JPH0370742A - Preparation of organic thin film and its use - Google Patents

Abstract

PURPOSE:To prepare an organic thin film having uniform, high pressure resistance and useful as a material for various sensors by sequentially cumulating single molecular layers on a cylindrical or column-like basic membrane, the single molecular layers being formed on the surface of water in a water tank. CONSTITUTION:Single molecular membranes are sequentially cumulated on a porous cylindrical basic membrane whose pores are filled or coated with a material mainly comprising a substance with a boiling point of 50 deg.C/760 to 150 deg.C/10<-4>mmHg to provide the objective organic thin film, the single molecular layers being formed by developing a solvent having both a hydrophilic portion and a hydrophobic portion on the surface of water in a water tank and subsequently compressing the formed membrane. The composite membrane of the organic thin films is used to prepare a selectively gas-transmissible membrane.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an improved method of the Langmuir-Prodgett method (hereinafter abbreviated as LB method), which is known as a method for producing organic thin films, and its uses, particularly its use. The present invention relates to a gas selective permeation membrane using a composite membrane obtained by the method.

(Prior art) Conventionally, an organic thin film using the LB method is produced by spreading an amphiphilic substance consisting of a hydrophilic part and a hydrophobic part on a water surface and then compressing it, and sequentially accumulating the formed monomolecular layer on a flat substrate. It was created by

This accumulation method includes ■ Vertical f! ■ dipping method (transferring the monomolecular layer by moving the solid substrate vertically up and down through the membrane surface), horizontal adhesion method (bringing a horizontally supported substrate into contact with the monomolecular film and pulling it up to remove the monomolecular layer) There are two ways to transfer the layers.

The organic Eil film formed by the vertical immersion method can have a cumulative film type of X type, Y type, or X type by changing the type of solid substrate and cumulative conditions.
Can be controlled by type.

The LB film created in this way has the following characteristics: (1) the functional parts have a certain orientation, and (2) it has a constant film thickness at the molecular level. It is used as a functional super-311Q-type precept in the required fields of electronics materials, resists, sensors, memory materials, nonlinear optical materials, separation M films, etc.

Among them, many attempts have been made to obtain highly permeable M membranes by taking advantage of the thin film properties of LB membranes, but all of these attempts have used flat plate-shaped porous materials. Therefore, in most cases, it is difficult to form a pinhole-free uniform cumulative film useful for gas separation, and there are no known examples showing good gas separation performance and gas permeation performance.

(Problems to be Solved by the Invention) The conventional LB films described above are all deposited on a planar porous or non-porous base film, and have a cylindrical shape or a cylindrical shape. There are no known examples in which an LB film has been accumulated on a shaped base film.

If LBL is placed on a cylindrical or cylindrical base film,
If an LB film with accumulated pJ can be obtained, the composite material can be used in a completely different way from the conventional composite material in which LBIIA is accumulated on a planar base film, and it will be extremely useful industrially. A new type of thin film material.

For example, compared to a planar composite membrane, in the case of a cylindrical or cylindrical composite membrane, a unit volume can be filled with a composite membrane having a high surface area.

Therefore, when a cylindrical or cylindrical composite membrane is used for applications that require a high surface area, such as separation membranes or sensors, it is possible to create a much more compact device compared to a flat composite membrane. .

Also, unlike planar composite membranes, cylindrical or cylindrical composite membranes have no directionality other than the axial direction, so when used in sensors, etc., signals from all directions other than the axial direction are uniformly transmitted. It also has the advantage of being detectable.

In the field of membrane materials, thin flat membrane composite membranes do not have self-supporting properties, so manufacturing a separation device filled with a large number of such composite membranes is complicated, but in the case of cylindrical composite membranes, ,
Since it is self-supporting, it is easy to manufacture a separation device filled with a large number of the composite membranes.

Furthermore, for boat fishing, the cylindrical composite membrane has higher pressure resistance than the cylindrical composite membrane, so it can be expected to have the advantage of being able to increase the differential pressure during separation operations.

