JPH04366140A - Anti-fog oil-repellent film and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly durable anti-fog oil-repellent monomolecular film or anti-fog oil-repellent monomolecular cumulative film. More specifically, in order to improve the anti-fog and oil-repellent properties of the surface of the transparent base material, the hydrophilic and highly oil-repellent surface formed with a nanometer-level film thickness is covered with a hydrophilic group to achieve anti-fog and oil repellency. The present invention relates to a fluorocarbon-based monomolecular film or a monomolecular cumulative film.

0002

BACKGROUND OF THE INVENTION Various proposals have been made to provide antifogging properties to surfaces that tend to fog up due to water vapor or water droplets, such as window glass, bathroom mirrors, and eyeglass lenses.

Conventionally, methods for improving the antifogging properties of base materials such as glass and plastics include coating hydrophilic coatings such as modified polyethylene glycol and poly(hydroxyethyl methacrylate), and coating various silicone resins. Many methods have been proposed.

0004

[Problems to be Solved by the Invention] However, since silicone resins have low transparency, in order to apply them while maintaining the color tone and gloss of the base material, it is necessary to make the coating thickness extremely thin. However, silicone-based resins have the disadvantage of low hardness and poor scratch resistance, so making the coating film thinner has the problem of deteriorating durability. Polyethylene glycol modified products, poly(hydroxyethyl methacrylate), and the like have similarly low abrasion resistance and poor durability.

[0005] In order to solve the above-mentioned conventional problems, the present invention utilizes a nanometer-thin monomolecular film with a uniform thickness and a cumulative film thereof, thereby achieving excellent anti-fog and oil repellency.
It also retains the color tone and gloss of the base material and is resistant to scratches.
The purpose of the present invention is to provide a fluorocarbon coating film with high scratch resistance and a hydrophilic surface.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the anti-fog oil-repellent film of the present invention has a fluorine-containing monomolecular film formed on the surface of the substrate through siloxane bonds with the substrate, and the chemically adsorbed monomolecular film It is characterized by having hydrophilic groups fixed on the surface of the membrane.

[0007] In the above structure, it is preferable that a chemically adsorbed monomolecular film containing fluorine is accumulated. Next, in the first production method of the present invention, a substrate containing a hydroxyl group 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 a chlorosilyl group at one end of the fluorocarbon surfactant, and washing and removing the excess of the activator remaining on the substrate using a non-aqueous organic solvent. The method is characterized in that it includes a step of forming a monomolecular film on the surface of which a hydrophilic group is fixed by reacting with the substrate.

In the above structure, as a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule,
Xp Cl3-p Si-R1 -(CF2)n
-R2 -SiXq Cl3-q (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 and q are 0 or 1 or 2), or R1-R2-(CF2)n-R3-SiXp
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) It is preferable to use a group (p is 0, 1 or 2).

Next, in the second production method of the present invention, a substrate containing a hydroxyl group on the surface is prepared, and a surfactant containing a chlorosilyl group at one end and a reactive functional unsaturated group at the other end is mixed. a step of bringing the substrate into contact with a non-aqueous solvent and reacting the hydroxyl group on the surface of the substrate with a chlorosilyl group at one end of the activator; washing and removing the excess activator remaining on the substrate using a non-aqueous organic solvent; A step of forming a monomolecular film on the substrate, a step of changing a reactive functional group on the surface of the substrate into a group active toward chlorosilyl groups, and a step of forming a fluorocarbon-based surfactant containing chlorosilyl groups at both ends of the molecule. a step of causing the active group on the surface of the monomolecule to react with the chlorosilyl group at one end of the fluorocarbon surfactant in contact with a non-aqueous solvent mixed with a surfactant to precipitate the active agent on the surface of the substrate; , After washing and removing the excess active agent remaining on the substrate using a non-aqueous organic solvent, the surfactant is reacted with water to accumulate a monomolecular film made of a surfactant containing a plurality of silanol groups on the substrate. It is characterized by including a process.

In the first and second manufacturing methods of the present invention, glass can be used as the substrate containing hydroxyl groups on the surface. Further, in the first and second manufacturing methods of the present invention, a plastic whose surface has been previously treated in a plasma atmosphere containing oxygen to make it hydrophilic can be used as the substrate containing hydroxyl groups on the surface.

[0011]

[Operation] According to the structure of the present invention described above, a fluorocarbon-based monomolecular film or a monomolecular cumulative film having a hydrophilic surface and an extremely thin nanometer-level film thickness with excellent antifogging and oil repellency is applied to the surface of a base material. Since it is formed in a chemically (covalently bonded) state, an anti-fog oil-repellent film with excellent scratch resistance and abrasion resistance can be obtained without impairing the original color tone or gloss of the base material.

