JPH06220218A - Thin hydrophilic film and its production - Google Patents

Abstract

PURPOSE:To obtain the subject film by introducing molecules of a compound having a hydrophilic group into a chemisorptive film immobilized on a substrate by chemical bonding and immobilizing the molecules on the film. CONSTITUTION:A chemisorptive film is formed on the surface of a substrate 1, and then molecules of a compound having a hydrophilic group, for example, at least one member selected from the group consisting of a saccharide, a cyclodextrin, a polyether, a polyalcohol, a polyethylene oxide, a poly-N- vinyllactam, a polymethacrylamide, a polymethacrylic acid, a polymethacrylic ester and a polyvinylamine are immobilized on the film by chemical bonding to form a thin hydrophilic film 4 of improved hydrophilicity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic thin film and a method for producing the same. More specifically, the present invention relates to a hydrophilic thin film in which a molecule having a hydrophilic group is fixed on the surface of a substrate by a chemical bond through a chemical adsorption film, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting hydrophilicity to a substrate, a chemical or resin containing a hydrophilic compound such as polyvinyl alcohol or polyethylene glycol is applied, or a hydrophilic film containing a similar compound is attached. The method is known.

Another method is to chemically modify the surface. For example, oxidation under a very strong reaction condition of irradiating high energy light such as excimer laser in an ozone atmosphere was also one method.
By this oxidation, new carboxyl groups and hydroxyl groups are newly created.

Regarding the basic technique for making a chemisorption film,
Journal of American Chemical Society Vol. 102, page 92 (J. Sagiv et a.
l. J. Am. Chem. Soc. , 102, 92
(1980)) and Langmuir Volume 6, page 851 (K. Ogawa et al., Langmui.
r, 6, 851 (1990)) and the like. This chemical adsorption method is a method of immobilizing a molecule called a chemical adsorbent having a chlorosilyl group on a substrate having a hydroxyl group on its surface through a dehydrochlorination reaction.

[0005]

However, in the method of applying a hydrophilic resin or attaching a hydrophilic film, there is a problem in terms of durability such as deterioration of transparency and easy peeling or scratching. there were.

Further, in the method of chemical surface modification by intense oxidation, even if the hydrophilicity is improved, some damage to the substrate is unavoidable. In some cases, rather than modification, carbonization is included. Curing and discoloration will occur.

In order to solve the above-mentioned conventional problems, the present invention provides a thin film having excellent hydrophilicity and transparency and durability, as well as the surface of the substrate, and a method for producing the same. The purpose is to provide.

[0008]

In order to achieve the above-mentioned object, the hydrophilic thin film of the present invention has a chemisorption film immobilized on the surface of a substrate by a chemical bond, and has a hydrophilic property in or on the molecule of the chemisorption film. A hydrophilic thin film into which a molecule having a group is introduced, wherein the hydrophilic molecule is a saccharide, a cyclodextrin, a polyether, a polyalcohol, a polyethylene oxide, a poly N-vinyl lactam, a poly It is characterized by being at least one molecule selected from methacrylamides, polymethacrylic acids, polymethacrylic acid esters, and polyvinylamines.

In the above structure, the chemisorption film is preferably covalently bonded to the substrate through at least one atom selected from C, Si, Ge, Sn, Ti, Zr, and S.

In the above structure, the chemical adsorption film is
It is preferably selected from monolayers and monolayers. In the above structure, the hydrophilic group is a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, a quaternary ammonium group, a quaternary phosphonium group, a thiol group, an amino group. And at least one selected from sulfate groups.

Further, in the above structure, H of one functional group selected from a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, and a thiol group is an alkali metal or an alkaline earth metal. It is preferably at least one selected from functional groups substituted with metal.

