JPS62266163A - Monomolecular film - Google Patents

Abstract

PURPOSE:To form a monomolecular film having desired hydrophilic groups provided to the surface thereof in desired quantity, by using a mixture of an org. compound having the same hydrophilic groups at both terminals thereof and an org. compound having a hydrophilic group at the single terminal thereof as a raw material. CONSTITUTION:A mixture of an org. compound having the same hydrophilic groups at both terminals thereof and an org. compound having a hydrophilic group at the single terminal thereof is used as a raw material and, by adequately selecting a protective group and the protective or de-protective condition thereof, a monomolecular film having a necessary amount of hydrophilic groups allowed to be present thereon can be formed on a hydrophilic base material by an LB method. In this case, as the org. compound, respectively one or more kinds of org. compounds represented by X-R-X and X'-R' (wherein X and X' are a hydrophilic group and R and R' are 8 or more, desirably, 14 or more hydrocarbon group) are used simultaneously.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention is an organic monomolecular film, which can be adsorbed to a hydrophilic substrate in particular, and which has a hydrophilic group on the gas side (opposite side to the substrate) during adsorption. Or, it relates to 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, a method for producing monomolecular films and cumulative films is to highly orient the molecules of an amphoteric substance on the water surface to form a monomolecular layer, and then transfer that monomolecular layer 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 [J9, due to the issue of thermodynamic stability, a hydrophobic film or a film should be placed on the gas side, which is the side opposite to the support of the film, that is, the Membrane with exposed part (
Is it necessary to set it to V configuration? If the hydrophilic group part is exposed on the gas side, 1↓C=b, and the device is carefully set up (J), the constituent molecules will be reversed and the surface will become hydrophobic.7.11- It is being

Therefore, it is extremely difficult to form a monomolecular film in which the hydrophilic groups are exposed to the gas side in the conventional G; Hydrophilic 'l] l Adsorbs the substance t!l Remove the substance from the stiff film and remove the new) real part from fat! This difficulty was a big problem for the students.

However, there are many hydrophilic groups that are generally rich in reactions and iJ1, and if such a film is created, reaction '1-1 is added to the surface of the intermediate molecular film or the cumulative film of A). I'm excited about what I can do. Utilizing the reactivity or hydrophilicity itself of hydrophilic groups, for example, insulating layers for semiconductor devices,
This means that protective lubricating layers for magnetic f' disk devices, layers with photoelectric conversion functions, optical information recording layers, optical information storage layers, etc. can be provided on the upper layer. be.

The purpose of the present invention is to provide a material that solves the above-mentioned problems. Specifically, it is capable of being adsorbed to a hydrophilic base material, and is capable of being adsorbed onto the gas side after adsorption. The purpose of the present invention is to provide an organic monomolecular film having a hydrophilic group on the side opposite to the base material.

[Means for solving and overcoming the problems] The present invention provides a general formula: Type 1 or 2 shown in
The presence of the species I- means a compound, and the general formula:
1, preferably 14 or more hydrocarbon groups) or (1.2) 100 organic compounds are simultaneously adsorbed onto a hydrophilic substrate under orientation control. lko3
− It is a monomolecular film characterized by the following.

The gist of the present invention is that the organic compound has the same hydrophilic compound at both ends and the same hydrophilic compound at one end.
Hydrophilic base material 1 using a 41 compound having 4 groups as a raw material
If 7 has hydrophilic/1-1 groups on both the base material side and the gas side, J
First, hang the hydrophilic 1/1 unit on the gas side as quickly as necessary! The purpose of the present invention is to provide a monomolecular film with a high molecular weight.

In the present invention, X and X' in the general formulas (T) and (II), which have hydrophilic groups in the monomolecular film in 43, include human [1 xyl group, carboxyl group, mercar 11- group,
Diocarboxyl group, di-17I carboxyl group, throughnoino group, sulfo group, carlevadyl group, diocarpamoyl group, amino group, substituted amine group, etc., and the monolayer-forming substance is a hydrophilic ↑1 group of these. An h-terminated compound having one of the following types at both ends.

It is an organic compound having a 1-group at one end, which is the same as the hydrophilic 14 groups of the above-mentioned organic compound, or has a hydrophilic group 1 different from the above.

In addition, R and R' in the general formulas <I> and (IT> are divalent and monovalent chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, or -.A and - these hydrocarbons, respectively. A part of the group contains a hydrocarbon group containing 1/j iJ: 2 or more) Tei-C(,) Good.