That is, since a monomolecular film containing fluorine is formed on the surface of the substrate through siloxane bonds (covalent bonds) with the substrate, it has excellent scratch resistance and abrasion resistance, as well as excellent antifogging and oil repellency. Furthermore, since hydrophilic groups are fixed on the surface of the chemically adsorbed monolayer, it also has excellent antifogging and oil repellency.

[0013] Furthermore, according to the preferred configuration of the present invention in which the chemically adsorbed monomolecular film containing fluorine is accumulated, it is possible to obtain a film with even better oil repellency. Further, according to the first manufacturing method of the present invention described above, the antifogging and oil-repellent monomolecular film of the present invention can be efficiently and rationally manufactured. Further, by repeating the first manufacturing method, a cumulative film can be obtained efficiently.

Further, according to the second manufacturing method of the present invention described above, the antifogging and oil-repellent monomolecular cumulative film of the present invention can be efficiently and rationally manufactured.

[0015]

[Example] In the present invention, glass or plastic (in the case of plastic, it is preferable to oxidize the surface to make it hydrophilic or use one with a hydrophilic surface) is prepared, and a chlorosilyl group is added to the molecule. The hydroxyl group on the surface of the substrate is reacted with the chlorosilyl group at one end of the fluorocarbon surfactant by contacting it with a non-aqueous solvent mixed with a fluorocarbon surfactant contained at both ends, thereby converting the surfactant into the fluorocarbon surfactant. A step of precipitating it on the surface of the substrate, washing and removing the excess active agent remaining on the substrate using a non-aqueous organic solvent, and then reacting it with water to form a surfactant containing a plurality of silanol groups on the substrate. By repeating the step of forming a monomolecular film containing fluorine several times to produce a hydrophilic and oil-repellent fluorine-based chemically adsorbed monomolecular cumulative film whose surface is covered with hydroxyl groups, It is possible to provide an antifogging and oil-repellent fluorocarbon chemisorbed monomolecular cumulative film whose surface is covered with hydroxyl groups.

At this time, Xp Cl3-p Si-R1 -(CF
2) n -R2 -SiXq Cl3-q (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, q is 0 or 1 or 2
) is conveniently used.

In addition, in the step of accumulating a fluorocarbon chemisorption monomolecular film, the above-mentioned film is brought into contact 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. A step of causing the hydroxyl group on the surface of the substrate to react with a chlorosilyl group at one end of the activator to precipitate the substance on the surface of the substrate, and washing and removing the excess activator remaining on the substrate using a non-aqueous organic solvent. A step of forming a monomolecular film on the substrate, and treatment with a chemical reagent,
Alternatively, the process of plasma treatment in a reactive gas or irradiation with an energy beam in a reactive gas to change the reactive functional groups on the substrate surface into groups active against chlorosilyl groups is repeated multiple times. Using a method for producing a fluorine-based chemically adsorbed monomolecular cumulative film, an antifogging oil-repellent fluorocarbon-based chemically adsorbed monomolecular cumulative film whose surface is covered with hydroxyl groups via a fluorine-containing siloxane monomolecular film is produced. Can be provided.

At this time, R as a surfactant containing a plurality of chlorosilyl groups at one end and a reactive functional group at the other end.
1-R2-(CF2)n-R3-SiXp
Cl3-p (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 a substituent such as H or an alkyl group) , p is 0 or 1
It is convenient to use or 2).

Examples of the chemical adsorbent used for accumulating a fluorocarbon chemically adsorbed monomolecular film having a hydrophilic surface 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 X3-n groups, n=1, 2, 3,
Almost all linear chlorosilane surfactants can be used, but in particular, fluorinated surfactants containing multiple chlorosilyl groups at both ends of the molecule can be used. Xp Cl3-p as carbon-based surfactant
Si-R1-(CF2)n-R2-SiXq
Cl3-q (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,
It is convenient to use q as 0, 1 or 2).

[0020] In addition, as another method for accumulating a fluorocarbon-based chemically adsorbed monomolecular film, a chlorosilane group (SiC
ln X3-n group, n = 1, 2, 3, Almost all can be used, but especially R1 -R2 -(CF2)n -R3 -S as a fluorocarbon surfactant.
iXp Cl3-p (n is an integer, R1 is an unsaturated group such as a vinyl group or acetylene group, or a dimethylsilyl group, R
2 and R3 represent 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; , Cl3Si-(CH2
)2-(CF2)6-(CH2)2-Si
Cl3 and CH2 =CH--(CF2)6-(C
H2)2-SiCl3, HSi(CH3)2
-(CH2)2-(CF2)6-(CH2)
Each will be explained using 2-SiCl3.

