JPH05193056A - Water and oil repellent base material and water and oil repelling treatment of surface of base material - Google Patents

Abstract

PURPOSE:To form a chemical adsorption polymer film enhanced in durability and having extremely high water and oil repelling effect by reacting a chlorosilane base chemical adsorbent with the functional group such as a hydroxyl group or an imino group on the surface of a base material such as glass, ceramics, a fiber, a metal, leather or cloth. CONSTITUTION:A base material 1 having a functional group such as a hydroxyl group 3 or an imino group is immersed in a solution prepared by dissolving a silane base chemical adsorbing substance containing a fluorocarbon group in a non-aqueous medium and taken out of the solution to be dried in an atmosphere containing almost no moisture to remove the non-aqueous solvent and the film of the silane base chemical adsorbing substance is formed on the surface of a monomolecular film. When this film is further exposed to the air, it generates the dehydrochlorination reaction with moisture in the air to be polymerized. At this time, the film 5 contains a large number of fluorine atoms and these fluorine atoms are reacted with moisture in air or the hydroxyl group, imino group or carboxyl group on the surface of the base material to form an -SiO bond or an -SiN < bond and the film is formed on the surface of the base material in a state chemically bonded through said bond.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for rendering a surface of a base material water and oil repellent. More specifically, the present invention relates to a method for making a surface of a substrate water- and oil-repellent by forming a water- and oil-repellent ultrathin film on the surface of metal, ceramic, glass, plastic, fiber, paper or the like.

Furthermore, the present invention relates to a water- and oil-repellent apparel member. More specifically, the present invention relates to a high-performance water-repellent, oil-repellent, and antifouling apparel member typified by ski wear, rain gear, sportswear, cloth for gloves, fur, leather, and the like.

[0003]

2. Description of the Related Art Conventionally, as a method for making surfaces of metals, ceramics, glass, plastics, fibers, papers, woods, etc. water and oil repellent, various resins and paints are impregnated or coated, polytetrafluoroethylene, etc. A method of applying or baking a fluororesin emulsion has been used.

[0004] Furthermore, it is an important task to prevent dirt and prevent rainy weather by treating ski wear, rain gear, sportswear, cloth for gloves, or fur and leather with water and oil repellency. Conventionally, for apparel materials such as textile products,
In order to impart water repellency while maintaining a certain level of breathability, a method has been proposed in which a fluorocarbon emulsion (fluororesin) is coated by a spray method or the like to provide a porous coating film having fine holes. .. As another means, a method has been proposed in which a resin such as urethane resin is thinly coated to provide a porous coating film having fine holes. As another means, it is known that thin fibers having a relatively high shrinkage ratio are woven at a high density and subjected to a high temperature treatment in a woven state to shrink them.

Further, natural fur such as mink is subjected to polisher processing using a coating liquid containing a silicone compound or a fluorine compound.

[0006]

However, the conventional method has a major drawback that the coating film is not chemically bonded to the surface of the substrate and thus has poor durability. There is also a problem that the appearance of the surface of the substrate itself is impaired. further,
The conventional method of coating a water repellent has little effect and has almost no durability. Further, the method of coating the resin on the surface of the member has drawbacks such as stuffiness when worn.
It has been an important subject in the improvement of apparel members to perform water / oil repellency treatment only on the fiber surface without impairing the gloss and texture of the fiber and the air permeability.

In order to solve the above-mentioned problems of the prior art, the present invention covers the surface of a substrate such as metal, ceramic, glass, plastic, fiber, paper and wood with an ultra-thin film having high durability. To provide a method of making it possible. Another object of the present invention is to provide a base material such as a water- and oil-repellent apparel member that is free from stuffiness when worn and has excellent durability, in order to solve the problems of the conventional art.

[0008]

In order to achieve the above object, in the water / oil repellent substrate of the present invention, the chemisorption polymer film containing a large number of water / oil repellent functional groups has a covalent bond containing —Si—. It is provided with a structure in which it is formed on the surface of the member through.

In the above structure, it is preferable that the water- and oil-repellent functional group is a fluorocarbon group and the covalent bond is a siloxane bond. Further, in the above configuration,
The base material is preferably at least one selected from fibers, metals, ceramics, glass, plastics and paper.

In the above structure, it is preferable that the base material is a fiber for apparel. Next, the water-repellent and oil-repellent treatment method for the substrate surface of the present invention is a method for forming a chemisorption polymer film on the substrate surface, which comprises applying a silane-based chemisorption substance containing a plurality of fluorocarbon groups and chloro groups. In a solution dissolved in a non-aqueous solvent, a step of immersing a base material containing a hydrophilic group on the surface, and removing the base material from the solution and drying in an atmosphere containing no or substantially no water, The method is characterized by including a step of removing the non-aqueous solvent and a step of taking out the treated product into the air.

