JPH04367721A - Chemically adsorbed fluorine contained laminated monomolecular film and method for preparing the same - Google Patents

Abstract

PURPOSE:To provide a chemically adsorbed fluorine contained thin laminated monomolecular film free from pinholes which has a good adhesion with a substrate and excellent water-oil repellent or hydrophilic oil-repellent properties and its preparation method. CONSTITUTION:A substrate 1 having hydroxy groups 2 on the surface is brought into contact with a solution containing compounds having more than one chlorosilyl groups at least at the ends of the molecule, for example CCl3 Si-(CH2)2-(CF2)6-(CH2)2-SiCl3. The treated substrate, after being washed, is reacted with water to form the first monomolecular film 3. The first monomolecular film 3 is again treated with the solution, washed and reacted with water to form the second monomolecular film. A laminated monomolecular film 4 is thus formed. The laminated film can have more than two layers.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorocarbon chemisorbed monomolecular cumulative film and a method for producing the same. More specifically, we are accumulating fluorocarbon-based chemically adsorbed monomolecular films that are intended to replace conventional fluorocarbon-based coatings used in electrical appliances, vehicles, industrial equipment, etc. that require water and oil repellency and hydrophilic and oil repellency. It is about invention.

0002

[Prior Art] The manufacturing method of fluorocarbon coating film, which has been widely used in the past, generally involves roughening the surface of a metal substrate such as Al (aluminum), steel, stainless steel, etc. using a wire brush or chemical etching, and then applying a primer. After coating, a paint made by suspending fine fluorocarbon powder such as polytetrafluoroethylene in ethanol, etc. is applied, and after drying, it is heated (baked) at about 400°C for about 1 hour to coat the surface of the substrate with fluorocarbon. Methods of baking the polymers have been used.

0003

[Problems to be Solved by the Invention] However, while this method is easy to manufacture, there is a limit to the adhesion with the base because the polymer and the base are only bonded by an anchor effect. Since the surface of the coating film was baked at a high temperature of 400° C., the surface was flattened and a good water- and oil-repellent surface could not be obtained. Therefore, it has been unsatisfactory as a manufacturing method for appliances, automobiles, industrial equipment, etc. that require water- and oil-repellent coating films.

Furthermore, a method of plasma treatment has been used to make the surface of the fluorocarbon coating film hydrophilic, but none of the methods have been satisfactory in terms of characteristics.

In view of the drawbacks of the conventional methods described above, the object of the present invention is to provide a fluorine-based coating film that has good adhesion to a substrate, is thin, has no pinholes, and has excellent water and oil repellency or hydrophilic and oil repellency. Provides an alternative method for creating thin films to improve the performance of equipment that requires water- and oil-repellent, hydrophilic, oil-repellent, heat-resistant, weather-resistant, and abrasion-resistant coatings such as those required for electrical appliances, vehicles, and industrial equipment. It's about letting people know.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the fluorine-based chemically adsorbed monomolecular cumulative film of the present invention has a first monomolecular film formed on the surface of a substrate through siloxane bonds with the substrate, A cumulative film having at least a second monomolecular film formed on its surface via siloxane cross-linking, characterized in that the cumulative film has at least a molecular chain containing fluorine in its side chain. .

In the structure of the cumulative film of the present invention, it is preferable that the surface of the outermost monomolecular film has hydroxyl groups and that the cumulative film has hydrophilic and oil-repellent properties. Further, in the structure of the cumulative film of the present invention, it is preferable that the surface of the outermost monomolecular film has a fluorocarbon group, and the cumulative film has water and oil repellency.