Next, in the method for producing a hydrophilic thin film of the present invention, a chemisorption film is fixed to the surface of a substrate by a chemical bond, and a molecule having a hydrophilic group is introduced into or on the molecule of the chemisorption film. A method for producing a conductive thin film, wherein a functional group is present in the chemical adsorption film, and the functional group is combined with a saccharide, a cyclodextrin, a polyether, a polyalcohol, a polyethylene oxide, a poly N-vinyllactam, It is characterized in that at least one molecule selected from polymethacrylamides, polymethacrylic acids, polymethacrylic acid esters, and polyvinylamines is covalently immobilized by a chemical reaction.

In the above structure, the raw material for forming the chemisorption film is represented by the functional group represented by the above (Chemical formula 1), the functional group represented by the above formula (Chemical formula 2) and the above formula (Chemical formula 3). Halogenated sulfonyl group, a halogenated sulfinyl group represented by the above formula (Formula 4), and a cyano group (-CN)
It is preferably a molecule having at least one functional group selected from

In the above structure, the hydrophilic group is a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, a quaternary ammonium group, a quaternary phosphonium group or a thiol group. It is preferably at least one selected from an amino group, an amino group, and a sulfate ester group.

Further, in the above constitution, H of one functional group selected from a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group and a thiol group is an alkali metal or an alkaline earth metal. It is preferably at least one selected from functional groups substituted with metal.

In the above structure, the chemisorption film is
It is preferably selected from monolayers and monolayers.

[0017]

According to the structure of the present invention, a hydrophilic thin film in which a chemical adsorption film is fixed to the surface of a substrate by a chemical bond and a molecule having a hydrophilic group is introduced into or on the molecule of the chemical adsorption film. And the molecule having hydrophilicity is
At least selected from sugars, cyclodextrins, polyethers, polyalcohols, polyethylene oxides, poly N-vinyl lactams, polymethacrylamides, polymethacrylic acids, polymethacrylic acid esters, and polyvinylamines. By using one molecule, it is possible to realize a thin film that is excellent in transparency and durability, and further has excellent hydrophilicity without damaging the surface of the substrate.

According to the manufacturing method of the present invention, the thin film of the present invention can be formed efficiently and rationally.

[0019]

EXAMPLE The hydrophilic thin film of the present invention is prepared by immobilizing molecules having a hydrophilic group by a chemical bond through a chemical adsorption film previously formed on a substrate. This makes it possible to dramatically increase the number of hydrophilic groups and the number of chemically adsorbed hydrophilic molecules as compared with the base or the base chemical adsorption film, thereby improving the hydrophilicity of the base surface.

The hydrophilic group of the molecule having a hydrophilic group is a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, or a thiol group, where H is an alkali metal or alkaline earth metal. Functional group substituted with metal, hydroxyl group, carboxyl group, sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphorous acid group, quaternary ammonium group, quaternary phosphonium group, thiol group, amino group or sulfate ester A group and the like are preferable. Only one kind of these hydrophilic groups may be contained, or two or more kinds thereof may be contained.

The molecule having a hydrophilic group is a monosaccharide,
Disaccharides, polysaccharides, polyethers, polyalcohols,
Poly (N-vinyl lactams) such as polyethylene oxides, hydroxylalkyl alcohols, poly (N-vinylpyrrolidone) and poly (N-vinylcaprolactam), poly (meth) acylamides such as polyacrylamide, polydiacetone acrylamide, polyacrylic acid, polyhydroxyalkyl Suitable are polymethacrylics such as acrylates, their polymethacrylates and polybimylamines such as polyvinylpyridine. Of these, only one type may be fixed, but two or more types may be fixed.

The hydrophilicity can be controlled by the density and type of hydrophilic group. As a method of controlling the density, there is a method of changing the density of hydrophilic groups of a molecule having a hydrophilic group. For example, a method of changing the number of hydroxyl groups or carboxyl groups in the molecule, or a method of controlling the reaction time of the reaction of fixing the molecule having a hydrophilic group onto the chemisorption film on the existing substrate, A method of controlling the density of the functional groups on the surface of the underlying chemisorption film formed to fix the molecule is considered. The control may be performed by combining the above methods.

