JPS62266172A - 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 different 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 and X' are respectively mutually different hydrophilic groups and R is a 8 or more C hydrocarbon group) having different 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' is protected by a hydrophobic 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 make it possible to form the monomolecular film having a necessary amount of the hydrophilic groups present on the atmospheric side thereof.

Description

Detailed Description of the Invention "Industrial Application Field" This invention is an organic monomolecular film, in particular, capable of being adsorbed onto a hydrophilic substrate, and which has a hydrophilic group on the gas side surface (opposite side to the substrate) after adsorption. 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 monomolecular film and cumulative film produced by this method are composed of a monomolecular film (A-linked molecules generally have a hydrophilic group only at one end of a long chain alkyl group). When producing a monomolecular film or a cumulative film composed of such constituent molecules, due to thermodynamic stability issues, a hydrophobic layer should be added to the abutment of the film, that is, the gas side opposite to the base material. (1) It is necessary to leave one part of the film structure exposed. If you leave the hydrophilic group exposed on the gas side and leave it for a while, it is known that in J, the constituent molecules will be inverted and the surface will become hydrophobic.

In the past, it was extremely difficult to form a monomolecular film in which the hydrophilic 1-1 group was exposed to the gas side. Hydrophilic 1) 1. Adsorbs a substance or reacts the substance with the membrane ■
This difficulty was cited as a major problem in implementing new features.

However, hydrophilic 1-1 groups are generally rich in reaction 1-1, and if such a film could be created, it would be possible to impart reaction 1-1 to the surface of a monomolecular film or each cumulative film. That will happen. This type of reaction of hydrophilic '1' or hydrophilic '1' can be used, for example, insulating layers for semiconductor devices, protective lubricating layers for magnetic disk devices, layers with photoelectric transfer function, optical This makes it possible to provide optical information storage layers, optical information storage layers, etc. on a monomolecular film.

The purpose of the present invention is to solve the problems mentioned above.
The objective is to provide a novel method for producing a monomolecular film, which can be adsorbed onto a hydrophilic abutment, and after adsorption, hydrophilic groups are added to the gas side, the hemlock base material, and the support side. An object of the present invention is to provide a method for producing an organic monolayer having the following properties.

[Means for Solving the Problems] The present invention has the general formula: Number of carbon atoms: 8 or more, preferably 1/1
After converting the hydrophilic groups at both ends of one or more organic compounds represented by the above hydrocarbon groups into hydrophobic/[11 protecting groups, general 2, 3
One or two types represented by the formula: X-R-X'() (wherein, This is a method for producing a monomolecular film, which is characterized in that the organic compound described above is simultaneously adsorbed onto a hydrophilic substrate while controlling its orientation using the Langmuir-Brosietz 1~ method.

The gist of the present invention is to use an organic compound having a hydrophilic group at both ends and an organic compound having a hydrophilic group at one end as a raw material.
When manufacturing and coating a monomolecular film having hydrophilic groups on both the base material side and the gas side using a hydrophilic method, the specific hydrophilic groups are used as part of the raw material. The hydrophilic/I-1 groups at both ends of an organic compound are protected with hydrophobic protecting groups, and used depending on the amount of hydrophilic-1/1 groups required on the surface. An object of the present invention is to provide a method for producing a monomolecular film in which a necessary amount of hydrophilic groups are present on the gas side.

X and X' in the general formula (I>) include a hydroxyl group, a carboxyl group, a mercapl group, a dicarboxyl group, a didiocarbo-4-syl group, a sulfino group,
Examples include a sulfo group, a carbamoyl group, a thiocarbamoyl group, an amino group, and a substituted amino group, and the compound has two of these hydrophilic groups at both ends. Moreover, the above general formula (T
X II in () in l) may also include the same groups as mentioned above. Here, X II may be the same as or different from X or X'.

Furthermore, in the general formulas (I> and (IT), R and R' each represent a divalent and monovalent chain-type saturated hydrocarbon group, a chain-type unsaturated hydrocarbon group, or a chain-type unsaturated hydrocarbon group, respectively. Some examples include hydrocarbon groups containing one or more (2) nylene groups.

R and R' may be the same or different.