Next, in the first production method of the present invention, a substrate containing hydroxyl groups on the surface is prepared, and the substrate is brought into contact with a non-aqueous solvent mixed with a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule. , a step of reacting the hydroxyl group on the surface of the substrate with the chlorosilyl group at one end of the fluorocarbon surfactant, washing and removing the excess active agent remaining on the substrate using a non-aqueous organic solvent, and then The method is characterized by comprising a step of reacting with water to form a first monomolecular film on the substrate via siloxane bonds, and then a step selected from A or B below. A: The step of forming the first monomolecular film is repeated at least once on the surface of the first monomolecular film to accumulate a second monomolecular film. B: A non-aqueous solvent mixed with a fluorinated surfactant consisting of a linear fluorocarbon molecule having a chlorosilyl group at one end and a fluorocarbon group at the other end on the surface of the first monomolecular film. to react the hydroxyl groups on the surface of the first monomolecular film and the chlorosilyl groups of the linear fluorocarbon molecules, and
to accumulate a monolayer of

In the first production method, Xp Cl3-p Si-R1 -(CF2
)n -R2 -SiXq Cl3-q (however, n
is an integer, R1 and R2 represent an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted;
X is H or a substituent of an alkyl group, p and q are 0 or 1
Or 2) is preferably used.

Next, in the second production method of the present invention, a substrate containing a hydroxyl group on the surface is prepared, and a non-aqueous solvent mixed with a surfactant containing a chlorosilyl group at one end and a reactive functional group at the other end is prepared. a step of reacting the hydroxyl group on the surface of the substrate with a chlorosilyl group at one end of the activator, and washing and removing the excess activator remaining on the substrate using a non-aqueous organic solvent; a step of forming a first monomolecular film, and a step of changing a reactive functional group on the surface of the first monomolecular film into a group active toward a chlorosilyl group, and then a step of forming a first monomolecular film selected from A or B below. It is characterized by including a process. A: A non-aqueous solvent mixed with a fluorine-based surfactant consisting of a linear fluorocarbon molecule having a chlorosilyl group at one end and a fluorocarbon group at the other end on the surface of the first monomolecular film. are brought into contact with each other to cause the hydroxyl groups on the surface of the first monomolecular film to react with the chlorosilyl groups of the linear fluorocarbon molecules, thereby accumulating a second monomolecular film. B: Said first
A non-aqueous solvent mixed with a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule is brought into contact with the surface of the first monolayer, and the reactive functional groups on the surface of the first monolayer are combined with the fluorocarbon surfactant. A step of reacting the chlorosilyl group at one end of the carbonated carbon-based surfactant, washing off the excess active agent remaining on the substrate using a non-aqueous organic solvent, and then reacting with water to form a second monomer. Accumulate molecular membranes.

In the second production method, R1 -R2 -(CF2)n -R3 -SiXp is used as a surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end.
Cl3-p (where n is an integer, R1 is an unsaturated group or a dimethylsilyl group, R2 and R3 represent an alkyl group or a substituent containing silicon or an oxygen atom, but may be omitted; X is H or a substituent of an alkyl group) group, p
It is preferable to use 0, 1 or 2).

In the second production method, HSi(CH3)2-R1-(CF2) is used as the surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end.
n -R2 -SiXp Cl3-p (where n is an integer, R1 and R2 represent an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted, X is H or a substituent of an alkyl group, p is 0 or 1 or 2
) is preferably used to chemically treat the HSi(CH3)2- group to convert it into a HO- group.

In the second production method, the surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end is CH2=CH-R1-(CF2)n-R.
2 -SiXp Cl3-p (where n is an integer, R
1, R2 represents an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted; X is H or a substituent of an alkyl group; p is 0, 1, or 2); It is preferable to irradiate the chlorosilyl group with a beam to convert it into an active functional group.

[0014] Furthermore, as a substrate containing a hydroxyl group on the surface,
It is possible to use metal, ceramic, or glass, and it is also possible to use plastic whose surface has been previously treated in a plasma atmosphere containing oxygen to make it hydrophilic.

[0015]

[Operation] According to the structure of the present invention, a siloxane monomolecular film containing at least fluorine can be formed on the surface of any substrate in an accumulated state through chemical bonds (covalent bonds) with the substrate. A thin cumulative film with good adhesion and no pinholes can be obtained.

Furthermore, since the outermost layer can be substituted with fluorocarbon groups or hydroxyl groups, it is possible to provide a thin film that can replace fluorine-based coatings with excellent water and oil repellency or hydrophilic oil repellency, and can be used in electrical appliances, vehicles, industrial equipment, etc. It is possible to improve the performance of products that require water and oil repellency, hydrophilic oil repellency, heat resistance, weather resistance, and wear-resistant coatings.