As exemplified above, LBWi! A cylindrical or cylindrical composite membrane using a cylindrical or cylindrical composite membrane can be expected to have many industrially useful features. It can be accumulated, but I couldn't predict it at all.

(Means for solving the problem) A possible method for obtaining a cylindrical composite membrane is to convert a flat composite membrane into a cylindrical one, but in this method,
It is difficult to maintain film uniformity at the joint. Furthermore, there is a limit to the size of the shape of a flat membrane to a cylinder, and microfabrication is difficult.

Therefore, as a result of further intensive study, the present inventors found that LBl1
It has been found that it is possible to directly accumulate 9 on a cylindrical or cylindrical base film.

It is possible to accumulate LB films on cylindrical or columnar base films, whether they are non-porous or porous; however, when LB films are accumulated on a porous base film, it is necessary to A more uniform monomolecular cumulative film can be obtained by accumulating a high-molecular-weight amphiphilic substance in the following base membrane and/or filling or coating the pores of the LB peritoneal pre-accumulation base membrane with a specific substance. The present invention was completed based on the discovery that

That is, the present invention: (1) Forming a monomolecular layer by spreading and compressing an amphipathic substance consisting of a hydrophilic part and a hydrophobic part on the water surface in an aquarium;
In the Langmuir-Prodgett method, in which the monomolecular layer is sequentially accumulated on a base film, the base film has a cylindrical or columnar shape. , the boiling point is 5
0℃/760ffIII+Hg"150℃/10-4m
A method for producing an organic thin film, which uses a base film filled or coated with a material whose main component is a substance in the mHg range, and after forming a thin film on the base film, the filled or coated material is removed by evaporation. It also has characteristics.

Furthermore, the present invention relates to a gas selective permeation membrane using a composite membrane produced by the method described in any one of the above-mentioned (2) items.

The technology of the present invention will be explained in more detail below.

The materials used for the cylindrical shape and columnar base film include ceramics such as quartz and glass, polysulfone, polyacrylonitrile, polyethylene, polyvinylidene fluoride,
Examples include organic polymers such as polyimide and cellulose; semiconductors such as gold gi-silicon such as aluminum, copper, and iron, and gallium-arsenic; however, these base films are substantially insoluble in water. is necessary.

In these cylindrical base films or columnar base films,
The diameter can be arbitrarily selected depending on the purpose of use, and those with a diameter of 0.01 mm to 50 m are usually used, preferably 0.01 mm to 2 m.
A range of 0III11 is used. In addition, when used as a hollow fiber for separation membranes such as gas separation, the effective area per unit volume of the Minmya module can be increased! This is usually used with a diameter of 0.01 m to 5 mm, preferably 0.01 m to 3 mm in diameter.
11, particularly preferably a diameter of 0.01a
Those in the range of ++a to law are used.

With a cylindrical base film or a cylindrical base film, it is possible to accumulate a monomolecular film regardless of whether it is non-porous or porous, and the shape of the base film can be appropriately selected depending on its use. In addition, in porous membranes, pores of various sizes can be used, but those with pore diameters in the range of 10 μm to 15 μm are usually used, and preferably those with pore diameters in the range of 10 μm to 5 μm. used. Furthermore, in a porous hollow fiber base membrane for a gas separation membrane, one having a pore diameter in the range of 10 μm to 1 μm is suitable.

If the pore size is too large, it becomes difficult to support a monomolecular film, and pinholes are likely to occur. On the other hand, if the pore size is too small, the permeation rate of the membrane becomes too low to be practical.

The amphiphilic substance used as the organic thin film in the present invention is
After spreading as a monolayer on the water surface, when pressure is applied,
The molecules are oriented with the hydrophilic groups facing the water side and the hydrophobic groups facing the air side.
Densely packed to form a monolayer. At this time, the range of surface pressure for forming a monomolecular film is usually 5 mN/m to 80 mN/m.
mN/m, preferably I OmN/m ~35 mN/m
It is. If it is less than 5mN/m, it will not be densely packed,
On the other hand, at 80 mN/m, the monomolecular film collapses, although it depends on the structure of the monomolecular film.