In the above method, CF _{3 is} used as the silane-based chemisorption substance containing a plurality of fluorocarbon groups and chloro groups.
_{- (CF 2) n -R-} SiX p Cl 3-p ( where, n is an integer, the substituent R comprises an alkyl group or a silicon or oxygen atom or a chemical bond,, X is H or an alkyl group, alkoxy group It is preferable to use a substituent selected as p, 0, 1 or 2).

In the above construction, it is preferable to use a hydrocarbon-based or fluorocarbon-based solvent as the non-aqueous solvent. Further, in the above structure, the hydrophilic group on the surface of the base material is preferably any one of a hydroxyl group, a carboxyl group, an imino group and an amino group.

Further, in the above structure, it is preferable to use a base material having a surface subjected to plasma treatment or corona treatment as the base material.

[0014]

According to the above construction, since the chemisorption polymer film containing a large number of water- and oil-repellent functional groups is formed on the surface of the member through the covalent bond including the -Si- bond, the water- and oil-repellency is improved. The base material can be excellent and have excellent durability.

That is, in the present invention, since an ultrathin film containing a large number of fluorine having extremely high water and oil repellency can be formed on the surface of the substrate through a chemical bond, it is possible to perform a highly durable water and oil repellency treatment. is there. When the base material is, for example, a fiber for apparel, an ultra-thin film of nanometer level is formed on the surface of the base material, so that the breathability of a woven fabric or a knitted fabric is not hindered and the stuffiness when worn is extremely high. Few. Further, according to the preferred constitution of the present invention in which the water- and oil-repellent functional group is fluorine and the covalent bond is a siloxane bond, an ultrathin film containing a large number of fluorine, which is extremely water- and oil-repellent, is chemically bonded. Since it can be formed on the surface of the apparel member through the above, it is possible to supply a highly durable water- and oil-repellent apparel member.

Next, according to the method of the present invention, a substrate having a hydrophilic group on its surface is immersed in a solution prepared by dissolving a silane-based chemical adsorbent containing a plurality of fluorocarbon groups and chloro groups in a non-aqueous solvent. After that, the base material is taken out of the solution and dried in an atmosphere containing almost no water to remove the non-aqueous solvent, whereby a coating film of the silane-based chemical adsorbent is formed on the surface of the base material. Then, when it is further taken out into the air, this coating film is polymerized by a dehydrochlorination reaction with moisture in the air. At this time,
Since the coating film also undergoes a dehydrochlorination reaction with the surface of the base material to form a covalent bond, an extremely water- and oil-repellent ultra-thin film bonded to the surface of the base material through a chemical bond can be formed.

A plurality of fluorocarbon groups and chloro groups are contained.
CF as a silane-based chemical adsorbent ₃(CF₂)₇(C
H₂)₂SiCl₃, CF₃(CF₂)_Five(CH₂)₂
SiCl₃, CF₃CH₂O (CH₂)₁₅SiCl₃,
CF₃(CH₂)₂Si (CH₃)₂(CH₂)₁₅Si
Cl₃, F (CF₂)_Four(CH₂)₂Si (CH₃) ₂
(CH₂)₉SiCl₃, CF₃COO (CH₂)₁₅S
iCl₃Can be used.

Further, it is convenient to use a hydrocarbon-based or fluorocarbon-based solvent as the non-aqueous solvent because it is not toxic. If the hydrophilic group on the surface of the base material is any of a hydroxyl group, a carboxyl group, an imino group, and an amino group, the silane-based chemisorbed substance is likely to covalently bond.

When a base material having a surface subjected to plasma treatment or corona treatment is used as the base material, a chemisorption film can be easily formed even if the material has low reactivity at the beginning.

[0020]

EXAMPLES The method of the present invention will be described more specifically with reference to the following examples. The following examples are representative water and oil repellent treatment methods relating to the present invention.

Further, a specific example of the case where the apparel member is subjected to the water / oil repellent treatment will be described. A solution prepared by dissolving a silane-based chemical adsorbent containing a plurality of fluorocarbon groups and chloro groups in a non-aqueous solvent, after immersing a member for apparel containing a hydroxyl group, an imino group or a carboxyl group on the surface, then apparel from the solution When the member for use is taken out and dried in an atmosphere containing almost no water to remove the non-aqueous solvent, a coating film of the silane-based chemisorbed substance is formed on the surface of the monomolecular film. Then, when it is further taken out into the air, this coating film is polymerized by a dehydrochlorination reaction with moisture in the air. At this time, since the coating film also undergoes a dehydrochlorination reaction with the surface of the apparel member to form a covalent bond, an extremely water- and oil-repellent ultra-thin film containing a large number of fluorine bonded to the surface of the apparel member through a chemical bond can be formed. .. Specific examples will be described below.