Further, according to the first and second manufacturing methods of the present invention, the cumulative film can be formed efficiently, rationally, and uniformly.

[0018]

EXAMPLES Examples of the chemical adsorbent used for accumulating a fluorocarbon chemically adsorbed monomolecular film and the method of accumulating a monomolecular film according to the present invention will be described below in order.

In the production of the fluorocarbon-based monomolecular cumulative film according to the present invention, chlorosilane groups (SiCln
-n group, n = 1, 2, 3, Xp Cl3-p Si-R1 -(CF2
)n -R2 -SiXq Cl3-q (However,
n is an integer, R1 and R2 represent an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted; X is H or a substituent such as an alkyl group; p and q are -(CF2)n-R-SiX
q Cl3-q (However, n is an integer, R represents an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted, X is a substituent such as H or an alkyl group, q is 0
or 1 or 2) is conveniently used.

[0020] In addition, as another method for accumulating a fluorocarbon-based chemically adsorbed monomolecular film, a chlorosilane group (SiC
If it is a linear chlorosilane surfactant that has a ln All can be used, but especially as fluorocarbon surfactants, R1-R2-(CF2)n-R3-Si
Xp Cl3-p (where n is an integer, R1 is an unsaturated group or dimethylsilyl group, R2 and R3 represent an alkyl group or a substituent containing silicon or oxygen atom, but may be omitted, X is H or an alkyl group, etc.) substituent, p
It is convenient to use 0 or 1 or 2), but below, Cl3Si-(CH2)2-(CF2)6
-(CH2)2-SiCl3, CF3-(C
F2)7-(CH2)2-SiCl3, CH
2 =CH-(CF2)6-(CH2)2-S
iCl3, HSi(CH3)2-(CH2)2
-(CF2)6 -(CH2)2 -SiCl3
Each will be explained using

Example 1 First, as shown in FIG. 1, a hydrophilic substrate 1 (metal, ceramic, glass, or other substrate with an oxidized surface may be used, but in the case of a water-repellent substrate such as plastic, the surface is Prepare (by treating it with chromic acid to oxidize and make it hydrophilic).
Figure 1(a)), after drying thoroughly, a substance containing multiple chlorosilyl groups at both ends of the molecule, such as Cl3Si-(CH
2)2-(CF2)6-(CH2)2-S
80 dissolved at a concentration of about 2 wt% using iCl3.
wt% hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used), 12 wt% carbon tetrachloride, 8 wt%
When a chloroform solution is prepared and the substrate is immersed for about 2 hours, the surface of the hydrophilic substrate contains a large number of hydroxyl groups 2, so either one of the substances containing multiple chlorosilyl (-SiCl) groups at both ends of the molecule. The SiCl group reacts with the hydroxyl group to cause a dehydrochlorination reaction, and the bond shown in Formula 1 below is generated over the entire surface of the substrate.

[0022]

[Chemical formula 1]

Then, the siloxane monomolecular film 3 represented by the following formula 2 is chemically bonded (covalently In the bonded state, a film thickness of approximately 15 angstroms could be formed (FIG. 1(b)).

[0024]

[Case 2]

Next, by repeating the chemical adsorption step to the water washing step once again, the bimolecular film 4 shown in FIG. 1(c) can be produced. By repeating the chemisorption process and water washing process for the required number of layers, a fluorocarbon chemisorption monomolecular cumulative film with a hydrophilic and oil-repellent surface covered with hydroxyl groups and extremely high adhesion strength was created. .