The hydrophilic part contains ketones, aldehydes,
Esters, amines, amides, alcohols, fatty acids, divalent metal salts of fatty acids, alkali metal salts of fatty acids, sulfuric esters,
Sulfonated products thereof or polymers containing these hydrophilic groups are suitable.

Further, as the hydrophobic moiety, fluorocarbons, saturated hydrocarbons, unsaturated hydrocarbons, and aromatic hydrocarbons are suitable, and the hydrophobicity becomes stronger as the number of carbon atoms increases. The number of carbon atoms in the hydrophobic moiety depends on its structure, but is usually in the range of 4 to 40, preferably 6 to 30, particularly preferably 8 to 25.

In L8g, a balance between hydrophobic and hydrophilic parts is required; if the number of carbon atoms is too small, the hydrophobicity will be insufficient and a good LB film will not be formed.On the other hand, if the number of carbon atoms is too large, the hydrophobicity will be insufficient. Too strong, also a good LB in this case
No film is formed.

By spreading the above substance on the water surface and applying pressure to form a monomolecular layer, transfer it directly onto the base film.
! It forms a thin film.

The monolayer constituent material used in the present invention may be a low-molecular substance having a pair of hydrophobic parts and a hydrophilic part in the molecule, or a plurality of hydrophobic parts and hydrophilic parts in the molecule. It may also be a polymeric substance having the following.

The structure of the organic thin film constituent material used in the present invention will be explained in more detail below.

(1) Low-molecular monolayer film constituents: The following low-molecular monolayer film constituents are listed in (1)
The one represented by is suitable.

R-A-X... (1) (However, R is an organic group, A is a divalent bonding group, and X represents a hydrophilic group.) Below, each will be specifically explained. explain.

First of all, I have it! Examples of the group R include alkyl groups which may be substituted with aromatic or alicyclic hydrocarbon groups, as well as unsaturated groups such as alkenyl and alkynyl groups. In addition, some of the carbon atoms such as alkyl groups may be substituted with other bonding groups, such as o, s, co, ester groups, aromatic groups, etc.

Long chain alkyl groups include myristyl, pentadecanyl, valmitinyl, stearyl, nonadecanyl, eicosanyl, heptadecanyl, heneicosanyl, behenyl,
Alkyl groups having 8 to 40 carbon atoms, such as tetragosanyl groups, are preferred.

These long chain alkyl groups may be branched,
Further, R has 4 to 25 carbon atoms, preferably 6 to 1 carbon atoms.
2 may be a polyfluoroalkyl group.

Examples of polyfluoroalkyl groups include those containing a fluorine-containing segment as shown below.

CF, +cFs (i is an integer from 0 to 20), CF.

\ CF 4 CF zh (ya is an integer from 0 to 1), / C.F.

HCF zA: c F z'f"j (n is an integer of 0 to 20), and as R, in addition to the polyfluoroalkyl group of the above structure, CF, = CF, oligomerization of CFlCFs-CFt A polyfluoroalkyl group or a polyfluoroalkylene group, which may have a branch that is bottomed by a thin film, or CF3CxF,O+C5FaO)'T-Ch-CO-, (k
is an integer of 0 to 6) It may be a fluorine-containing group containing an ether structure such as.

A in the above-mentioned (1) is a divalent linking group,
An alkylene group, an arylene group, or an alkylene group or arylene group containing oxygen or sulfur is preferred.

In addition, X in the above-mentioned - Shuso (1) is an anionic group, -COO--3(h-1S, Off-1-0SO
Examples include s-PO2-, especially COO- and -5
03 is desirable.

As a specific example of general formula (1), CH3(CHz)zCmiC-C3C(C1lx)sCO
Oh.

11CmiC(C112) + acOOOHljls(C
)It)++SOJ 1 CFs(CFt)qCIhCHiCOO)I.

etc.

The low-molecular monomolecular film-constituting substances are preferably those listed above, but are not limited to these as long as they are substantially insoluble in water.

(2) Polymer monolayer material: Examples of polymer monolayer materials include those consisting of a polymer main chain portion forming a hydrophilic portion and a hydrophobic portion. It will be done.