Example 1 First, a glass substrate (metal, ceramic,
Prepare any surface-containing plastic, fiber, etc. that has a functional group that causes a dehydrochlorination reaction with a chlorosilyl group such as a hydroxyl group, imino group, or carboxyl group on the surface) (Fig. 1 (a)), and after washing , a fluorocarbon group, a silane-based chemical adsorbate having a plurality of chloro groups, e.g. _{CF 3 - (CF 2) n} -R-SiX p Cl 3-p ( where, n is an integer, R represents an alkyl group or Substituent containing silicon or oxygen atom, or chemical bond, X is H or a substituent such as alkyl group or alkoxy group, p is a substance represented by 0, 1 or 2), for example, CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ SiCl ₃ was dissolved in a fluorocarbon solvent (for example, Asahi Glass: Aflude) at a concentration of 1 wt% to obtain a solution of 10
Soak for about a minute, and then wash with an organic solvent without containing water (preferably a relative humidity of 5
% Or less) When the solvent is evaporated and dried in an atmosphere, the coating film 2 is formed with a film thickness of about 200 angstroms by the silane-based chemical adsorbent having a fluorocarbon group and a plurality of chloro groups remaining on the surface. .. At this time, a part of the silane-based chemisorbed substance reacts with the hydroxyl group 3 on the surface of the base material to dehydrochlorinate to form a siloxane bond (-SiO-) 4, and is fixed on the surface of the base material (Fig. 1 (b)). .. Therefore, when the base material is further moved to an atmosphere containing water (relative humidity of about 30% or more), the chlorosilyl group remaining in the substance containing the fixed fluorocarbon group and chlorosilyl group in the coating film is removed from the water content in the air. And dehydrochlorinating to polymerize. Since the coating film thus prepared contains a large amount of fluorine and is bonded to the surface of the substrate by the siloxane bond 4, the ultra-thin film 5 having extremely high water and oil repellency is formed on the surface of the substrate (FIG. 1 (c). )).

The ultrathin film was covalently bonded to the base material through a siloxane bond, and was not peeled off by rubbing or washing. The wetting angle to water was about 150 degrees.

Example 2 A processed nylon-ABS resin (polymer alloy) substrate 11 was prepared (FIG. 2 (a)), and after washing, it was a silane group having a fluorocarbon group and a plurality of chloro groups. Chemisorbents such as CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiC
Immerse l ₃ in a solution of 1 wt% in a hydrocarbon solvent (normal hexane) for about 20 minutes, and then, without washing with an organic solvent, in an atmosphere containing almost no water (preferably a relative humidity of 5% or less) When the solvent is evaporated and dried by, the coating film 12 is formed with a film thickness of about 100 angstroms from the silane-based chemical adsorbent remaining on the surface. At this time, a part of the chlorosilane-based chemisorbed substance reacts with the imino group 13 on the surface of the substrate to dehydrochlorinate to form a siloxane bond (-SiO-) 14, which is fixed on the surface of the substrate (Fig. 2 (b). )). Therefore, when the base material is further moved to an atmosphere containing water (relative humidity of about 30% or more), the coating and the remaining chlorosilyl groups of the fixed chlorosilane-based chemical adsorbent react with water in the air and dehydrochlorination. And polymerized. The coating film thus formed contains a large amount of fluorine and is bonded to the surface of the base material by -SiN <bond 14, so that the ultra-thin film 15 having extremely high water and oil repellency is formed on the surface of the base material (Fig. 2 (c)).

The ultra-thin film was covalently bonded to the substrate via -SiN <bond, and was not peeled off by rubbing or washing. The wetting angle to water was also very high at 130 degrees.

In the above embodiment, the chlorosilane-based chemistry is used.
CF as an adsorbent₃(CF₂) ₇(CH₂)₂Si
Cl₃, CF₃(CF₂)_Five(CH₂)₂SiCl₃To
I used it, but in addition to this, CF₃CH₂O (CH₂)₁₅S
iCl₃, CF₃(CH₂) ₂Si (CH₃)₂(CH
₂)₁₅SiCl₃, F (CF₂)_Four(CH₂)₂Si
(CH₃)₂(CH₂)₉SiCl₃, CF₃COO
(CH₂)₁₅SiCl₃Etc. were available.