Example 2 After accumulating a two-layer monomolecular film in Example 1, a substance containing a plurality of chlorosilyl groups at one end and the other end substituted with carbon trifluoride, such as F3 C-(CF2)7 -(CH2
)2 -SiCl3, a solution of 80 wt% hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used), 12 wt% carbon tetrachloride, and 8 wt% chloroform dissolved at a concentration of about 2 wt% was prepared, and the cumulative film was prepared. When the substrate is immersed for about 2 hours, the surface of the cumulative film contains a large number of hydroxyl groups 2, so that the SiCl group of the substance containing multiple chlorosilyl groups at one end and substituted with carbon trifluoride at the other end and the hydroxyl group. reacts, a dehydrochlorination reaction occurs, and a bond shown in the following formula 3 is generated over the entire surface of the substrate.

[0027]

[Chemical formula 3]

Therefore, when the excess surfactant remaining on the surface of the substrate is removed by thorough washing with an organic solvent, the surface of the substrate is covered with fluorocarbon groups, which is water- and oil-repellent and has extremely high adhesion strength. A chemically adsorbed monomolecular cumulative film 5 could be produced (FIG. 2).

[0029] In the above example, Cl3 Si-(
CH2)2-(CF2)6-(CH2)2
-SiCl3,F3C-(CF2)7-(CH
2) Although 2-SiCl3 was used, the following compounds can also be used as other examples.

Cl3Si-(CH2)2-(CF
2)8-(CH2)2-SiCl3, Cl(
CH3)2Si-(CH2)2-(CF2)
6-(CH2)2-SiCl3, Cl(CH3
)2 Si-(CH2)2-(CF2)8-
(CH2)2-SiCl3, Cl3Si-(C
H2)2-(CF2)6-(CH2)2-
Si(CH3)2Cl, Cl3Si-(CH2
)2-(CF2)8-(CH2)2-Si(
CH3)2Cl, F3C-(CF2)9-(
CH2)2-SiCl3, F3C-(CF2
)5-(CH2)2-SiCl3, CF3C
H2O(CH2)15SiCl3, CF3(C
H2)2Si(CH3)2(CH2)15S
iCl3 , CCF3 (CF2 )2 Si(CH3
)2 (CH2)9 SiCl3, CF3 CO
O(CH2)15SiCl3, etc.

Example 3 First, as shown in FIG. 3, a hydrophilic substrate 1 (metal, ceramic, glass, or other substrate with an oxidized surface may be used, but in the case of a water-repellent substrate such as plastic, the surface is Prepare (by treating it with chromic acid to oxidize and make it hydrophilic).
In Figure 3(a)), after drying thoroughly, a substance containing multiple chlorosilyl groups (-SiCl) at one end and a vinyl group at the other end, such as CH2 = CH-(CF2)6 -(C
Using H2)2-SiCl3, a solution of 80 wt% hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used), 12 wt% carbon tetrachloride, and 8 wt% chloroform dissolved at a concentration of about 2 wt% was prepared, and the substrate was heated for about 2 hours. When immersed, the surface of the hydrophilic substrate has 2 hydroxyl groups.
contains a large number of chlorosilyl groups (-S) at one end.
The hydroxyl group reacts with the SiCl group of a substance containing a plurality of iCl) containing a vinyl group at the other end to cause a dehydrochloric acid reaction, and a monomolecular film 6 shown in the following chemical formula 4 is generated over the entire surface of the substrate (Fig. 3(b)).

[0032]

[C4]

Therefore, the substrate is thoroughly washed with an organic solvent to remove excess surfactant remaining on the surface of the substrate, and then subjected to an energy beam (electron beam, ion beam, etc.) in a reactive gas atmosphere.
When irradiated with gamma rays, ultraviolet rays, etc. (for example, irradiated with an electron beam of about 5 Mrad in the air), a monomolecular film 7 consisting of molecules represented by the following formulas 5 to 7 was formed in a state of chemical bonding with the surface ( Figure 3(c)).

[0034]

[C5]

[0035]

[C6]

[0036]

[C7]

Next, CH2=CH-(CF2)6
By repeating the chemical adsorption process using -(CH2)2-SiCl3 and the water washing process once again, a bilayer film 8 containing fluorocarbon groups as shown in FIG. 3(d) was created.

Thereafter, by repeating the chemical adsorption process to the energy beam irradiation process for the number of layers required, a fluorocarbon chemical whose surface is covered with hydroxyl groups, imino groups, etc. has hydrophilic oil repellency and extremely high adhesion strength. We were able to create an adsorbed monomolecular cumulative film.