The proportions of the compound of general formula (I) and the compound of general formula (IT>) can be selected as appropriate depending on the number of hydrophilic groups required on the monolayer surface, but usually The compound of general formula (4) is 37% or more, preferably 10-1%.
Presence of more than mol%! 1. In addition, each compound i may be used alone, or if necessary, two or more types may be used in combination. 1. Preparation of the middle molecular film of the present invention For example, the following Z method and C row can be used to form a monomolecular film containing a substance with hydrophilic endpoints at both ends. -B]-1
To go 4r according to the law to 1 is a movement. Both ends (for compounds with hydrophilic groups (,1,
The molecules are arranged as a monomolecular film under the water surface.
It is necessary to convert it to 阜. Hydrophobic protecting groups that can be used for this purpose include ethers containing trialkylsilyl groups, dihydropyranyl groups, etc. Appropriate ones generally used in the field of organic synthetic chemistry may be used, such as ester-based protecting groups, ester-based protecting groups, and amide-based protecting groups such as trifluoroacetic acid amide.

In preparing a monomolecular film, both hydrophilic groups may be protected and only one side may be peeled off on the water surface, or only one side may be protected from the beginning. When both hydrophilic groups are protected, the concentrations of various ions in the water and the concentration of the water should be adjusted so that only one side is I]f2 protected on the water surface and returns to the original hydrophilic group and is oriented as a monomolecular film on the water surface. It is necessary to appropriately select various conditions such as temperature and development time on the water surface. Similarly, when only the hydrophilic P1 group on one side is protected, it is necessary to appropriately select the above conditions so that the protecting group does not come off on the water surface. In general, the water may contain metal ions that form a monolayer salt on the water surface.

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 with only 11 hydrophilic groups protected on one end and a compound having a hydrophilic group at one end were simultaneously processed by the Langmuir-Prodgett method to obtain a hydrophilic 1t
, copy it onto i. The resulting monolayer has a hydrophobic surface! Since it is protected by , it can be made into a free hydrophilic group by immersing it in an appropriately prepared reagent solution or exposing it to an appropriate reagent vapor.

[Operation] Using a mixture of organic compounds having the same hydrophilic group at both ends and an organic compound having a hydrophilic group at one end as raw materials, appropriately selecting the protecting group and its protection or deprotection conditions. Accordingly, a monomolecular film having a desired amount of hydrophilic groups on the surface can be produced on a hydrophilic substrate by the Langmuir-Prodgett method.

In order to produce the novel monomolecular film of the present invention, [jl, both ends (this is done by hydrophobicizing the hydrophilic groups at both ends or one end of a compound having the same hydrophilic group to a hydrophobic 14M). Also, it is necessary to deprotect after copying the hydrophilic group 4.Since the protection by hydrophobic groups is for arranging the monolayer on the water surface, both ends must be protected at the same time. In this case, it is necessary to deprotect only one side on the water surface. Deprotection after transfer to a hydrophilic substrate is a means to provide the desired hydrophilic group on the surface.

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

Example 1 Add 2.2 times the amount of dimethylisopropylsilyl chloride and 2.2 times the amount of triethylamine to a solution of 1.16-dicarpoxyhexane-4-nadecane (4 mmol) in tetrahydrofuran (2), and heat at 50 °C for 30 minutes. I did.O'
After cooling to 100 ml, add 30 ml of hexane and wash with O'C water (3 x 30 yf). After drying with magnesium Ia acid, remove the solvent under reduced pressure, ) Hekylidecane is 17. This substance is 25μ...0β and octadecanoic acid 2
5μmOj! Dissolve it in 10 Biao of chloroform and make pl
+ was developed on a hydrochloric acid aqueous solution prepared at a concentration of 4.5, and transferred onto a quartz substrate while maintaining the surface pressure at 25 dyn/cm.The surface energy of the substrate surface as transferred was calculated from the contact angle of the droplet. When calculated, it was 19 elg/cm2, indicating that it was very hydrophobic.

Subsequently, this substrate was immersed in an aqueous solution of hydrochloric acid with a pH of 4.0, and then thoroughly washed with water to obtain a monomolecular film made of an isomerotic mixture of 1,16-dicarpoxyhexadecane and octadecanoic acid on the substrate. . The surface energy of the substrate surface is 48
It had a large hydrophilicity of el''G/Cm2.

The high hydrophilicity of this monomolecular film did not change at all even after being left at room temperature for one week.

