JPS62266171A - Preparation of monomolecular film - Google Patents

Abstract

PURPOSE:To obtain a monomolecular film having a necessary amount of hydrophilic groups present on the atmospheric side thereof, by using a necessary amount of a compound obtained by protecting the hydrophilic groups at both terminals of an org. compound having the same hydrophilic groups at both terminals thereof by a hydrophobic protective group as a part of a raw material. CONSTITUTION:A mixture of an org. compound represented by X-R-X (wherein X is a hydrophilic group and R is a 8 or more hydrocarbon group) having the same hydrophilic groups at both terminals thereof and an org. compound represented by X'-R' (wherein X' is a hydrophilic group and R' is 8 or more C hydrocarbon group) having a hydrophilic group at the single terminal thereof is used as a raw material. Both of the hydrophilic groups at both terminals of the compound represented by X-R-X in the raw material is protected by a hydrophobic protective group and this protected compound is used corresponding to the amount of the hydrophilic groups necessary on the surface of a monomolecular film with respect to the compound represented by X'-R' to form the monomolecular film having a necessary amount of the hydrophilic groups on the atmospheric side thereof by an LB method.

Description

Detailed Description of the Invention [Industrial Application Field] This invention is capable of adsorbing onto an organic monomolecular film, especially a hydrophilic group H, and after adsorption, a hydrophilic group is added to the gas side surface (the side opposite to the base material). Alternatively, the present invention relates to a method for producing an organic monomolecular film characterized by having a reactive hydrophilic 1-1 group.

[Prior Art] Monomolecular films and cumulative films of organic compounds have many uses. In the field of electronics, for example, applications are being considered for insulating films for semiconductor devices with precisely controlled film thickness, protective lubricant films for magnetic disk drives, photoelectric conversion films, optical information recording films, optical information storage films, etc. has been done. For these purposes, a method for producing monomolecular films and cumulative films is a method in which amphiphilic substances are highly oriented on the water surface to form a monomolecular layer, and the monomolecular layer is transferred onto a substrate. The so-called Langmuir-Blodgett method is often used.

[Problems to be solved by the invention] However, one molecule of the monomolecular film or cumulative film produced by this method generally has a hydrophilic group at only one end of the long chain alkyl group. When producing a monomolecular film or a cumulative film made of such constituent molecules, it is necessary to prepare the film abutment, i.e., the side opposite to the base material, due to thermodynamic stability issues. It is necessary to have a membrane structure in which the hydrophobic part is exposed on the gas side. It is known that the surface (J1) becomes hydrophobic.

Therefore, conventionally it has been very difficult to form a monomolecular film with hydrophilic groups exposed to the gas side.
This difficulty has been a major problem in creating new functions (=t'j-) by adsorbing a substance or reacting a substance with a membrane.

However, many of the hydrophilic 1!1 groups are generally highly reactive, and if such a film could be created, it would be possible to impart the reaction '1 (1) to the surface of a monomolecular film or its cumulative film.Hydrophilic 1! (1-This kind of reactivity or (51
Hydrophilicity ↑1 itself can be used to create, for example, insulating layers for semiconductor tom necks, protective lubrication for disk devices, etc., layers with photoelectric conversion functions, optical information recording layers, etc. It is possible to provide a scientific information storage layer etc. on the upper molecular membrane.
This means that you will be able to do it.

The purpose of the present invention is to provide a novel method for producing a monomolecular film in order to solve the problems described above.
Specifically, hydrophilic / 1 no 1 support 1. -': l17 & can be shielded, and after absorption, the gas side, sui1, i.e. group I, l
Production of Koshin molecular film having hydrophilic groups on the opposite side
1 [Means for Solving Problems 1] The present invention (j, general formula: Number of carbon atoms is 6
Hydrophilic 1 at both ends of one or more organic compounds represented by 3 or more, preferably 14 or more hydrocarbon groups
After substituting No. 1 group with a hydrophobic protecting group, the general formula: A monomolecular film that is simultaneously adsorbed on a hydrophilic substrate with one or more organic compounds represented by -) using the Langmuir-Brosietz method while controlling the orientation. This is a manufacturing method.

The gist of the present invention is to produce Langmi core products 1 by using organic compounds having the same hydrophilic group at both ends and an organic compound having a hydrophilic group at one end as raw materials.
When producing a monomolecular film having hydrophilic groups on both the substrate side and the gas side on a hydrophilic substrate using the ~ method, the same hydrophilic 1 By using hydrophilic groups at both ends of the terminal compound protected with hydrophobic protecting groups depending on the amount of hydrophilic groups required on the surface, the required amount of hydrophilic groups on the gas side can be obtained. The purpose of the present invention is to provide a method for producing a monolayer film that has previously existed.

