JPS62266166A - Preparation of monomolecular film - Google Patents

Abstract

PURPOSE:To provide a hydrophilic group to the atmospheric side of a monomolecular film after formation, by preliminarily protecting only one hydrophilic group of an org. compound having different hydrophilic groups at both terminals thereof being a raw material by a hydrophobic protective group. CONSTITUTION:An org. compound having different hydrophilic groups at both terminals thereof is used as a raw material and, by adequately selecting a protective group and the de-protective condition thereof, a monomolecular film having hydrophilic groups provided to the surface thereof can be formed on a hydrophilic base material by an LB method in such a state that only one hydrophilic group is protected. In this case, as the org. compound, one or more kinds of a compound represented by X-R-X' (wherein X and X' are respectively mutually different hydrophilic groups and R is 8 or more, desirably, 14 or more C hydrocarbon group) is used alone or a mixed state.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention is capable of adsorbing onto an organic monomolecular film, particularly a hydrophilic substrate, and after adsorption, a hydrophilic group, Alternatively, the present invention relates to a method for producing an organic monomolecular film characterized by having a reactive hydrophilic 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, methods for producing monomolecular films and cumulative films include 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-Prodgett method is often used.

[Problems to be Solved by the Invention] However, the material molecules constituting the monomolecular film and the cumulative film produced by this method generally have a hydrophilic group at only one end of a long chain alkyl group. When producing a monomolecular film or a cumulative film made of such constituent molecules, due to thermodynamic stability issues, it is necessary to add a hydrophobic portion to the gas side, which is the side opposite to the membrane abutment and shank 15 base material. Exposure! Is it necessary to have a film structure with ale<? It is known that even if the hydrophilic group portion is exposed on the gas side, if left untreated, the 33<C> constituent molecules will undergo inversion and the surface will become hydrophobic.

Therefore, in the past, the hydrophilic groups were exposed to the gas side j, l−j l
It is very difficult to form a monomolecular film of the following shape, and therefore, after producing a monomolecular film or a cumulative film, the second step is to absorb a hydrophilic substance to rejuvenate the film. This difficulty was associated with the human problem in creating new functions by reacting substances with molecules.

However, hydrophilic groups are generally rich in reactive groups, and if it is possible to create a film that does so, it is possible to have reactive groups ("t") on the surface of a monomolecular film or a cumulative film. 'J can be done.Hydrophilic'1) One such <r reaction'
[) 1 or hydrophilic / There is a possibility that the amount of information stored on a single molecule will increase.

OBJECTS OF THE INVENTION (To solve one or more of the problems mentioned above,
A method for producing a new 4F monolayer (;-impatiently).
Production of an open-mouthed monomolecular film that is Fi and has one hydrophilic ↑ group on the gas side after absorption and on the side opposite to the base material 3j
Our goal is to provide the QR method.

[Means for Solving the Problems] The present invention is based on the general formula:
(1-< indicates a hydrocarbon group having 8 or more carbon atoms, preferably 14 or more) After converting 11 groups to hydrophobic protected y^, -C, the orientation is controlled to 'C-hydrophilic 7 using Langmicoarp's method, and the non-absorption is specially prevented. There is a method C for producing a monolayer.

The gist of the present invention is! A compound having 14 hydrophilic stars at both ends is 1 trillion rl, and Langmi 1 Arp [-1 is applied to a hydrophilic base material 10 on both the base material side and the gas side. When producing a monomolecular film with hydrophilic groups, only one hydrophilic group of the raw material, an organic compound having different hydrophilic groups at both ends, is protected by a hydrophobic protecting group. It is.

The hydrophilic group of the monomolecular film in the present invention is the general formula (
X and X' in I) include a hydroxyl group, a carboxyl group, a mercap-1 group, a thiocarboxyl group, a diguocarboxyl group, a sulfino group, a sulfo group, a carbamoyl group, an amino group, and a substituted 7 amino group. The monolayer-forming substance is an organic compound having two of these hydrophilic groups at both ends.

Further, in the general formula (I>, R is a divalent chain-type saturated hydrocarbon group, a chain-type unsaturated hydrocarbon group, or one or more T-nylene groups in a part of these hydrocarbon groups). Examples include hydrocarbon groups containing

These compounds may be used alone or in combination of two or more if necessary.
= , no.

According to the method of the present invention, both ends are hydrophilic and l! i. ,,1
% (bar) with a hydrophobic group; One C goes off.

4T straw, - Hydrophilic 1] 1 group Hydrophobic = 11 groups (
If you convert it to J (-'), it is exactly equivalent to the amphiphilic substance which is normally 1 [1 to 11 (, 2) or C'.