As a method of immobilizing the molecule having the hydrophilic group on the base chemical adsorption film, the functional group on the chemical adsorption film chemically reacts with the functional group of the molecule having the hydrophilic group, A method is preferable in which a molecule having a hydrophilic group can be firmly fixed by forming a covalent bond or an ionic bond. The reaction at the time of fixation may be any reaction as long as it is a so-called chemical reaction such as polymerization, coupling, addition, substitution and exchange reaction.

Further, after the molecule having the hydrophilic group is fixed on the inner surface of the chemisorption film, the chemisorption agent is reacted with the hydrophilic group to form the chemisorption film again. A cumulative film may be formed by repeatedly fixing molecules having a hydrophilic group.

It is suitable to evaluate the hydrophilicity by measuring the contact angle with water and evaporative drying time of water droplets. The higher the hydrophilicity, the smaller the contact angle to water. Further, the evaporative drying time of water droplets becomes shorter as the hydrophilicity becomes higher.

By forming the hydrophilic film of the present invention, the density of hydrophilic groups on the surface can be improved. Therefore, when a new chemical adsorption film or the like is formed on this film, A film having a higher film density than ever before is formed.
That is, the principle of forming the chemisorption film is at least the functional group represented by the formula (Formula 1), the functional group represented by the formula (Formula 2), the halogenated sulfonyl group represented by the formula (Formula 3), By using a molecule having one selected from the group consisting of a halogenated sulfinyl group and an aldehyde group represented by the formula (Formula 4) as a chemical adsorbent, a hydrophilic group on the substrate and the functional group undergo a condensation reaction, A chemical adsorbent is fixed on the substrate.

When a hydrophilic film is fixed and a chemisorption film is further formed thereon, the density of chemisorption molecules increases. Therefore, for example, when a film-constituting molecule having an alkyl group is used, the water repellency of the film is clearly improved, and conversely, it can be confirmed that the hydrophilic property of the underlying hydrophilic film is improved by the improvement of the water repellency.

As the substrate on which the underlying chemisorption film is fixed, H of the hydroxyl group, the carboxyl group, the sulfonic acid group, the sulfinic acid group, the phosphoric acid group, the phosphorous acid group and the thiol group is an alkali metal on the surface thereof. Functional group substituted with or alkaline earth metal, hydroxyl group, carboxyl group, sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphorous acid group, quaternary ammonium group, quaternary phosphonium group, thiol group,
Examples thereof include those having at least one functional group selected from amino groups, and chemisorption membranes which are already immobilized on a substrate having the above-mentioned functional group and have the above-mentioned functional group on the membrane. Not limited to.

When the surface of the substrate has no or a small amount of the above-mentioned functional groups, UV / ozone treatment, oxygen plasma treatment, treatment with a compound oxidant such as potassium permanganate solution is carried out to modify the surface, It is effective to create or increase functional groups.

As a method of fixing the chemisorption film to the substrate, there is a method of bringing the substrate into contact with a solution in which a liquid and / or gaseous raw material for chemisorption is dissolved. Not limited to.

When the solution is provided here, the solvent to be used is preferably composed of molecules containing no active hydrogen. For example, when the chemical adsorbent has a long-chain alkyl group, a mixed solvent of hydrocarbons and halogenated carbons is used. When the chemical adsorbent has a carbonyl group, halogenated hydrocarbons and aromatics are used. It is suitable to use,
It is not limited to these.

After fixing the chemisorption film on the substrate,
The method of adding the step of removing unreacted molecules is easy to form a monomolecular film and a monomolecular cumulative film. Examples include, but are not limited to, halogenated carbons, ethers, lactones, esters, nitriles, amides, and the like.

The present invention will be described in detail below, but the present invention is not limited to the following specific examples. (Example 1) First, an adsorption solution A was prepared.