Example 1 First, as shown in FIG. 1, a transparent substrate 1 (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 treated with dichromic acid or O2 plasma). (Fig. 1 (
a)) After thorough drying, a substance containing multiple chlorosilyl groups at both ends of the molecule, such as Cl3Si-(CH2)
2-(CF2)6-(CH2)2-SiCl
80wt% dissolved at a concentration of about 1wt% using
When a solution of hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used), 12 wt% carbon tetrachloride, and 8 wt% chloroform 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. , the SiCl group of either one of the substances containing a plurality of chlorosilyl (-SiCl) groups at both ends of the molecule reacts with the hydroxyl group, and a dehydrochlorination reaction occurs over the entire surface of the substrate, and the following (chemical formula 1)
The combination shown in is generated.

[0022]

[Chemical formula 1]

Therefore, by further washing thoroughly with an organic solvent to remove the excess surfactant remaining on the substrate surface and washing with water, a siloxane monomolecular film 3 represented by the following (Chemical formula 2) was obtained.
It was possible to form a film with a thickness of about 15 angstroms in a state in which it was chemically bonded (covalently bonded) to the surface (Fig. 1(b)).

[0024]

[Case 2]

Next, by repeating the chemical adsorption step to the water washing step once again, a bimolecular film 4 as shown in FIG. 1(c) was formed. 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. .

Note that this film showed hydrophilicity even though it was a fluorocarbon monomolecular film. It also had excellent anti-fog and oil repellency, as well as excellent abrasion resistance and durability. Furthermore, in the above example, Cl3Si-(CH2)2-(C
F2)6-(CH2)2-SiCl3 was used, but Cl3Si-(CH2)2-(CF2)
8 -(CH2)2 -SiCl3 and Cl(CH3
)2 Si-(CH2)2-(CF2)6-
(CH2)2-SiCl3, Cl(CH3)2
Si-(CH2)2-(CF2)8-(CH2
)2-SiCl3, Cl3Si-(CH2)
2-(CF2)6-(CH2)2-Si(C
H3)2Cl, Cl3Si-(CH2)2-
(CF2)8-(CH2)2-Si(CH3
)2 Cl etc. were available.

Example 2 First, as shown in FIG. 2, a glass substrate 1 similar to that in Example 1 was prepared (FIG. 2(a)), and after thoroughly drying, a plurality of chlorosilyl groups (-SiCl) were attached to one end. Substances containing a reactive functional group (e.g. vinyl group) at one end, such as CH2=CH-(CF2)6-(CH2)2
- Using SiCl3, 80wt% hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used) dissolved at a concentration of about 2wt%, 12wt% carbon tetrachloride, 8w
When a t% 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 one end contains a plurality of chlorosilyl groups (-SiCl) and the other end contains vinyl. The SiCl group of the group-containing substance and the hydroxyl group reacted to cause a dehydrochloric acid reaction, and a monomolecular film 5 shown below (Chemical formula 3) was formed over the entire surface of the substrate (Figure 2
(b)).

[0028]

[Chemical formula 3]

Therefore, the substrate is thoroughly washed with an organic solvent to remove the 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 6 containing molecules represented by the following formulas 4 to 6 was formed in a state of chemical bonding with the surface. (Figure 2(c)).

[0030]

[C4]

[0031]

[C5]

[0032]

[C6]

Next, CH2=CH-(CF2)6
By repeating the chemical adsorption process using -(CH2)2-SiCl3 and the water washing process once again, the bilayer film 7 containing fluorocarbon groups as shown in FIG. 2(d) could be created.

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

Note that this film showed hydrophilicity even though it was a fluorocarbon monomolecular film. It also had excellent anti-fog and oil repellency, and was also excellent in durability. Example 3 First, as shown in Fig. 3, a plastic substrate 1 is prepared, the surface is treated with dichromic acid to oxidize and make it hydrophilic, and then thoroughly dried (Fig. 3(a)), and one end is coated with chlorosilyl. Group (
-SiCl) 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 reacted with the hydroxyl group to cause a dehydrochloric acid reaction, and a monomolecular film 8 shown below (Chemical formula 7) was formed over the entire surface of the substrate (FIG. 3). b)).

[0036]

[Chemical 7]

Therefore, after thoroughly washing with an organic solvent to remove the 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 9 represented by the following (Chemical formula 8) was formed in a state chemically bonded to the surface (FIG. 5(c)).