Here, examples of the polymer main chain portion exhibiting hydrophilicity include those containing ionic groups and those containing polar groups such as ester bonds and amide bonds.

Below, examples of polymeric monolayer film constituents will be explained in more detail.

(1) When the hydrophobic part and the polymer main chain have an ionic bond: In this case, it is represented by the following general formula (n), but (II
), when Z is a cationic group-containing polymer, Y must be a group containing an anionic group and a hydrophobic part; conversely, if 2 is an anionic group-containing polymer, ,
Y must be a group containing a cationic group and a hydrophobic part. Further, it is desirable that n be 10 or more.

Examples of polymers in which Z is anionic include the following.

The compound represented by I [[] below consists of a polyamic acid and an amine having a long-chain alkyl group (in the formula, R
' is a tetravalent Ia group, R2 is a divalent organic group, and n is an integer of 10 or more.

The polyamic acid represented by the above -inclusion (iff) is selected from a tetravalent aromatic organic group such as the following formula (■): (indicates a divalent group such as F 3 ) or a substituted derivative thereof.

Examples of the tetracarboxylic dianhydride represented by (IV) include pyromellitic acid, 3°4.3.4"
-benzophenonetetracarboxylic acid, 3,4.3", 4
-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, bis(3,4-dicarboxyphenyl)sulfone, 2,2-bis(3 ,4-dicarboxyphenyl)propane, butanetetracarboxylic (in the formula,
R1 is a tetracarboxylic dianhydride represented by the following formula (): (same as in general formula (III)) and R1 is represented by the following formula (): % formula % () (wherein Rt is the same as in general formula (1)) The diamine is produced by a conventionally known method for producing polyamic acid.

In the above formula, examples of R1 include dianhydrides of tetracarboxylic acids such as acids.

On the other hand, R2 is usually selected from divalent aromatic groups such as phenylene, naphthylene, biphenylene, and a biphenylene derivative group connected by a divalent group similar to X in R1.

Examples of the diamine represented by the above-mentioned compound (V) include metaphenylenediamine, paraphenylenediamine,
, 4゛-cyaminobiphenyl, 33°-methylene dianiline, 4.4''-methylene dianiline, 4,4゜-ethylene dianiline, 4゜4゜-isopropylidene dianiline, 3,4' oxydianiline , 4,4°-oxydianiline, 4.4°-thiodianiline, 3,3″-carbonyldianiline, 4,4′-carbonyldianiline,
3.3'-sulfonyl dianiline, 4,4''-sulfonyl dianiline, 1.4''-naphthalenecyan, 1,5
Examples include °-naphthalenediamine and 2,6'-naphthalenediamine.

Furthermore, the amines having a long-chain alkyl group used in the present invention are -
・ ・ ・ ・ (Vl) ■ R' (wherein, R3, R4, and R5 are hydrogen atoms or the above-mentioned -
Indicates an alkyl group represented by R in I), at least one of which is R. ).

In addition, as a monomolecular film constituent substance of a polymer containing an ionic group, in the above-mentioned -incorporation (If), when Z is a polymer containing an anionic group, -c as an anionic group is used.
oo--so,-,os.

Examples of Y include a combination of a cation such as an ammonium cation, a pyridinium cation, or a phosphonium cation, and a group containing a hydrophobic moiety represented by R in (1). Ru.

Specific examples include the following.

On the other hand, examples of polymers in which Z is cationic include polymers containing cations such as ammonium cations, pyridinium cations, or phosphonium cations.

In addition, Y in this case is -COO-30s-1O
Those containing an anionic group such as S 03-P Os- and a hydrophobic portion represented by R in the general formula (■) are used.

Specific examples include those shown below.

H3 (CHz)u (2) When the hydrophobic part and the polymer main chain part are connected by a polar group; As mentioned above, as the polar linking group, ester bonds, amide bonds, etc. are used, and specific examples thereof include: Examples include the following polymers.

The structure of the monomolecular film and the structure of the components have been shown above. Next, a method for forming a monolayer will be described.