Hexadecane, carbon tetrachloride and chloroform were mixed in a weight ratio of 80: 12: 8 to dissolve a chemical adsorbent (4-chloromethylphenyl) trichlorosilane at a concentration of about 1% by weight. Was prepared as the adsorption solution A.

As shown in FIG. 1, a glass substrate 1 was used as a hydrophilic substrate, washed with an organic solvent, and then immersed in an adsorption solution A for 3 hours. By this treatment, first, a dehydrochlorination reaction is caused between Si—Cl of (4-chloromethylphenyl) trichlorosilane and OH of the glass substrate 1,
The chemical adsorption film was formed on the surface of the glass substrate 1.

[0036]

[Chemical 5]

Next, 1% of chloroform was added as a non-aqueous solvent.
After washing for 0 minutes and further for 10 minutes with water, a chemisorption monomolecular film 3 as shown in FIG. 2 was formed. This monomolecular film was firmly fixed to the substrate and was water repellent. The contact angle of water was measured and found to be 65 °.

The film formation was determined by Fourier transform infrared absorption spectrum (FTIR) measurement at 1610, 1400 (attribution:
Benzene skeleton), 1440 (attribution: CH ₂ Cl), 10
This could be confirmed by obtaining a signal characteristic of this structure at 80 (attribution: Si—O) cm ⁻¹ .

Next, the glass substrate 1 having this chemisorption monomolecular film 3 was dipped in a dimethyl sulfoxide solution containing about 5% by weight of glucose. And the solution at 60 ℃
And reacted for 2 hours.

Thereafter, 10 minutes of methanol cleaning and 10 minutes
It was washed with water for a minute. Then, the chemical adsorption film 4 as shown in FIG. 3 was formed. This film was firmly fixed to the substrate and was rich in hydrophilicity. The contact angle of water on this chemically adsorbed film was 5 °, showing hydrophilicity.

According to Fourier transform infrared absorption spectrum (FTIR) measurement, 3600 (attribution: OH)
cm ^-1 of the signal appear newly, also by the strength of the signal of 1080 cm ^-1 was increased, it was confirmed that the glucose is fixed.

Example 2 First, an adsorption solution B was prepared. Hexadecane, carbon tetrachloride and chloroform were mixed at a weight ratio of 80: 12: 8 in a mixed solvent of 4- (2- (trichlorosilyl) ethyl) benzenesulfonyl chloride as a chemical adsorbent at a concentration of about 1% by weight. It was prepared by dissolving it in, and this was designated as adsorption solution B.

As in Example 1, the glass substrate 1 was used as the hydrophilic substrate, washed with an organic solvent, and then immersed in the adsorption solution B for 2 hours. By this process, first 4- (2-
Si-Cl of (trichlorosilyl) ethyl) benzenesulfonyl chloride and OH of the glass substrate 1 caused a dehydrochlorination reaction, and a chemical adsorption film was formed on the surface of the glass substrate 1 due to the bond of (Chemical Formula 6).

[0044]

[Chemical 6]

Then, chloroform washing for 10 minutes and 10
After washing with water for a minute, a chemisorption monomolecular film 5 as shown in FIG. 4 was formed. This monomolecular film was firmly fixed to the substrate and was water repellent. The contact angle of water was measured and found to be 62 °.

The film formation was carried out by Fourier transform infrared absorption spectrum (FTIR) measurement at 1595, 1490 and 141.
0 (attribute: benzene skeleton), 1380, 1180 (attribute: O = S = O), 1080 (attribute: Si-O) cm ^-1
The formation of a film was confirmed by obtaining a signal characteristic of this structure.

The glass substrate 1 having this chemisorption monomolecular film 5 was dipped in a dimethyl sulfoxide solution containing about 5% by weight of polyethylene oxide having an average molecular weight of 350 and represented by HO (CH ₂ CH ₂ O) _n H. Let Then, the solution was brought to 60 ° C. and reacted for 3 hours.