Example 2 1.16-dihyde [゛11-hexylidecane (4...mo
To a solution of b) in tetrahydrofuran (20 ml) was added isolinear dimedelisopropylsilyl chloride and an equal amount of triethylamine and heated at 50'C for 30 minutes. O'C
After cooling to , add 30 ml of hexadiene and wash with O'C water (3 x 30 mff). After drying with magnesium sulfate,
Remove the solvent under reduced pressure and purify with a silica gel column to obtain 1
6-(dimethylisopropylsilyloxyxadecanol was obtained. 25 pmo p of this material and 125 p of hexadecane
10ml of f1mol! It was dissolved in chloroform, developed in 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, we get
It was 18erg/cm2, and was extremely 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 1,16-cyhydroxyhexa-1-nadecane and hexadenkaic acid on the substrate. It's 1q. The surface energy of the substrate surface was as large as /18er(]/Cm2, indicating high hydrophilicity. The high hydrophilicity of this monomolecular film did not change at all even after it was kept in a lJ apparatus at room temperature for one week.

Next, this isomerotic mixture of 1,16-cyhydroxyhexadec'cane and hexadencaic acid was oriented and adsorbed as a monolayer on a quartz substrate, and the hydrophilic 1-1 groups (
Here, an experiment was conducted using the reactivity of hydroxyl acid M).

Polymer 0=C=N-CF2 (C2F40), - (CF20) with a molecular weight of about 3000
q-CF2-N=C=0 (p:q=1:1, each structural unit is irregular ill) was dissolved in Freon, and 0.08
A wt% solution was prepared. This solution was spin-coated onto the UI substrate having hydroxyl groups on the surface at a rotation speed of 2500 times/min, baked at IoO'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 the surface energy of the obtained substrate was 48 to 15er (1/C
It was found that there was a significant decrease in m2.

If the hydroxyl groups and isocyanate groups have not reacted (if they do, the polymer should be removed from the monomolecular film by washing with Freon. Therefore, the reactivity of the hydrophilic groups on the monomolecular film of the present invention It can be seen that the hydroxyl groups on the surface of the monomolecular film react with the isocyanate groups at the terminals of the polymer.

Example 3 16-(dimethylisopropylsilyloxy)hexadecanol prepared in Example 2 20 μmO! and 130 μmo β of hexadecane was dissolved in 10 d of chloroform,
It was developed on distilled water and transferred onto a quartz substrate while keeping the surface pressure at 25 dyn/cm2. The surface energy of the surface of the substrate as copied was calculated from the contact angle of the droplet and was found to be 18ero/cm2, indicating extremely high hydrophobicity.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to obtain a monomolecular film made of a 2:3 mixture of 1,16-cyhydroxyhexa-4-nadecane and hexadecanoic acid on the substrate. Ta. The surface energy of the substrate surface was as large as 48 erg/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 16-(dimethylisopropylsilyloxy)bek4nadecanol 5μmoβ prepared in Example 2 and 12
Defeat to Shin V Decanoic acid 45/lloj! 10m (! of Kuro 1
] Volum), spread on distilled water, and reduce the surface pressure to 2.
It was copied onto a quartz substrate while maintaining the pressure at 5 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 208r (1/Cm",
It was extremely hydrophobic.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to form a monomolecular film of 1 q of a mixture of 1,16-cyhydroxyhexadecane and hexadecanoic acid on the substrate. is. The surface energy of the substrate surface was 49er (1/C.

Example 5 45 μm of 16-(dimethylisopropylsilyloxy)hexadecanol prepared in Example 2 and 5 μm Oβ of hexadecanoic acid were dissolved in 10 d of chloroform and spread on distilled water, keeping the surface pressure at 25 dyn/Cm2. The surface energy of the surface of the substrate as it was transferred is calculated from the contact angle of the droplet to be 1.
7erg/ε...2, indicating extremely high hydrophobicity.

Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to obtain a monomolecular film made of a 9:1 mixture of 1,16-hydroxyhexadecane and hexadecanoic acid on the substrate. . The surface energy of the substrate surface was as high as 49 erg/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.

[Effects of the Invention] As explained above, since the monomolecular film of the present invention has hydrophilic groups on its surface, various applications are expected by utilizing the reactivity of the new hydrophilic groups or the hydrophilicity itself. Ru.

Claims (1)

[Claims] (1) 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); General formula: X'-R' (wherein, X' is a hydrophilic group and R' is a hydrocarbon group having 8 or more carbon atoms) A monomolecular film characterized by being adsorbed onto a flexible substrate with controlled orientation.