First, an organic solvent solution of a monomolecular film constituent material is spread on the water surface to form a monomolecular layer, and then this monomolecular layer is transferred onto the base film.

Organic solvents used here include, for example, hydrocarbon solvents such as hexane and octane; aromatic solvents such as benzene, toluene, and xylene; chlorine solvents such as dichloromethane, chloroform, and carbon tetrachloride; diethyl ether, dibutyl ether Examples include ether solvents such as ether solvents, and fluorine solvents such as freon, but they are required to be substantially immiscible with water. In addition, these organic solvents and dimethylformamide, N,N-dimethylacetamide, N
-Methyl-2-pyrrolidone, dimethyl sulfoxide, and other polar solvents can be used in combination.

The concentration of a solution containing an amphiphile that forms a monolayer is
Usually 0. 01~10mmol/j! , preferably 0
．． 05~5mmol/j! The range is selected. Also, -
In packaging (ff), n, which represents the degree of polymerization of the polymer, is not particularly limited, but when placed on a porous membrane, it is preferably in the range of 200,000 to 40,000. If n is less than 20, a stable LB film will not be formed on the porous membrane, and there is no particular upper limit for n, but if n is more than 40,000, it will be difficult to dissolve in the solvent and difficult to use. It is.

In addition, when defining the size of the polymer represented by -closing <n> by the weight average molecular weight, it is usually determined that the polymer has a weight average molecular weight of 3,000 or more, although it also depends on the structure of the repeating unit. is used, preferably having a weight average molecular weight of 5,00
The number used is 0 or more, particularly preferably 10,000 or more. Although there is no particular upper limit to the weight average molecular weight, it is easy to use a weight average molecular weight of about 20 million from the viewpoint of solubility.

In addition, in monomolecular films containing reactive groups (e.g. double bonds, triple bonds) in the hydrophobic part, even if the reaction is carried out after accumulation on the base film,
The reaction may be carried out during development on the water surface and then transferred onto the base film.

In addition to the above methods, the method for forming the monolayer may be changed as appropriate as long as the properties of the monolayer are not impaired.

For example, in case (II) above, when a hydrophilic polymer such as CH-M Hz is used, this hydrophilic polymer is made into a 0.01 to 10 mmol/l aqueous solution in advance, and the above-mentioned solution is added thereto. - Adding an organic solvent solution of a carboxylic acid containing an alkyl chain or a quaternary ammonium salt represented by R in the compound (I) to form CH on the interface.

There is a method to form an amphiphilic monolayer as shown in the following.

Next, a cylindrical shape and a cylindrical base film in which a monomolecular film is accumulated will be described.

Cylindrical and cylindrical base films that accumulate monolayers, as long as they are non-porous, can be accumulated as well as flat base films, whether they are low-molecular monolayers or polymer monolayers. Ru. On the other hand, for porous cylindrical base membranes, low-molecular monolayers,
It is possible to accumulate even monomolecular films of polymers.

However, if you want to form a uniform film without pinholes like Gas 9111M, ■ the weight average molecular weight is 3.
．． Using monolayer constituents with a high molecular weight of 000 or more,
Furthermore, (1) it is preferable that the porous membrane has a molecular fraction [170,000 or less], and more preferably (1) before stacking the monomolecular film, surface treatment is performed by filling or covering the pores of the base film to form a cumulative film. A method that removes the surface treatment material after formation is desirable.

A membrane with a molecular weight cut off of 70,000 or less is a membrane that blocks 90% or more of @ff quality with a weight average molecular weight of 70,000 or less. For example, weight average molecular weight 7
A membrane that excludes 90% or more of dextran with a weight average molecular weight of 0.000 or 90% of albumin with a weight average molecular weight of I65°OOO.
The above-excluded membranes can be mentioned.

There is no lower limit as long as there is gas permeability, but if the pore diameter is too small, there is a problem that the amount of gas permeation will be low. Therefore, a material with a pore diameter of 10 Å or more is usually used.

Materials used for surface treatment include those that are solid at room temperature and those that are liquid at room temperature, and their boiling point is 50"C/760+
Preferably, m*Hg=150°C/10-'mlHg.