After that, 10 minutes of methanol washing and 10 minutes
It was washed with water for a minute. Then, the chemical adsorption film 6 as shown in FIG. 5 was formed. This film was firmly fixed to the substrate and was rich in hydrophilicity. When the contact angle of water was measured on this chemically adsorbed film, it was 3 °, showing hydrophilicity.

The film formation was 2920, 2860 according to Fourier transform infrared absorption spectrum (FTIR) measurement.
(Assignment: —CH ₂ —) It was confirmed that polyethylene oxide was immobilized by the increase in the intensity of the signal at 1080 cm ⁻¹ .

(Example 3) The chemical adsorption film 6 prepared in Example 2 was again immersed in the adsorption solution B for 15 minutes. By this treatment, the bond shown in Chemical formula 7 was formed on the chemical adsorption film 6.

[0051]

[Chemical 7]

Next, 10 minutes of chloroform washing and 10
After washing with water for a minute, a chemical adsorption film 7 as shown in FIG. 6 was formed. This chemisorption film was firmly fixed to the substrate and was water repellent. The contact angle of water was measured and found to be 67 °.

The film formation was 1595, 149 according to Fourier transform infrared absorption spectrum (FTIR) measurement.
0, 1410 (attribute: benzene skeleton), 1380, 11
80 (attribute: O = S = O), 1080 (attribute: Si-
It was confirmed that the intensity of (O) cm ⁻¹ was increased.

Further, the glass substrate 1 having the chemical adsorption film 7 was dipped in a dimethyl sulfoxide solution containing about 5% by weight of the polysaccharide as shown in FIG. 7, and the liquid temperature was 60.
The temperature was raised to 0 ° C. and the reaction was performed for 2 hours.

This is a 10 minute methanol wash and 10 minutes.
After washing with water for a minute, the chemical adsorption film 8 as shown in FIG. 8 could be accumulated. This film was firmly fixed to the substrate and was rich in hydrophilicity.

The film formation was determined by Fourier transform infrared absorption spectrum (FTIR) measurement to be 3650 (attribution: O
-H), 2920,2860 (attributable: -CH ₂ -), 1
It was confirmed that the polysaccharide was immobilized by the increase in the intensity of the signal at 080 cm ^-1 .

This chemisorption film 8 was extremely hydrophilic, and when the contact angle of water was measured, the water droplets spread too much and the contact angle was almost 0 ° and could not be measured. Example 4 Using the same method as in Example 3, a hydrophilic film was first formed on the chemisorption film on the glass substrate as shown in FIG. This membrane was again extremely hydrophilic.

Next, an adsorption solution C was prepared. Hexadecane, carbon tetrachloride and chloroform in a weight ratio of 80:12:
About 8 decadyltrichlorosilane (C ₁₈ H ₃₇ SiCl ₃ ) which is a chemical adsorbent was added to a mixed solvent mixed in a ratio of 8
It was prepared by dissolving it at a concentration of%, and this was designated as adsorption solution C.

The glass substrate having the hydrophilic film 9 thus prepared was immersed in the adsorption solution C for 2 hours. Then 1
By passing through the chloroform washing for 0 minutes and the water washing for 10 minutes, the chemical adsorption cumulative film 10 was formed on the hydrophilic film 9 as shown in FIG.

The film formation could be confirmed by Fourier transform infrared absorption spectrum (FTIR) measurement, where the signals at 2960 to 2860 (attribution: CH ₃ , —CH ₂ —) and 1080 cm ⁻¹ increased.

Further, the contact angle with water was measured and found to be 110 °, which was extremely rich in water repellency. (Comparative Example 1) Each of the glass substrates used in Examples 1 and 2 was provided with the same kind of untreated glass substrate at three locations on each of three places.
A μl drop of water was dropped and left in air at room temperature. Then, before any water drops evaporate and disappear, 3
It took 5 minutes.

