions or sodium ions as glabellar ions may swell again when it comes into contact with water. If you want to impart water resistance to this film, add potassium chloride, calcium chloride, or barium nitrate to the phlegm-dried film.

After being immersed in a saturated solution of a salt containing metal ions with lower hydration energy than lithium ions and sodium ions, such as lead acetate, for at least 1 hour, preferably for at least 6 hours, the lithium ions and interlayer ions are dried again. Sodium ions can be exchanged for metal ions of the salt.

The film thus obtained does not swell again when it comes into contact with water. Also, if you want to make a film that has a high affinity with organic substances.

Organic ions can also be introduced as interlayer ions using a similar method. Note that the above description is based on the case where nine interlayer ions are exchanged after forming into a film, but it is possible to form a film using an inorganic layered compound as a raw material in which the interlayer ions of the inorganic layered compound are exchanged with desired metal ions or organic ions in advance. It's okay.

Further, in the production method of the present invention, by incorporating an operation of incorporating a fibrous substance into the film, the production method can produce a 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, the length of this fibrous substance is 1 to 100 mI.
n.

A diameter of preferably 5 to 5 Qmm, preferably 1 to 25 μm, preferably 6 to 15 μm is suitable. The content is 1 to 40% by weight based on the inorganic layered compound.

You may also use a fibrous substance added to it.

Note that 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. .

Furthermore, by incorporating a pressurizing step into the manufacturing method of the present invention, a manufacturing method that can produce a film with even better toughness can be achieved. The pressurizing process in this case is
It may be carried out before the drying of the lume, during drying, or in the case of drying, before the polymerization and after the 9 polymerizations.

t-9 In addition, the present invention A relates to a method for producing a single inorganic film, and in addition to this method, a method of laminating a material made of an organic substance, an inorganic substance, or a metal on one or both sides of the film, or By further incorporating a method of sandwiching a film-like material obtained by the present invention with the film obtained in the present invention, it is possible to create a manufacturing method that can produce films that can be used in a wider range of applications. The methods of stacking are bonding method and laminating method.

Examples include, but are not limited to, vapor deposition methods.

The present invention is a method for manufacturing an inorganic film by making an inorganic layered compound (A) contain 9 types of polymerizable functional groups, and then polymerizing this (B), so that the compound is densely packed between the molecules of the inorganic layered compound. It can penetrate into the inorganic layered compound and interact strongly with the inorganic layered compound, resulting in the following excellent effects. Namely.

(Film No. 11 has excellent toughness and flexibility, and its heat resistance is not limited to that of the impregnated or mixed compound, but exhibits heat resistance as an inorganic material.

(2) Electrical properties of the film 1 For example, corona resistance is not limited to the properties of the compound contained, but shows the electrical properties of an inorganic material.

The film produced according to 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 C-type discs, and for capacitors.

Used for insulating X-rays (transformers, coils, motors, high-temperature magnets), electrical insulation for printed circuit boards, construction materials such as decorative board films and wall films, and diaphragm seals for fuel cells, etc. be able to. Among these, particularly preferred uses are electrical insulation and magnetic recording.

Next, a method for measuring characteristic values used in the present invention will be explained.

! 11 Strength and elongation Strength and elongation as used in the present invention refer to breaking strength and elongation at break when tensile, and were conducted using an Instron type tensile test according to the method published in J.Eng. 8-Z-1702. Measured using a machine.

121 Toughness P In order to quantitatively express toughness, it is defined by the following formula, and the larger P is, the better the toughness is.

Here, A is the strength of the film (kg/mm"), and B is the elongation (chi). If P is 40 or more, the toughness is judged to be good, and if P is less than 40, the toughness is judged to be poor. .

(3) Flexibility After repeating the operation of bending a film with a length of 15 Qmm and a width of 10 mm in half 180 degrees along the longitudinal direction 20 times, observe the film. If there is no change, the flexibility is good and there are cracks in the film. If it entered or broke at the bent part, it was judged as having poor flexibility.

(4) Heat Resistance Using a gas nozzle (height: 160 mm, inner diameter: 20 mm) specified in J.E. 5-A-1522, sub-air was passed through a moisture device to determine combustibility and non-combustibility. For nonflammable materials, the strength of the film is measured and the strength is 9 or 80.
When the retention rate was 1 or more, it was indicated by ○, when the retention rate was 50 inches or more and less than 80%, it was indicated by △, when it was less than 50 degrees, it was indicated by X, and when it was burned, it was indicated by XX.

Next, embodiments of the present invention will be described based on Examples.

Example 1 Sodium tetrasilicic mica [indicative formula=IJaM
An inorganic layered compound represented by g2.5(st4o,.)F.

When the powder (manufactured by Topie Corporation) 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. While stirring the suspension of sodium tetracylindrical squid from which this precipitate had been removed, acrylamide monomer (manufactured by Ishizu Pharmaceutical ■, EXT
RA pURg ) was added.

After the solid content of the acrylamide monomer was adjusted to 25% by weight based on the solid content of the sodium tetrasilicic mica, stirring was performed well to obtain a homogeneous suspension.

This mixed suspension was cast onto a glass plate to a uniform thickness of 2.
24 hours at room temperature, then 1 hour at 80°C using a gear opener, and then 120°C.
It was dried at ℃ for 1 hour. The film formed on the glass plate was peeled off from the glass plate to obtain a 40 μm thick film. This film was pressurized at a pressure of 2t/♂ at room temperature, and then thermally polymerized at 180°C for 2 hours in nitrogen gas to form I
After irradiating the electron beam of Q b, qrcLd, 2 more
The final film was heat treated at 50°C for 15 minutes. The toughness P of this film was 40, and the toughness 1 was good.

It also had good flexibility. The heat resistance was also good (indicated by a circle).

Example 2. Comparative Examples 1 to 5 Montmorillonite [Indicative formula] NaO, 55A12.6
7 Mg*, 5s (s 14Q 13) (On),
An inorganic layered compound represented by A powder of 1 Kunipia "G" manufactured by Kunimine Kogyo ■ was immersed in distilled water and purified in the same manner as in Example 1 to prepare a suspension having a concentration of montmorillonite of 4 parts by weight. The same acrylamide monomer as used in Example 1 was added, and the solid content of the acrylamide monomer was adjusted to 25% by weight based on the solid content of montmorillonite.

Stir well to obtain a homogeneous suspension.

This mixed suspension was cast onto a glass plate to a uniform thickness of 2.
Spread it out to make a thick paste, and leave it at room temperature for 24 hours, then use gear open for 1 hour at sO'c, and then leave it for 12 hours.
It was dried at 0°C for 1 hour. After thermally polymerizing this film at 180°C for 2 hours in nitrogen gas, IQ Mra
11. The final film was irradiated with the electron beam of d and further heat-treated at 250° C. for 15 minutes. As shown in Table 1, this film has a strength of 20 kg/mm! , elongation is 5%
The 9 toughness P showed a large value of 50. Furthermore, both flexibility and heat resistance were good.

In methods other than the manufacturing method of the present invention, Comparative Examples 1 to 1 in Table 1
As shown in No. 5, it was not possible to obtain an inorganic film that was strong, flexible, and had excellent heat resistance.

Claims (1)

[Scope of Claims] The inorganic layered compound (A) contains at least −° types of monomers (B) of polar compounds having 0 polymerizable functional groups. An inorganic film that is impregnated or mixed to polymerize the (B)! In the manufacturing method of , before impregnating with the (B),
Alternatively, a method for producing an inorganic film, which comprises forming the composition into a film before or after polymerizing (B).