[0038]

[Chemical formula 8]

Next, HSi(CH3)2-(CH
2)2-(CF2)6-(CH2)2-S
By repeating the chemisorption process using iCl3 and the H2O2 treatment process once again, a bilayer film 10 containing fluorocarbon groups as shown in FIG. 3(d) was created.

[0040] Similarly, H2O2 is extracted from the chemical adsorption step.
By repeating the treatment process for the required number of layers, a fluorocarbon-based chemically adsorbed monomolecular cumulative film with a hydrophilic and oil-repellent surface covered with hydroxyl groups and extremely high adhesion strength was created.

[0041] This film also exhibited hydrophilicity, although it was a fluorocarbon monomolecular film. It also had excellent anti-fog oil repellency, abrasion resistance, and durability. In addition, in the final adsorption step, Cl3Si-(CH2)2-(CF2
)6-(CH2)2-SiCl3 further improved the hydrophilicity.

[0042]

As explained above, according to the present invention, a fluorocarbon-based monomolecular film or a monomolecular cumulative film with a hydrophilic surface and an extremely thin film thickness on the nanometer level, which has excellent antifogging and oil repellency, Since it is formed chemically (covalently) bonded to the surface of the base material, it does not impair the original color tone or gloss of the base material, and provides an anti-fog oil-repellent film with excellent scratch resistance and abrasion resistance.

Further, according to the preferred configuration of the present invention in which the chemically adsorbed monomolecular film containing fluorine is accumulated, it is possible to obtain a film with even better oil repellency. Further, according to the first manufacturing method of the present invention described above, the antifogging and oil-repellent monomolecular film of the present invention can be efficiently and rationally manufactured. Further, by repeating the first manufacturing method, a cumulative film can be obtained efficiently.

Furthermore, according to the second manufacturing method of the present invention described above, the antifogging and oil-repellent monomolecular cumulative film of the present invention can be efficiently and rationally manufactured.

[Brief explanation of drawings]

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

FIG. 3 is a process conceptual diagram used to explain the method for producing an antifogging and oil-repellent fluorocarbon chemically adsorbed monomolecular cumulative film whose surface is coated with a fluorocarbon group according to the present invention.

[Explanation of symbols]

1 Base 2. Hydroxyl group 3 Hydrophilic fluorocarbon monolayer

Claims (7)

[Claims] 1. An anti-fog repellent, characterized in that a monomolecular film containing fluorine is formed on the surface of a substrate via a siloxane bond with the substrate, and a hydrophilic group is fixed to the surface of the chemically adsorbed monomolecular film. Oil slick. 2. The anti-fog oil-repellent film according to claim 1, wherein a chemically adsorbed monomolecular film containing fluorine is accumulated. 3. 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 containing a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule. A step of reacting the carbon-based surfactant with the chlorosilyl group at one end, and washing off the excess active agent remaining on the substrate using a non-aqueous organic solvent, and then reacting with water to make the surface hydrophilic. A method for producing an anti-fog oil-repellent film, comprising the step of forming a monomolecular film in which groups are fixed on the substrate. 4. Xp Cl3-p Si-R1 -(CF
2) n -R2 -SiXq Cl3-q (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 , q is 0 or 1 or 2), or R1-R2-(CF2)n-R3-SiXp
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) The method for producing an anti-fog oil-repellent film according to claim 3, wherein p is 0, 1 or 2). 5. A substrate having a hydroxyl group on its surface is prepared, and the substrate is brought into contact with a non-aqueous solvent mixed with a surfactant containing a chlorosilyl group at one end and a reactive functional unsaturated group at the other end,
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, and forming a monomolecular film on the substrate. a step of forming a reactive functional group on the substrate surface into a group active toward chlorosilyl groups, and a non-aqueous solvent mixed with a fluorocarbon surfactant containing chlorosilyl groups at both ends of the molecule. a step of causing the active group on the surface of the monomolecule to react with the chlorosilyl group at one end of the fluorocarbon surfactant to precipitate the active agent on the surface of the substrate, and using a non-aqueous organic solvent. It is characterized by comprising a step of washing and removing the excess active agent remaining on the substrate and reacting it with water to accumulate a monomolecular film made of a surfactant containing a plurality of silanol groups on the substrate. A method for producing an anti-fog oil-repellent film. 6. The method for producing an anti-fog oil-repellent film according to claim 3, wherein glass is used as the substrate containing hydroxyl groups on the surface. 7. The method for producing an anti-fog oil-repellent film according to claim 3, wherein the substrate having a hydroxyl group on its surface is a plastic whose surface has been previously treated in an oxygen-containing plasma atmosphere to make it hydrophilic.