Then, water drops were similarly dropped and left on the glass substrate having the hydrophilic film prepared in Examples 1 and 2. Then, it took 20 minutes for the water drops on the hydrophilic film 4 (Example 1) to disappear, and 12 minutes for the water drops on the hydrophilic film 6 (Example 2) to disappear.

From the above, it was confirmed that by forming the film of the present invention on the substrate, water droplets evaporate and dry quickly. This is because the higher the hydrophilicity, the better the water droplets spread, the larger the contact area with the air, and the easier the evaporation.

From the above, it was confirmed that the membrane of the present invention is hydrophilic. (Comparative Example 2) An untreated glass substrate of the same type as the glass substrate used in Example 4 was used as the adsorption solution C prepared in Example 4.
It was soaked in 2 hours. Then, after 10 minutes of chloroform washing and 10 minutes of water washing, a chemisorption monomolecular film 11 as shown in FIG. 11 was formed. The film formation was 29 by Fourier transform infrared absorption spectrum (FTIR) measurement.
60-2860 _{(Attribution: CH 3, -CH 2 -)} , 147
0 (Attribution: -CH ₂ -), 1080 (attributable: Si-O)
This could be confirmed by obtaining a signal characteristic of this structure at cm ⁻¹ .

The contact angle of the thus formed film with water was measured. It was 93 °. As a result, Example 4
It was confirmed that the chemisorption accumulation film 10 prepared in step 1 was more water-repellent by 17 ° than this film.

This is because the number of hydroxyl groups can be dramatically increased as compared with the glass substrate by first fixing polyethylene oxide to form a hydrophilic film in Example 4, and therefore the number of hydroxyl groups is further accumulated. This is because the molecular density of the chemisorption single molecule is improved. That is, the chemisorption monomolecular film can be formed more densely on the film made of polyethylene oxide than on the glass substrate. Thus, it was shown that the water repellency of the film formed above was improved, and conversely, the hydrophilicity of the film formed by fixing polyethylene oxide was higher than that of glass.

It was also confirmed that the same film can be formed by using a chemical adsorbent other than those used in Examples 1 to 4. As described above, the hydrophilic thin film of the present invention is more hydrophilic than glass generally known as hydrophilic. Therefore, it is extremely practical as one of the new methods for surface modification. For example, by forming this film on glass, glass with high anti-fogging property can be prepared. Further, the hydrophilic thin film of the present invention can be used for applications where it has not been possible to do so chemically or under various circumstances, although it has been conventionally desired to be hydrophilic. For example, for surface modification of biocompatible materials, it is clear that the hydrophilic membrane of the present invention is more suitable than any other material in terms of hydrophilicity, stability and film thickness. The range of use is extremely wide.

[0068]

As described above, according to the present invention, a thin and strong hydrophilic film can be efficiently and rationally produced. That is, in the hydrophilic thin film, saccharides, cyclodextrins, polyethers, polyalcohols, polyethylene oxides, poly N-vinyl lactams, polymethacrylamides, polymethacrylic acids, polymethacrylic acid esters, Since it contains at least one compound selected from polyvinylamines, not only transparency and durability can be maintained, but also excellent hydrophilicity can be imparted without damaging the surface of the substrate.

[Brief description of drawings]

FIG. 1 is an enlarged view of a glass substrate of Example 1 of the present invention at a molecular level

FIG. 2 is a molecular level enlarged view of the chemisorption monolayer according to Example 1 of the present invention.

FIG. 3 is a molecular level enlarged view of the chemisorption film of Example 1 of the present invention.

FIG. 4 is a molecular level enlarged view of the chemisorption monolayer according to Example 2 of the present invention.

FIG. 5 is a molecular-level enlarged view of the chemisorption film of Example 2 of the present invention.