Those that are liquid at room temperature include p-xylene, octane, etc., and those that are solid at room temperature include n-octadecane, 1,1,2.2-tetrachloro-1,2-
Examples include difluoroethane. All of these materials are desirably insoluble in water and do not substantially dissolve or swell the base film or monomolecular film. It is also suitable to use agar as a material other than the above for surface treatment.

Specific examples of methods for treating the surface include simply immersing it in a treatment material solution (heating it above its melting point if it is solid at room temperature), or reducing the pressure inside the hollow fiber while immersing it to make holes. Examples include a method of occlusion.

As for the method for removing the treatment material after the monomolecular film has been accumulated, it is preferable to reduce the pressure inside the hollow system at room temperature or while heating. At this time, the heating temperature is preferably a temperature at which the base film and the aTN film do not change, and is usually in the range of 0° C. to 150° C., but is not limited thereto.

In the organic thin film accumulation method, the cumulative film type can be changed to X type, X type, etc. by changing conditions such as surface pressure, temperature, and accumulation rate.
It can be controlled as Y type or Z type.

The cumulative speed is preferably about 0.5 to 20 C11/min, since the accumulated film may peel off if it is too fast.

(Example) Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

synthesis of.

Polyamic acid was produced from 4,4°-oxydianiline and pyromellitic anhydride in the same manner as described in JP-A No. 62-275134, and hexadecyldimethylamine was added thereto to obtain the formula (■) The compound bottomed out.

The weight average molecular weight of the compound of formula (■) is based on the European Pol
ymer, Journal, 13°375 pages (197
As a result of conversion according to the conversion formula described in 7) and taking long chain alkyl into consideration, it was 6,800.

A 1:1 mixed solution of the obtained compound of formula (■) in toluene, N, N-dimethylacedeamide (repeating unit standard concentration 1
mmol/j was spread on the water surface in the accumulation tank of the LB film accumulation device.

The surface pressure-area curve of this monomolecular film of polyamic acid derivative is shown in Figure 1.The curve shows a sharp rise compared to Figure 1, which indicates that this monomolecular film constituent material forms a clean monomolecular film. I can see that you are doing it.

Next, the monomolecular film on the water surface was accumulated on a cylindrical quartz substrate with a diameter of 1.5c+e under a pressure of 26 mN/++n using the vertical immersion method, resulting in a Z-type film with a cumulative ratio of 0.96. Ta.

Cumulative number of operations and ultraviolet absorption spectrum of polyamic acid derivative monomolecular film accumulated on cylindrical quartz substrate 2 5
The relationship with the extinction coefficient at 8 nm is shown in FIG. 2, and it can be seen that good accumulation of the LB film is achieved because this graph shows a linear relationship.

Furthermore, the shape of the absorption spectrum was consistent with that of a polyamic acid derivative separately produced by a solvent casting method.

Example 2 The polyamic acid derivative monolayer prepared in Example 1 was deposited on a non-porous polysulfone hollow fiber with a diameter of 1 cm under a pressure of 30 mN/m using the vertical dipping method, resulting in a Y-shaped film with a thickness of 10 mN/m. The cumulative ratio was 1.8 based on the number of times the layers were stacked. In addition, when the surface pressure is 15 mN/m, it becomes a Z-type film, and 1
The cumulative ratio when the number of laminations was 0 was 1.0.

Example 3 The polyamic acid derivative monomolecular film prepared in Example 1 was coated with an outer diameter of 1.5 mm that could exclude 90% or more of albumin with a molecular weight of 50,000. 4wa, inner diameter 0. When accumulated on a porous hollow fiber of am polyacrylonitrile under a surface pressure of 30 mN/m, a type 2 membrane was obtained. The cumulative ratio was 0.85 after 10 laminations.

Example 4 Repeating unit standard concentration 0.2 mmol/j! To an aqueous solution of polyallylamine having a weight average molecular weight of 160,000, 10
．． 12-pentacosadionic acid 0゜1 m m o
1/j! A chloroform solution of was added dropwise.

FIG. 3 is a surface pressure-area curve of the material.