Both terminals used in the present invention 1 <-i hydrophilic 1> 1
The substance on the right of the group has the same hydrophilic ↑ JI Jt on both ends. Compared to the substance with 11
It has 'Pj tl that it is easy to indemnify. As a hydrophobic protecting group that can be used for this purpose ('', 1.
- Realkylsilyl group, dimethylisopropylsilyl group, 1-heralkylsilyl group such as dimethyl9-si !protecting group, ] helinol [l [l] acetic acid j' mido, etc.). ,,these hydrophobic・l
'l When selecting a protective box, -) is used for the compound of formula (T).
・Only one hydrophilic group of 1 is selectively protected,
and a hydrophilic group (selected in consideration of the fact that the hydrophobic protecting group on the surface is easily deprotected after forming a monomolecular film on A. Also, as a method of introducing the hydrophobic protecting group, directly one of the hydrophilic groups The method may be a method in which a hydrophilic group is converted into a hydrophobic protecting group, or a method in which both hydrophilic groups are converted into a hydrophobic protecting group and then only one of the protecting groups is deprotected.

Using a compound in which one hydrophilic group is protected with a hydrophobic protecting group in this way, it is oriented as a monomolecular film on the water surface and transferred onto a hydrophilic substrate by the Langmico-Arplojet method. To prevent the protective group from being removed at the water surface,
It is necessary to appropriately select various conditions such as the concentration of various ions in water, the temperature of the water, and the time of development on the water surface. Furthermore, the water may contain metal ions that form a salt of a monomolecular film on the water surface.

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. .

[Action 1 Using an organic compound having different hydrophilic groups at both ends as a raw material, only the hydrophilic 1 NoroJ of the protective group 11; (by appropriately selecting the protective strip 1'1, y)] After protecting
By Lang Mini L-f[1] method, a hydrophilic substrate is coated with a hydrophilic layer on the surface. Iko1 (1
It is possible to create molecular membranes. According to the method of the present invention, one end is hydrophilic ↑/l! ; 4 with ice cubes ↑) 1 H, 1q4
Since J is made more hydrophobic, it can be easily oriented as a monomolecular film on the water surface. After copying the mother tree 1 thick onto the material, deprotection is performed on the surface [i.
EXAMPLES Next, the present invention will be explained with reference to examples.

Example 16 - Akan (4111moJ)
! ) in tetrahydrofuran (20mi2) solution with 2-
21H! of dimethylisoprop I-1 virsilyl chloride and 2.2 times the amount of triethylamine were added, and the
Heated at ℃. After cooling to O'C, 30 m of hexane was added and washed with an aqueous solution of hydrochloric acid (3X 3M) at pH 4,5 at 0 °C, followed by distilled water (3X 30 ml) at 0 °C. After drying over magnesium sulfate, The solvent was removed under reduced pressure;
16-(dimethylisopropylsilyloxy)hexadecanoic acid was obtained. This substance was dissolved in chloroform, spread on distilled water, and transferred onto a quartz substrate while maintaining the surface pressure at 25 dyn/Cm2. Calculating the surface energy of the surface of the substrate as it was copied from the contact angle of the droplet, it is 1
8erg/cm2, and was extremely hydrophobic.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to obtain a monomolecular film of 16-hydroxyhexadecanoic acid on the substrate. The surface energy of the substrate surface was as large as 49erg/Cm2, indicating 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, the 16-hydroxyhexadecanoic acid obtained in this example was oriented and adsorbed as a monolayer on a stone substrate, and the hydrophilic groups (here, hydroxyl groups) on the surface of this monolayer were reacted. We conducted an experiment using gender.

Polymer 0=C=N-CF2(C2F40)p-(CF20)q with a molecular weight of about 3000
-CF2-N=C=0(+):Q=1:1, each structural unit is irregular) was dissolved in Freon, and 0.08% by weight
A solution was prepared. This solution was spin-coated onto the quartz substrate having hydroxyl groups on its surface at a rotation speed of 2500 times/min, baked at 100° C., and then washed with Freon.

When the surface energy of the obtained substrate was compared with that before contacting with the polymer, it was found that it was 49 to 16 erg/cm before contact.
It was found that the number decreased significantly to 2.

If the hydroxyl group and isocyanate group do not react,
Washing with Freon should cause the polymer to separate from the monolayer. Therefore, it can be seen that the reactivity of the hydrophilic groups on the monomolecular film of the present invention is effectively utilized, and the hydroxyl groups on the surface of the monomolecular film react with the isocyanate-1 groups at the terminals of the polymer.

[Effects of the Invention] As explained above, the monomolecular film removed by the method of the present invention has hydrophilic groups on its surface.
Various applications are expected by utilizing the reactivity or hydrophilicity of the 41 groups.

-11-'

Claims (1)

[Claims] (1) General formula: X-R-X' (wherein, X and X' are different hydrophilic groups, R
represents a hydrocarbon group having 8 or more carbon atoms) After converting one hydrophilic group of one or more organic compounds represented by (representing a hydrocarbon group having 8 or more carbon atoms) into a hydrophobic protecting group, using the Langmuir-Blodget method. A method for producing a monomolecular film characterized by adsorption on a hydrophilic substrate while controlling orientation.