X and X' in the general formulas (T) and (TI>, which are the hydrophilic 1i groups of the monomolecular film in the present invention, are human[-1xyl group, carboxyl l\l group, buocarboxyl group, dithio carboxyl group,
Examples include sulfino group, sulfur group, carbamoyl group, -1-ocarpayl group, amino group, substituted amino group, etc., and the monolayer-forming substance has one of these hydrophilic groups at both ends. and an organic compound having a hydrophilic group at one end that is the same or different from the hydrophilic group of the organic compound (J).

Furthermore, the general formula (I) and (TI) Gi2a3
R and R' are divalent and monovalent chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups 11j, or a part of these hydrocarbon groups having one, two or more phenylene groups, respectively. Examples include hydrocarbon groups containing

R and R' may be the same or different.

The proportions of the compound of the general formula (1) and the compound of the general formula (IT) can be appropriately selected depending on the fabric of the hydrophilic group required on the monolayer surface, but usually the compound of the general formula (I
> is present in an amount of 3 mol % or more, preferably 10 mol % or more. Further, each compound may be used alone, or if necessary, two or more types may be used in combination.

According to the method of the present invention, for compounds having hydrophilic groups at both ends, the hydrophilic groups at both ends are protected with hydrophobic groups, and only one side is deprotected on the water surface. By this, a monomolecular film can be formed using the Langmuir-Blodgett method. Hydrophobic protecting groups that can be used for this purpose include trialkylsilyl groups such as trimethylsilyl group, dimedylyisopropylsilyl group, dimethyltajaribdelsilyl group, ether type protecting groups including dihydropyranyl group, etc. Appropriate ones may be used among those generally used in the field of organic synthetic chemistry, such as ester protecting groups and amide protecting groups such as trifluoroacetic acid amide. When selecting these hydrophobic protecting groups, one is selected that allows only one side of the protecting group to be removed on the water surface under appropriate conditions.

On the other hand, compounds with a hydrophilic group at only one end do not need to protect the hydrophilic group and are usually used as is, but compounds with hydrophilic groups at both ends can be deprotected simultaneously under appropriate deprotection conditions. If it is deprotected, it may be protected by a hydrophobic protecting group.

In this way, using a compound in which the hydrophilic groups at both ends of the compound of general formula (I> are protected with hydrophobic↑)1 protecting groups and a compound of general formula (II), Remove only one of the protective groups of the compound >, align it as a monomolecular film, and transfer it onto a hydrophilic substrate using the Langmuir-Blodgett method. Conditions such as concentration, water temperature, and development time on the water surface must be appropriately selected.

Furthermore, the water may contain metal ions that form a salt of a monomolecular film on the water surface.

In the method of the present invention, both hydrophilic groups at both ends of the compound of formula (I) are made hydrophobic, which is advantageous in that it is more easily soluble in general organic solvents than when only one end is made hydrophobic. . In the Langmuir-Blodgett method, it is necessary to dissolve the raw material in an organic solvent, so it is desirable that the solubility of the raw material is high. Furthermore, it is thought that there are many cases in which it is easier to protect simultaneously than selectively protecting one side with a hydrophobic protecting group, so the advantage of this method is not only in solubility.

Since the surface of the resulting monomolecular film is protected with a hydrophobic protecting group, it can be made into free hydrophilic groups by immersing it in an appropriately prepared reagent solution or by exposing it to an appropriate reagent vapor. can.

[Function] A mixture of a compound of general formula (1) having the same hydrophilic group at both ends and a compound of general formula (II) having a hydrophilic group at one end is used as a raw material, and the protecting group and its protection conditions are Alternatively, by appropriately selecting deprotection conditions, a monomolecular film having a desired amount of desired hydrophilic groups on the surface can be produced on a hydrophilic substrate by the Langmuir-Blodgett method. According to the method of the present invention, the general formula (
The hydrophilic groups at both ends of the compound I) are made hydrophobic with hydrophobic protecting groups, and as long as conditions are provided such that only one side of the protecting group is deprotected on the water surface, it can be oriented as a monomolecular film, It can be transferred onto a hydrophilic substrate.The general formula (
Deprotection of the hydrophobic protecting group of I> is a means to provide the desired hydrophilic group on the surface.