As shown in FIG. 3, the curve shows a sharp rise, indicating that this monomolecular film constituent material can form a clean monomolecular film.

The monomolecular film has an outer diameter of 0°41m5 at a surface pressure of 30mN/m.
．． The inner diameter is 0.33 mm and the pore size has a weight average molecular weight of 70.0.
When 00 dextran was accumulated in a porous polysulfone hollow fiber capable of excluding 90% or more, a Z-type membrane was obtained. The cumulative ratio was 0.97 for 10 times.

Example 5 A monomolecular film formed in the same manner as in Example 4 was subjected to a surface pressure of 30
When accumulated at mN/m on polyacrylonitrile porous hollow fibers of the same specifications as those used in Example 3, a Z-type membrane was obtained. The cumulative ratio was 0.88 for 10 times.

Example 6 Repeating unit standard concentration 0.2 mmol/j! O, 1 m of dimethyl distearyl ammonium was added to an aqueous solution of sodium polystyrene sulfonate having a weight average molecular weight of 170,000.
mol/j! A chloroform solution was added dropwise. FIG. 4 is a surface pressure-area curve of the material. From FIG. 4, it can be seen that the curve shows a sharp rise, indicating that this monomolecular film-forming substance forms a clean monomolecular film.

When the monomolecular membrane was accumulated on a porous polysulfone hollow fiber of the same standard as that used in Example 4 at a surface pressure of 30 mN/m, a Z-type membrane was obtained. The cumulative ratio was 0695 for 10 times.

Example 7 The tip of a porous polysulfone hollow system with an outer diameter of 0.41 m, an inner diameter of 0.33 m, and a pore diameter capable of excluding 90% of dextran with a weight average molecular weight of 70,000 was hardened with epoxy resin, and then heated at 40'C. The hollow fiber surface was treated by immersing it in liquid n-octadecane, reducing the pressure inside the hollow fiber to 05 mHH, and holding it for 3 minutes.

When a polyamic acid derivative monomolecular film prepared in the same manner as in Example 1 was deposited on this hollow fiber by a vertical dipping method under a pressure of 25 mN/m, a Y-shaped film was obtained. 10 times Jll
l, the cumulative ratio was 1.0.

Example 8 Example 1 was applied to hollow fibers surface-treated in the same manner as Example 7.
Prepare a monolayer under the same conditions as lo.

Accumulated times. The cumulative film type was a Y-type film, and the cumulative ratio was 1°0.

Example 9 A polysulfone hollow system of the same specifications that was surface-treated in the same manner as in Example 7 was coated with 0.1 mmol/j! of polyvinyl stearate (manufactured by Aldrich). A toluene solution of was spread on the water surface and a monomolecular layer formed by compressing it to 25 mN/m was accumulated 110 times, resulting in a Y-shaped film. The cumulative ratio for 110 times was 0.86.

FIG. 5 is a surface pressure-area curve for polyvinyl stearate, and the curve has a sharper rise than this figure. This shows that this monomolecular film constituent material is a clean monomolecular film.

Example IO: Surface treated in the same manner as in Example 7, with an outer diameter of 0°41,
A 30 m polyvinyl stearate monolayer prepared in Example 9 was coated on a porous polysulfone hollow fiber with an inner diameter of 0.33 mm.
It was accumulated 95 times under a pressure of N/m. The cumulative film type was a Y-type film, and the cumulative ratio after 95 times was 0.91.

Example 11 Room temperature, 0.2 mg/f! The surface was treated in the same manner as in Example 7 using an agar aqueous solution. Outer diameter 0.41M, inner diameter 0.3
A polyamide M derivative monolayer prepared in Example I was applied to a 3 m++ porous polysulfone hollow fiber at a surface pressure of 25 mN/m.
When the film was accumulated 10 times, the cumulative ratio was 0.94, and the cumulative film type was a Z-type film.

Example 12 The polyamic acid derivative monomer prepared in Example 1 was applied to a porous polysulfone hollow fiber with an outer diameter of 0.41 m5 and an inner diameter of 0.33 m, which had been surface-treated using n-octane in the same manner as in Example 7. When the molecular film was accumulated at a surface pressure of 25 mN/m, the cumulative ratio was 0.93 after 10 accumulations. The cumulative film type was a Y-type film.