FIG. 6 is a molecular level enlarged view of the chemisorption film of Example 3 of the present invention.

FIG. 7: Structural formula of the polysaccharide used in Example 3 of the present invention

FIG. 8 is a molecular level enlarged view of the chemisorption film of Example 3 of the present invention.

FIG. 9 is a molecular level enlarged view of the hydrophilic film of Example 4 of the present invention.

FIG. 10 is a molecular level enlarged view of the chemisorption cumulative film of Example 4 of the present invention.

FIG. 11 is a molecular level enlarged view of the chemisorption monolayer of Comparative Example 2 of the present invention.

[Explanation of symbols]

 1 glass substrate 2 hydroxyl group 3,5,11 chemisorption monolayer 4,6,7,8 chemisorption film 9 hydrophilic thin film 10 chemisorption monolayer

Claims (10)

[Claims] 1. A hydrophilic thin film in which a chemisorption film is fixed to a surface of a substrate by a chemical bond, and a molecule having a hydrophilic group is introduced into or on the molecule of the chemisorption film, wherein The molecule having is a saccharide, a cyclodextrin, a polyether, a polyalcohol, a polyethylene oxide, a poly N-vinyl lactam, a polymethacrylamide, a polymethacrylic acid, a polymethacrylic acid ester, and a polyvinylamine. A hydrophilic thin film comprising at least one molecule selected from the group. 2. The chemisorption film comprises a substrate, C, Si, Ge, and
The hydrophilic thin film according to claim 1, wherein the hydrophilic thin film is covalently bonded via at least one atom selected from Sn, Ti, Zr, and S. 3. The hydrophilic thin film according to claim 1, wherein the chemisorption film is selected from a monomolecular film and a monomolecular accumulating film. 4. The hydrophilic group is a hydroxyl group, a carboxyl group,
Sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphorous acid group, quaternary ammonium group, quaternary phosphonium group,
The hydrophilic thin film according to claim 1, which is at least one selected from a thiol group, an amino group, and a sulfate ester group. 5. A functional group H selected from a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, and a thiol group is substituted with an alkali metal or an alkaline earth metal. The hydrophilic thin film according to claim 4, which is at least one selected from the functional groups described above. 6. A method for producing a hydrophilic thin film, wherein a chemisorption film is fixed to a surface of a substrate by a chemical bond, and a molecule having a hydrophilic group is introduced into or on the molecule of the chemisorption film. A functional group is allowed to exist in the adsorption film, and the functional group, sugars, cyclodextrins, polyethers,
Polyalcohols, polyethylene oxides, poly N
-A hydrophilic thin film characterized by immobilizing at least one molecule selected from vinyl lactams, polymethacrylamides, polymethacrylic acids, polymethacrylic acid esters, and polyvinylamines by a covalent bond by a chemical reaction. Manufacturing method. 7. A raw material for forming a chemisorption film is a functional group represented by the general formula (Formula 1), a functional group represented by the general formula (Formula 2), or a halogen represented by the general formula (Formula 3). 7. The method for producing a hydrophilic thin film according to claim 6, which is a molecule having at least one functional group selected from a sulfonyl group, a halogenated sulfinyl group represented by the general formula (Formula 4), and a cyano group (—CN). . [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] 8. The hydrophilic group is a hydroxyl group, a carboxyl group,
Sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphorous acid group, quaternary ammonium group, quaternary phosphonium group,
The method for producing a hydrophilic thin film according to claim 6, wherein the hydrophilic thin film is at least one selected from a thiol group, an amino group, and a sulfate ester group. 9. A functional group H selected from a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, and a thiol group is substituted with an alkali metal or an alkaline earth metal. The method for producing a hydrophilic thin film according to claim 8, wherein the hydrophilic thin film is at least one selected from the functional groups described above. 10. The method for producing a hydrophilic thin film according to claim 5, wherein the chemisorption film is selected from a monomolecular film and a monomolecular cumulative film.