[Example] Next, the present invention will be explained by examples.

Example 1 1.16-dicarpoxyhexadecane (4mmOf!)
To a solution of tetrahydrofuran (2 (7!)) was added 2.2 times the amount of triethylamine of dimethylisopropylsilyl chloride and heated at 50°C for 30 minutes.After cooling to O'C, 30 ml of hexane was added and the mixture was heated to O'C.
Rinse with water (3 x 307) L/. After drying over magnesium sulfate, the solvent was removed under reduced pressure to obtain 1,16-bis(dimedylisopropylsilyloxycarbonyl)hexylnadecane. 25μ...op of this substance and 25μmob of octadecanoic acid for 10m! ! The sample was dissolved in chloroform, developed on an aqueous hydrochloric acid solution prepared to have a pl+ of 4.5, and transferred onto a quartz substrate while maintaining the surface pressure at 25 dyn/Cm2. When the surface energy of the surface of the substrate as copied was measured from the contact angle of the droplet, it was found to be 18er.
g/c...2, and was very hydrophobic.

Next, this substrate was immersed in an aqueous solution of I) 114.0 hydrochloric acid and thoroughly washed with water to form a monomolecular film made of a mixture of equal amounts of 1,16-dicarpoxyhexyl-nodenonone and octadecanoic acid on the substrate. It's 1q. The surface energy of the substrate surface is 48 fl! It was large as ro/CllI2 and showed high hydrophilicity. The high hydrophilicity of this monomolecular film did not change at all even after being left at room temperature for one week.

Next, a hydrophilic group (carboxyl group in this case) on the surface of this monomolecular film is placed on a quartz substrate on which this isopropylene compound of 1,16-dicarpoxyhexadecane and octadecanoic acid is oriented and adsorbed as a monomolecular film. Here's how to make the most out of your reactions.

Molecular weight approximately 3000 (r) Hand union 0=C=N-CF2(02F40)p-(CF20)q
-CF2-N=C=0 (p:q=1:1, each structural unit is irregular) was dissolved in Freon to prepare a solution of 0.08 monomers. This solution was spin-coated onto the quartz substrate having carboxyl groups on its surface at a rotation speed of 2,500 times/min, and after baking at 100°C,
(I washed it.

When comparing the surface energy of the obtained substrate 1"-1 with that before contacting with the hand coalescence, it was found that the surface energy of the obtained substrate was 4) (from 21e"
It was found that q/Cm2 was significantly reduced. 3゜If the carboxyl group and the sardine ana-1~ group had not reacted, the cleaning-C-hand combination by Freon would have been eroded away from the middle float membrane. It's a lotus. Therefore, the reactivity of the hydrophilic 1) group in the inner float membrane produced by the method of the present invention is effectively utilized, and the carboxyl group on the monomolecular membrane surface reacts with the isocyanonate group at the end of the polymer. I understand that.

Practical tS Example 2 1,16-bis(dimethylisopropylsilyloxycarminyl)hexadecane 5fnomO synthesized in Example 1
f! And A phtadecanoic acid 45μmof! 'IOm(!
It was dissolved in glue [ ] and developed on an aqueous hydrochloric acid solution adjusted to pH 4.5, and the surface pressure was adjusted to 256 yn/cm2.
The image was transferred onto a quartz substrate while maintaining the same temperature. Calculate the surface energy of the surface of the substrate as it was copied from the contact angle of the droplet by -1
g,,,,-Iko.

Subsequently, this substrate was immersed in an aqueous hydrochloric acid solution with a pH of 4.0, and then thoroughly washed with water to obtain a monomolecular film made of a mixture of 1,16-dicarpoxyhexadecane and octadecanoic acid on the substrate. . The surface energy of the substrate surface is /1
It was as large as 7erg/cm2 and showed high hydrophilicity. The high hydrophilicity of this monomolecular film did not change at all even after being left at room temperature for one week.

[Effects of the Invention] As explained above, since the monomolecular film obtained by the method of the present invention has hydrophilic groups on its surface, it can be Various applications are expected.

Claims (1)

[Claims] (1) Both ends of one or more organic compounds represented by the general formula: X-R-X (wherein, X is a hydrophilic group and R is a hydrocarbon group having 8 or more carbon atoms) After converting the hydrophilic group into a hydrophobic protecting group, the general formula: 1. A method for producing a monomolecular film, which comprises simultaneously adsorbing one or more organic compounds shown on a hydrophilic substrate using the Langmuir-Blodgett method while controlling orientation.