Example 4 After forming a one-layer monomolecular film in Example 3, a substance containing a plurality of chlorosilyl groups at one end and substituted with carbon trifluoride at the other end, for example, F3 C-(CF2)7 -(CH2
)2 -SiCl3, 80 wt% hexadecane (toluene, xylene,
Dicyclohexyl, etc.), 12wt% carbon tetrachloride, 8wt% chloroform solution is prepared and the substrate on which the cumulative film has been formed is immersed for about 2 hours.The surface of the cumulative film contains a large number of hydroxyl groups and imino groups. Therefore, the SiCl group of a substance containing multiple chlorosilyl groups at one end and substituted with carbon trifluoride at the other end reacts with the hydroxyl group to cause a dehydrochlorination reaction, and the bond shown in the following chemical formula 8 is formed over the entire surface of the substrate. generated.

[0040]

[Chemical formula 8]

Therefore, when the excess surfactant remaining on the surface of the substrate is removed by thorough washing with an organic solvent, the surface of the substrate is covered with fluorocarbon groups, which is water- and oil-repellent and has extremely high adhesion strength. A chemically adsorbed monomolecular cumulative film 9 could be produced (FIG. 4).

[0042] In the above example, in the final adsorption step, C
l3Si-(CH2)2-(CF2)6-(
If CH2)2-SiCl3 is used, a fluorocarbon-based chemically adsorbed monomolecular cumulative film having a hydrophilic surface can be produced.

Furthermore, in the above embodiment, CH2=CH-
(CF2)6-(CH2)2-SiCl3 and F3C-(CF2)7-(CH2)2-Si
Although Cl3 was used, the following compounds can also be used.

CH2=CH-(CF2)8-(CH2)
2-SiCl3F3C-(CF2)9-
(CH2)2-SiCl3F3
C-(CF2)5-(CH2)2-SiCl
3 CF3 CH2 O(CH2 )
15SiCl3 CF3 (CH2 )2 Si(
CH3 )2 (CH2 )15SiCl3 F(
CF2 )4 (CH2 )2 Si(CH3 )2
(CH2 )9 SiCl3 CF3 COO(C
H2)15SiCl3, etc.

Example 5 First, as shown in FIG. 5, a hydrophilic substrate 1 (metal, ceramic, glass, or any other substrate with an oxidized surface may be used; however, in the case of a water-repellent substrate such as plastic, the surface is Prepare (by treating it with chromic acid to oxidize and make it hydrophilic).
In Figure 5(a)), after being thoroughly dried, a substance containing a plurality of chlorosilyl groups (-SiCl) at one end and a dimethylsilyl group (HSi(CH3)2-) at the other end, such as H
Si(CH3)2-(CH2)2-(CF2
)6-(CH2)2-SiCl3, 2w
80wt% hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used) dissolved at a concentration of about t%, 1
When a 2wt% carbon tetrachloride and 8wt% chloroform solution is prepared and the substrate is immersed for about 2 hours, the surface of the hydrophilic substrate contains a large number of hydroxyl groups 2, so a plurality of chlorosilyl groups (-SiCl) are added to one end. The SiCl group of the substance containing a dimethylsilyl group at the other end reacts with the hydroxyl group to cause a dehydrochloric acid reaction, and a monomolecular film 10 shown in the following formula 9 is formed over the entire surface of the substrate (FIG. 5(b)) ).

[0046]

[Chemical formula 9]

Therefore, after thoroughly washing with an organic solvent to remove excess surfactant remaining on the surface of the substrate, KF
and H2O containing KHCO3, MeOH, THF
2 solution for about 10 hours, a monomolecular film 11 represented by the following chemical formula 10 was formed in a state chemically bonded to the surface (FIG. 5(c)).

[0048]

[Chemical formula 10]

Next, HSi(CH3)2-(CH
3)2-(CF2)6-(CH2)2-S
By repeating the chemisorption process using iCl3 and the H2O2 treatment process once again, a bilayer film 12 containing fluorocarbon groups as shown in FIG. 5(d) was created.