If a substrate whose surface has been roughened in advance by about 10 to 0.1 μm is used, Example 1
And the water repellent angle is about 160 degrees and 1 respectively.
A 70 degree one was obtained.

Example 3 First, a processed cotton cloth for raincoats (fur is used as long as the surface of the fiber or the like contains a functional group that causes a dehydrochlorination reaction with a chlorosilyl group such as a hydroxyl group, an imino group or a carboxyl group on the surface) Or anything like leather, etc. (Fig. 1
(A)), washed and the following general formula CF ₃ having a plurality of fluorocarbon groups and chlorosilyl groups _{- (CF 2) n -R-} SiX p Cl 3-p ( where, n is an integer, R represents an alkyl A group or a substituent containing a silicon or oxygen atom, or a chemical bond, X is H or a substituent such as an alkyl group or an alkoxy group, and p is a substance represented by 0, 1 or 2). For processing, dilute with a non-aqueous solvent before use.

Specific examples of the silane-based chemical adsorbent represented by the above general formula include, for example, CF ₃ (CF ₂ )
_{There is 7} (CH ₂ ) ₂ SiCl ₃ . 1 wt% of this compound in a fluorocarbon solvent (eg Asahi Glass: Aflude)
By immersing the solvent in the dissolved solution for about 10 minutes and then evaporating and drying the solvent in an atmosphere containing almost no water (preferably a relative humidity of 5% or less) without washing with an organic solvent, the surface of the cotton fiber 1 is Residual silane-based chemisorption material with a film thickness of about 200 Å 2
Is formed. At this time, a part of the silane-based chemisorbed substance reacts with the hydroxyl group 3 on the surface of the cotton fiber to dehydrochlorinate to form a siloxane bond (-SiO-) 4, and is fixed on the fiber surface (Fig. 1 (b)). .. Then, when the cotton cloth is further transferred into an atmosphere containing water (relative humidity of about 30% or more), the coating film on the surface of the fiber and the remaining chlorosilyl groups of the silane-based chemisorbed substance fixed on the surface of the fiber are Dehydrochlorination reaction is carried out to polymerize. Since the coating film thus prepared contains a large amount of fluorine and is bonded to the cotton fiber surface by the siloxane bond 4, the ultrathin film 5 having extremely high water and oil repellency is formed on the cotton fiber surface (see FIG. 1 ( c)).

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S
By adding pyridine (any alkali that does not react with the chlorosilyl group and does not contain water) to a solution of iCl ₃ dissolved in aflude, it can be treated without degrading the cotton cloth. It was The reason for this is that the hydroxyl group (—OH group) or carboxyl group of cotton fiber and the CF
_{3 (CF 2) 7 (CH} 2) Although dehydrochlorination by reaction with ₂ SiCl ₃ of chlorosilyl groups (-Cl group) occurs, cotton by the hydrochloric acid is expected to acid degradation. However, if pyridine is added in a considerable amount, dehydrochlorination seems to be neutralized by pyridine and does not damage the cotton fiber.

The ultrathin film containing fluorine thus obtained was covalently bonded to the cotton fiber through a siloxane bond, and was not peeled off by rubbing or washing. In addition, the wetting angle of the water-repellent and oil-repellent treated cotton cloth with water was about 170 degrees.

Example 4 Prepared nylon fiber 11 (FIG. 2)
(A)), after washing, a plurality of fluorocarbon groups and chloro groups
Silane-based chemisorbents with individual substances such as CF₃(C
F ₂)_Five(CH₂)₂SiCl₃A fluorocarbon solvent
20 minutes in a solution containing 1 wt% of (normal hexane)
Immerse once and then wash without washing with organic solvent.
It contains almost no water (preferably less than 5% relative humidity)
Bottom) After evaporation of the solvent and drying in an atmosphere, it remains on the surface.
100 angstrom with the above-mentioned silane-based chemisorbent
The coating film 12 is formed with a film thickness of about 10 μm. At this time, part
Substances containing fluorocarbon groups and chlorosilane groups of
-SiN <bond 14 by dehydrochlorination reaction with the imino group 13 on the surface
And is fixed on the surface of the fiber base material (FIG. 2 (b)). So
The fiber further contains water (relative humidity of about 30% or less).
(Above) When transferred to an air atmosphere, this coating and the fixed
Residual chlorine content of substances containing fluorocarbon and chlorosilyl groups
The rosilyl group is polymerized by dehydrochlorination reaction with moisture in the air.
To be done. The coating film created in this way contains a large amount of fluorine.
Including -SiN <Because it is bonded to the fiber surface with bond 14,
Ultra thin film 15 with extremely high water and oil repellency is formed on the fiber surface
(FIG. 2 (c)).