Example 13 1.1,2.2-Tetrafluoro-1,2-dichloroethane was heated to 40°C to make it liquid, and then it was applied to a porous polysulfone hollow fiber with an outer diameter of 0.41 m and an inner diameter of 0.33 m. The surface was treated in the same manner as in Example 7, and the surface pressure was 30 mN/
When the polyamic acid monomolecular film prepared in Example 11 was accumulated using m, the cumulative ratio was 0.85, and the cumulative film type was a Y-type film.

Example 14 The hollow fiber obtained in Example 7 was heated to 80°C, and the inside of the hollow system was treated with a reduced pressure of 0.05 kg Hg for 3 hours, and the amount of gas permeation was measured. (c4-5TP/
ca-cmmHg~sec), Q Hz -1,3
5x 10-' (cd-3TP/c11-cmHg・
sec), aR”z=2.6 was obtained.

Example 15 The gas permeation amount of the hollow fiber obtained in Example 8 was measured in the same manner as in Example 14, and Q ox -6,22X10-'
(d-5TP/d-CmmHg~5eC),
Q sz -1゜97XIQ-''(d-3TP/
cd -cmNg-sec), α verse = 3.2 was obtained.

Example 16 The gas permeation amount of the hollow fiber obtained in Example 9 was measured in the same manner as in Example 14, and Q, □-5, 23X10-' (d
・5TP)c(・cmHg-sec)
, Q sz =2゜04X10-' (a
i-3TP/cd-cmmHg~sec), α:”
z-2,56 was obtained.

Example 17 The gas permeation amount of the hollow fiber obtained in Example IO was measured in the same manner as in Example 14, and Q at -5,34x10-'
(cd-3TP/cd ・cmHg~sec) %
Q old = 1゜65 x 10-” (cd-5TP
/cd-ctsHg-sec], α2S=a,2 was obtained.

(Effects of the Invention) By the method of the present invention, it is possible to accumulate an LB film on a cylindrical or cylindrical base film useful for various electronic materials or various sensor materials that require a high surface area including gas sensors. be.

Further, a composite membrane in which an LB membrane is accumulated on a porous cylindrical (hollow fiber) base membrane is useful as a highly permeable separation membrane material.

Surface pressure of body monolayer (m N/m) - area (person 2
/unit) is a curve graph showing the relationship.

FIG. 2 is a curve graph showing the relationship between the cumulative number of operations and the extinction coefficient of the polyamic acid derivative monolayer according to Example 1.

FIG. 3 is a curve graph showing the relationship between surface pressure and area of 10.12-pentacosasioninic acid and polyallylamine according to Example 4.

FIG. 4 is a curve graph showing the relationship between surface area and surface pressure of polystyrene sulfonic acid and dimethyldistyallylammonium.

FIG. 5 shows the surface pressure (mN/m)-area (person”/unit) of polyvinyl stearate according to Example 9.
It is a curve graph showing the relationship.

[Brief explanation of drawings]

FIG. 1 is a polyamic acid derivation according to Example 1. area ()<2/untt) Figure 2 Cumulative number of operations surface pressure

Claims (3)

[Claims] (1) A Langmuir method in which an amphiphilic substance consisting of a hydrophilic part and a hydrophobic part is spread on the water surface in an aquarium and compressed to form a monomolecular layer, and the monomolecular layer is sequentially accumulated on a base film. A method for producing an organic thin film in the Projet method, characterized in that the base film has a cylindrical or cylindrical shape. (2) The pores of the porous cylindrical base membrane are prepared in advance so that the boiling point is 50℃/760mmHg to 150℃/10^-^4mm.
A claim characterized in that a base film filled or coated with a material whose main component is a substance in the Hg range is used, and after forming an organic thin film on the base film, the filled or coated material is removed by evaporation. The method for producing an organic thin film according to item (1). (3) A gas selective permeation membrane using a composite membrane produced by the method according to any one of claims (1) and (2).