The ratio of the compound of general formula (I) and the compound of general formula (II) to be used can be appropriately selected depending on the amount of hydrophilic groups required on the monolayer surface, but usually the compound of general formula (I
>3 mol% or more, preferably 10 mol% or more of the compound. 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 a compound having one hydrophilic group 1) at both ends, the hydrophilic groups at both ends are protected with the hydrophobic group 1), and only one side is deprotected on the water surface. By giving conditions, Langmuir Brodziets 1~
A method can be used to form a medium molecular film. Hydrophobic protecting groups that can be used for this purpose include trialkylsilyl groups such as trimethylsilyl group, dimedyliisopropylsilyl group, and dimedyl tert-butylsilyl group, ether protecting groups including dihydropyranyl group, etc.
Similarly, suitable ones may be used among those generally used in the field of organic synthetic chemistry, such as ester protecting groups and amine F-based protecting groups such as amine F trifluoroacetate. When selecting these hydrophobic protecting groups, it is preferable that the hydrophilic groups at both ends of the compound of general formula (I>) be protected at the same time by a common protecting group introduction means, and specific examples include: For compounds that have both a hydroxyl group and a mercapto group (Jf, i~realkylsilyl(dio)ether type iJI, for compounds that have both a hydroxyl group and a carboxyl group, Te1~rahydrobilanyl) ether,
Examples include ester-type protecting groups.

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, a compound in which the hydrophilic groups at both ends of the compound of the general formula (1) are protected with a hydrophobic protecting group and a compound of the general formula (IT
), remove only one of the protecting groups of the compound of general formula (I>) on the water surface, orient it as a monomolecular film, and transfer it onto a hydrophilic substrate by the Langmuir-Prodgett method.

Generally, when different types of hydrophilic groups are protected by a common means of introducing a protecting group, the ease of deprotection of the two protected groups differs considerably. Therefore, in this method, Langmuir
Among the different hydrophilic groups at both ends protected by hydrophobic protecting groups by chemical species in the aqueous phase used in the Projet method or water itself, only the hydrophobic protecting group at one end is deprotected and a single molecule is formed on the water surface. Leave it to form a film. The hydrophobic protecting group at the other end must not be deprotected until it forms a monolayer using the Langmuir-Brosietz method.
It is necessary to appropriately select conditions such as water temperature and development time on the water surface so that only one desired deprotection occurs and the other conditions do not occur. Note that metal ions that form salts of raw materials may be added to the water.

In the method of the present invention, both hydrophilic groups at both ends of the compound of formula (I> are made hydrophobic, so it is advantageous in that it is more easily soluble in general organic solvents than when only one end is made hydrophobic. In the Langmuir-Prodgett method, it is necessary to dissolve the raw material in an organic solvent, so it is desirable that the solubility of the raw material be greater than 1. It is thought that there are many cases in which simultaneous protection is easier than protection with a protective group, so the advantage of this method lies only in solubility (and not in protection).

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. .

[Effect] A mixture of a compound of general formula (I>) having different hydrophilic groups 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 type of protecting group and Langmuir By appropriately selecting the state of the aqueous phase used in the Projet method, only one hydrophilic group of the compound of general formula (I) protected at both ends is deprotected at the water surface, and then the hydrophilic substrate is It is possible to produce a monomolecular film having a desired amount of hydrophilic groups on the surface.According to the method of the present invention, among the hydrophilic groups made hydrophobic by the hydrophobic retaining FJW at both ends, Since only one side is deprotected on the water surface, the compound of the general formula (D) can be easily deprotected as a monolayer along with one compound on the water surface, leaving a hydrophobic protective layer only on the other end. Deprotection after transfer to a hydrophilic substrate is a means to provide the desired hydrophilic groups on the surface.

[Example] The present invention will be described in detail below using Examples.

Example 1 16-Divido1]xyhekylide'canoic acid (4 mmo
1 to 11 furan (2(7) solution to 2.2
Double amount of dimethyl isobu [i ~
Liedylamine was added and heated at 50°C for 30 minutes.

After cooling to O'C, add 30 mffJln of hexane and heat to 0°.
Washed with water (3 x 30 mf!). After drying over magnesium sulfate, the solvent was removed under reduced pressure to obtain 16-(dimebroisopropylsilyl[]oxy)hequinade'canoic acid dimedylisopropylsilyl ester (hereinafter referred to as 1-IDFE) was obtained.It was developed on a Jn acid aqueous solution prepared with HDEF 25μmof! and hexadecanoic acid.The surface pressure was set to 25d.
Transferred onto a quartz substrate while maintaining yn/Cm2.