[0050] Similarly, H2 O2 is extracted from the chemical adsorption step.
By repeating the treatment process for the required number of layers, it was possible to create a fluorocarbon chemisorbed monomolecular cumulative film whose surface was covered with hydroxyl groups, which was hydrophilic and oil-repellent and had extremely high adhesion strength.

[0051] In the above example, in the last adsorption step, C
F3-(CF2)7-(CH2)2-SiC
By using l3, it is possible to produce a fluorocarbon chemisorbed monomolecular cumulative film whose surface is water- and oil-repellent.

[0052]

[Effects of the Invention] According to the present invention, a fluorocarbon monomolecular film containing at least fluorine can be formed on the surface of any substrate in an accumulated state through chemical bonds (covalent bonds) with the substrate. Since the outermost layer can be substituted with fluorocarbon groups or hydroxyl groups, it is possible to provide a thin film that has good adhesion to the substrate, has no pinholes, and has excellent water and oil repellency or hydrophilic oil repellency as an alternative to fluorine-based coating films, making it ideal for electrical appliances. Water and oil repellency and hydrophilic oil repellency required for vehicles, industrial equipment, etc.
It has the effect of improving the performance of equipment that requires heat-resistant, weather-resistant, and wear-resistant coatings.

[Brief explanation of drawings]

FIG. 1 is a process conceptual diagram used to explain the method for producing a hydrophilic and oil-repellent fluorocarbon chemisorption monomolecular cumulative film whose surface is covered with hydrophilic groups according to the present invention.

FIG. 2 is a process conceptual diagram used to explain the method of manufacturing a water- and oil-repellent fluorocarbon-based chemically adsorbed monomolecular cumulative film whose surface is covered with fluorocarbon groups according to the present invention.

FIG. 3 is a process conceptual diagram used to explain the method of manufacturing a hydrophilic and oil-repellent fluorocarbon-based chemically adsorbed monomolecular cumulative film whose surface is covered with hydrophilic groups according to the present invention.

FIG. 4 is a process conceptual diagram used to explain the method of manufacturing a water- and oil-repellent fluorocarbon-based chemically adsorbed monomolecular cumulative film whose surface is covered with fluorocarbon groups according to the present invention.

FIG. 5 is a process conceptual diagram used to explain the method of manufacturing a hydrophilic and oil-repellent fluorocarbon-based chemically adsorbed monomolecular cumulative film whose surface is covered with fluorocarbon groups according to the present invention.

[Explanation of symbols]

1 Base 2 Hydroxyl group

Claims (11)