The ultra-thin film was covalently bonded to the fiber via -SiN <bond, and was not peeled off by rubbing or washing. After weaving the water- and oil-repellent treated nylon fiber into a cloth, the wetting angle to water was measured and found to be extremely high at about 170 degrees.

In the above examples, the substances containing a fluorocarbon group and a chlorosilane group are CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ In addition to these, the following substances could also be used.

CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
Cl ₃ F (CF ₂ ) ₄ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (C
H ₂ ) ₉ SiCl ₃ CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃

[0036]

As described above, when the method of the present invention is used, a solution of a silane-based chemisorbent containing a fluorocarbon group in a non-aqueous solvent is added to the surface of the solution, and a functional group such as hydroxyl group 3 or imino group is formed on the surface of the solution. After immersing the base material 1 containing a group, removing the base material from the solution and drying it in an atmosphere containing almost no water to remove the non-aqueous solvent, the surface of the monomolecular film is coated with the silane-based chemical adsorption substance. A film is formed. Then, when the coating film is further exposed to the air, the coating film is polymerized by a dehydrochlorination reaction with moisture in the air. At this time, the coating film 5 contains a large amount of fluorine and reacts with moisture in the air or with a hydroxyl group, an imino group or a carboxyl group on the surface of the base material to form -SiO- or -SiN <.
It is formed in a state of being chemically bonded to the surface of the base material through a bond. As a result, an ultra-thin film having an extremely high water / oil repellency effect can be formed on the surface of the base material through a chemical bond, so that highly durable water / oil repellency treatment can be performed very easily.

Further, according to the present invention, an ultra-thin film having an extremely high water / oil repellency effect can be formed on the surface of a substrate through a covalent bond. Therefore, a highly durable water / oil repellant-treated apparel member can be manufactured at low cost. There is an effect that can be provided in.

[Brief description of drawings]

FIG. 1 is a process cross-sectional view used for explaining a water / oil repellent treatment method for a substrate which is a first and a third embodiment of the present invention.

FIG. 2 is a process cross-sectional view used for explaining a water and oil repellent treatment method for a substrate which is the second and fourth embodiments of the present invention.

[Explanation of symbols]

 1,11 Base material 2,12 Coating film 3 Hydroxyl group 13 Imino group 4 Siloxane bond 14 -SiN <bond 5,15 Water- and oil-repellent ultra-thin film

Claims (9)

[Claims] 1. A water- and oil-repellent substrate in which a chemisorption polymer film containing a large number of water- and oil-repellent functional groups is formed on the surface of a member via a covalent bond containing a —Si— bond. 2. The water- and oil-repellent functional group is a fluorocarbon group, and the covalent bond is a siloxane bond.
The water- and oil-repellent base material described. 3. The water- and oil-repellent substrate according to claim 1, wherein the substrate is at least one selected from fibers, metals, ceramics, glass, plastics and paper. 4. The base material is a fiber for apparel.
The water- and oil-repellent base material described. 5. A method for forming a chemisorption polymer film on a surface of a base material, which comprises applying a silane chemisorption substance containing a plurality of fluorocarbon groups and chloro groups to a solution prepared by dissolving the silane chemisorption material in a non-aqueous solvent. A step of immersing the base material containing a hydrophilic group, a step of removing the base material from the solution and drying it in an atmosphere containing no or substantially no water, and removing the non-aqueous solvent; A method for treating a water-repellent and oil-repellent surface of a base material, the method including the step of taking out a product into the air. 6. A silane-based chemical adsorbent containing a plurality of fluorocarbon groups and chloro groups, which is CF _3- (CF ₂ ) _n -R-SiX _p Cl _3-p (where n is an integer and R is an alkyl group). Group or a substituent containing a silicon or oxygen atom, or a chemical bond, X is H
Or a substituent selected from an alkyl group and an alkoxy group,
The water- and oil-repellent treatment method for a substrate surface according to claim 5, wherein p is 0, 1 or 2). 7. The water- and oil-repellent treatment method for a substrate surface according to claim 5, wherein a hydrocarbon-based or fluorocarbon-based solvent is used as the non-aqueous solvent. 8. The water- and oil-repellent treatment method for a substrate surface according to claim 5, wherein the hydrophilic group on the substrate surface is any one of a hydroxyl group, a carboxyl group, an imino group and an amino group. 9. The surface of the base material is treated with plasma,
Alternatively, the water-repellent and oil-repellent treatment method for a substrate surface according to claim 5, wherein a substrate subjected to corona treatment is used.