The surface energy of the surface of the substrate as copied was calculated from the contact angle of the droplet and was 18 erg/cm'', indicating that it was very hydrophobic.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to form a monomolecular film made of an isopropylene mixture of 16-droxyhex+J'decanoic acid and hexadecanoic acid on the substrate. is. Surface of the board surface Tne)L4-Ha50
ero/cm” Tojinkiku, 1!'71 Ishimizu・1no1
showed that. The highly hydrophilic nature of this monomolecular film did not change at all even after it was left at room temperature for one week.

Next, on a quartz substrate on which this 16-hydro-oxyhexylidecanoic acid and hexadecanoic acid are oriented and adsorbed at the same time as the monolayer, the hydrophilic groups on the surface of the monolayer (here In this article, we conducted an experiment using the reaction of hydroxyl group.

Polymer 0=C=N-CF2(C2F40)p- (CF20) with a molecular weight of about 3000
q-CF2-N=C=0 (p:q=1:1, each structural unit (informal 111))...♂11- was dissolved in Freon, and a 0.08% by weight solution was obtained. This solution was coated on the quartz base (10) with water groups on the surface at a rotational speed of 2,500 times/min, and then baked at 100 °C. , washed with Freon.

The surface energy of the obtained substrate is brought into contact with the polymer 1! When compared with before contact, it was 50 to 16 erg/c before contact.
It was found that there was a significant decrease in m2.

-Sushi hydroxyl group and isocyanate-1~ group are reacting.
If so, the polymer should be removed from the monolayer by washing with Freon. Therefore, the reactivity of the hydrophilic groups of the monomolecular film l- produced by the method of the present invention is effectively utilized, and the hydroxyl groups on the surface of the monomolecular film are
It can be seen that it has already reacted with the 1-group.

Example 2 l-IDEE 2Of1mof synthesized in Example 1 and 30μmoρ of hexadecanoic acid were mixed with chlor[]fosilum (1h
+ff), expand in distilled water] and reduce the surface pressure to 2.
It was copied onto a quartz substrate while maintaining the density at 5 hn/cm2.

The surface energy of the surface of the substrate as copied is calculated from the contact angle of the droplet - 12'', -, and is 1 'r'erg/cm2,
It was extremely hydrophobic.

Next, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to form a monomolecular film made of a 2:3 mixture of droxybekyl-nadecanoic acid and hexadecanoic acid on the substrate. Obtained. The surface energy on the surface of the substrate is 49
It exhibited high hydrophilicity as compared to erO/Cm2. The high hydrophilic property of this monomolecular film does not change at all even if it is left at room temperature for a week.1. 【won.

Example 3 IDEE 5!1 mo β synthesized in Example 1 and 45 μmol hexadecanoic acid! was dissolved in chloroborum (10d), spread on distilled water, and the surface pressure was adjusted to 25 dyn/c.
It was copied onto a quartz substrate while maintaining the area at m2. The surface energy of the substrate surface as it is copied is calculated from the contact angle of the droplet by h
When calculated, it was 18 erg/cm'', indicating extremely high hydrophobicity.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to obtain 16-hydroxyhex1.
An 11-molecule film was obtained consisting of a 1:9 mixture of napecanoic acid and hexadecanoic acid.The surface energy of the substrate surface was 48
er(]/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.

Example 4 11DFE synthesized in Example 45μmoj! and 5 μmol hexadecanoic acid! in chloroform (10mf2
>, spread on distilled water, and reduce the surface pressure to 25 fjv.
It was transferred onto a quartz substrate while maintaining n/Cl112.

When the surface energy of the surface of the substrate as copied was calculated from the contact angle of the droplet, it was 18 erg/Cm2, indicating that it was extremely hydrophobic.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and washed with water to obtain a monomolecular film made of a 9:1 mixture of 16-hydroxyhexadecanoic acid and hexadecanoic acid. The surface energy of the substrate surface is 48era
/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.

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

-15, β-ray

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 the hydrophilic groups at both ends of one or more organic compounds represented by the formula into hydrophobic protecting groups, the general formula: ' (wherein, X'' is a hydrophilic group, and R' is a hydrocarbon group having 8 or more carbon atoms) at the same time using the Langmuir-Blodgett method with one or more organic compounds represented by A method for producing a monomolecular film characterized by adsorption on a hydrophilic substrate while controlling orientation.