[Claims] 1. A cumulative film in which a first monomolecular film is formed on the surface of a substrate through siloxane bonds with the substrate, and at least a second monomolecular film is formed on the surface of the first monomolecular film through siloxane crosslinks. The fluorine-based chemically adsorbed monomolecular cumulative film is characterized in that the cumulative film contains at least a molecular chain containing fluorine in its side chain. 2. The fluorine-based chemically adsorbed monomolecular cumulative film according to claim 1, wherein the surface of the outermost monomolecular film has hydroxyl groups, and the cumulative film has hydrophilic and oil-repellent properties. 3. The fluorine-based chemically adsorbed monomolecular cumulative film according to claim 1, wherein the surface of the outermost monomolecular film has a fluorocarbon group, and the cumulative film has water and oil repellency. 4. A substrate having a hydroxyl group on its surface is prepared, and the hydroxyl group on the surface of the substrate is brought into contact with a non-aqueous solvent mixed with a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule, so that the hydroxyl group on the surface of the substrate and the fluoride A step of reacting the carbon-based surfactant with the chlorosilyl group at one end, washing off the excess surfactant remaining on the substrate using a non-aqueous organic solvent, and then reacting with water to form a carbon-based surfactant on the substrate. forming a first monomolecular film through siloxane bonds, and then the following A
A method for producing a fluorine-based chemically adsorbed monomolecular cumulative film, comprising a step selected from B or B. A: The step of forming the first monomolecular film is repeated at least once on the surface of the first monomolecular film to accumulate a second monomolecular film. B: A non-aqueous solvent mixed with a fluorinated surfactant consisting of a linear fluorocarbon molecule having a chlorosilyl group at one end and a fluorocarbon group at the other end on the surface of the first monomolecular film. are brought into contact with each other to cause the hydroxyl groups on the surface of the first monomolecular film to react with the chlorosilyl groups of the linear fluorocarbon molecules, thereby accumulating a second monomolecular film. 5. Xp Cl3-p Si-R1 -(CF2
)n -R2 -SiXq Cl3-q (however, n
is an integer, R1 and R2 represent an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted;
X is H or a substituent of an alkyl group, p and q are 0 or 1
or 2), the method for producing a fluorine-based chemically adsorbed monomolecular cumulative film according to claim 4. 6. A substrate having a hydroxyl group on the surface is prepared, and the hydroxyl group on the surface of the substrate is removed by contacting it with a non-aqueous solvent mixed with a surfactant containing a chlorosilyl group at one end and a reactive functional group at the other end. and a chlorosilyl group at one end of the activator, and washing away excess activator remaining on the substrate using a non-aqueous organic solvent to form a first monomolecular film on the substrate. and a step of converting a reactive functional group on the surface of the first monolayer into a group active toward a chlorosilyl group, and then a step selected from A or B below. A method for producing a chemisorbed monomolecular cumulative film. A: On the surface of the first monolayer,
A non-aqueous solvent mixed with a fluorine-based surfactant consisting of a linear fluorocarbon molecule having a chlorosilyl group at one end and a fluorocarbon group at the other end is brought into contact with the first monomolecular film. The hydroxyl groups on the surface react with the chlorosilyl groups of the linear fluorocarbon molecules to accumulate a second monomolecular film. B: The reactivity of the surface of the first monomolecular film is determined by contacting the surface of the first monomolecular film with a nonaqueous solvent mixed with a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule. A step of reacting a functional group with a chlorosilyl group at one end of the fluorocarbon surfactant, washing off excess of the active agent remaining on the substrate using a non-aqueous organic solvent, and then reacting with water. , to accumulate a second monolayer. 7. R1 as a surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end;
-R2-(CF2)n-R3-SiXpCl
3-p (However, n is an integer, R1 is an unsaturated group or a dimethylsilyl group, R2 and R3 represent an alkyl group or a substituent containing silicon or an oxygen atom, but may be omitted, X is H or a substituent of an alkyl group) 7. The method for producing a fluorine-based chemically adsorbed monomolecular cumulative film according to claim 6, wherein p is 0, 1 or 2). [Claim 8] A surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end,
HSi(CH3)2-R1-(CF2)n
-R2 -SiXp Cl3-p (where n is an integer, R1 and R2 represent an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted, X is H or a substituent of an alkyl group, p is 0 or 1 or 2), the HSi(CH3)2- group is chemically treated to form HO
The method for producing a fluorine-based chemically adsorbed monomolecular cumulative film according to claim 6, wherein the fluorine-based chemical adsorption monomolecular cumulative film is converted into a - group. [Claim 9] As a surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end.
CH2=CH-R1-(CF2)n-R2-S
iXp Cl3-p (where n is an integer, R1, R2
represents an alkyl group or a substituent containing a silicon or oxygen atom, but may be omitted; X is H or a substituent of an alkyl group; 7. The method for producing a fluorine-based chemically adsorbed monomolecular cumulative film according to claim 6, wherein the chlorosilyl group is converted into an active functional group. 10. Claim 4 or 6, wherein metal, ceramic, or glass is used as the substrate having a hydroxyl group on the surface.
A method for producing a fluorine-based chemically adsorbed monomolecular cumulative film as described in . 11. The production of a fluorine-based chemically adsorbed monomolecular cumulative film according to claim 4 or 6, wherein the substrate having a hydroxyl group on its surface is a plastic whose surface has been previously treated in a plasma atmosphere containing oxygen to make it hydrophilic. Method.