JP2886814B2 - Water and oil repellent substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate whose surface is made water and oil repellent. More specifically, the present invention relates to a substrate having a water- and oil-repellent surface formed by forming a water- and oil-repellent ultra-thin film on the surface of metal, ceramic, glass, plastic, fiber, paper, or the like. Furthermore, the present invention
The present invention relates to a member for water / oil repellent apparel. More particularly, the present invention relates to a high-performance water-repellent, oil-repellent, stain-resistant apparel member represented by ski wear, rain gear, sports wear, glove cloth, fur, leather, or the like.

[0002]

2. Description of the Related Art Conventionally, as a method for making a surface of metal, ceramic, glass, plastic, fiber, paper, wood, etc. water- and oil-repellent, various resins or paints are impregnated or coated, and polytetrafluoroethylene or the like is used. A method of applying or baking a fluororesin emulsion has been used.

[0003] Further, it is important to prevent water and oil repellency of ski wear, rain gear, sports wear, glove cloth, or fur or leather from the viewpoint of dirt prevention and rainy weather measures. Conventionally, for apparel members such as textile products,
In order to impart water repellency while maintaining a certain degree of air permeability, a method has been proposed in which a fluorocarbon-based 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 a urethane resin is thinly coated to provide a porous coating film having fine holes. As another means, it is also known that fine fibers having a relatively high shrinkage ratio are woven at a high density, and the fibers are shrunk by high-temperature treatment in a woven state.

Further, natural fur such as mink is polished using a coating solution containing a silicone compound or a fluorine compound.

[0005]

However, the conventional method has a serious drawback that the coating film is not chemically bonded to the surface of the substrate and has poor durability. There is also a problem that the aesthetic appearance of the surface of the substrate itself is impaired. further,
The conventional method of coating with a water repellent had little effect and had little durability. Further, the method of coating the surface of the member with a resin has a drawback such as stuffiness when worn.
It is an important issue in improving apparel members to perform water / oil repellent treatment only on the fiber surface without impairing the gloss and texture of the fiber and the air permeability.

The present invention solves the above-mentioned problems of the prior art by covering the surface of a base material such as metal, ceramic, glass, plastic, fiber, paper, wood or the like with a highly durable ultra-thin film. Provide technology for Another object of the present invention is to provide a base material such as a water-repellent and oil-repellent apparel member which is free from stuffiness when worn and has excellent durability in order to solve the above-mentioned problems of the prior art.

[0007]

In order to achieve the above object, the water- and oil-repellent substrate of the present invention has a fluorocarbon group.
Chemisorption polymer film containing a large number of functional groups of the water-repellent and oil-repellent containing the, in which a structure that is directly bonded formed on the substrate surface via covalent bonds including -Si- bond.

[0008] In the above configuration, it is preferable shared bond is a siloxane bond. In the above configuration, the base material is preferably at least one selected from fibers, metals, ceramics, glass, plastics, and paper. Further, in the above configuration, it is preferable that the base material is a fiber for apparel.

Next, a method for obtaining a substrate having a surface subjected to a water / oil repellent treatment according to the present invention comprises the steps of: using a silane-based chemisorbing substance containing a plurality of fluorocarbon groups and a plurality of chloro or alkoxyl groups in a non-aqueous solvent; And a step of immersing a substrate containing a hydrophilic group on the surface thereof, and removing the substrate from the solution and drying the substrate in an atmosphere containing no or substantially no moisture, and the non-aqueous solvent And forming a chemically adsorbed polymer film on the surface of the substrate by removing the treated product into the air.

In the above method, CF _{3 is} used as a silane-based chemisorbing 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 alkylene 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 0, 1 or 2) for the selected substituent, p.

In the above structure, it is preferable to use a hydrocarbon-based or fluorocarbon-based solvent as the non-aqueous solvent. Further, in the above configuration, 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.

In the above structure, it is preferable to use a substrate whose surface is subjected to plasma treatment or corona treatment as a substrate material. According to the configuration, since the chemically adsorbed polymer film containing a large number of water- and oil-repellent functional groups is formed on the surface of the base material through a covalent bond including a -Si- bond, the water- and oil-repellency is excellent. In addition, a substrate having excellent durability can be obtained.

That is, in the present invention, an ultra-thin film containing a large number of fluorines having extremely high water and oil repellency can be formed on the surface of the base material through chemical bonding. is there. When the base material is, for example, an apparel fiber, a nanometer-level ultra-thin film is formed on the surface of the base material. Few. According to the preferred configuration of the present invention in which the water- and oil-repellent functional group is fluorine and the covalent bond is a siloxane bond, the ultra-thin film containing a large number of extremely high water- and oil-repellent fluorine is chemically bonded. Since it can be formed on the surface of the apparel member through the intermediary, it is possible to supply the durable water- and oil-repellent treated apparel member.

Next, according to the method for producing a water- and oil-repellent substrate of the present invention, a silane-based chemically adsorbed substance containing a plurality of fluorocarbon groups and chloro or alkoxyl groups is dissolved in a non-aqueous solvent. After immersing the substrate containing a hydrophilic group on the surface in the solution, the substrate is taken out of the solution and dried in an atmosphere containing almost no water to remove the non-aqueous solvent. A coating of the system chemisorbed material is formed. Then, when the coating film is further taken out into the air, the coating film is depolymerized with water in the air to undergo a dehydrochlorination reaction to be polymerized. At this time, since the coating film also undergoes a dehydrochlorination reaction with the substrate surface to form a covalent bond, an extremely thin water- and oil-repellent thin film bonded to the substrate surface through a chemical bond can be formed.

It should be noted that a plurality of fluorocarbon groups and chloro groups are contained.
CF as a silane-based chemisorbent _Three(CF_Two)₇(C
H_Two)_TwoSiCl_Three, CF_Three(CF_Two)_Five(CH_Two)_Two
SiCl_Three, CF_ThreeCH_TwoO (CH_Two)_FifteenSiCl_Three,
CF_Three(CH_Two)_TwoSi (CH_Three)_Two(CH_Two)_FifteenSi
Cl_Three, F (CF_Two)_Four(CH_Two)_TwoSi (CH_Three) _Two
(CH_Two)₉SiCl_Three, CF_ThreeCOO (CH_Two)_FifteenS
iCl_ThreeEtc. can be used.

It is convenient to use a hydrocarbon-based or fluorocarbon-based solvent as the non-aqueous solvent because there is no toxicity. When 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 chemisorbing substance is easily covalently bonded.

When a substrate whose surface is subjected to plasma treatment or corona treatment is used as a substrate material, a chemically adsorbed film can be easily formed even if the material has low reactivity at first.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described more specifically with reference to the following examples. The following examples are representative water / oil repellent treatment methods according to the present invention.

Further, a specific example in the case where the apparel member is subjected to water / oil repellent treatment will be described. In a solution obtained by dissolving a silane-based chemisorbing substance containing a plurality of fluorocarbon groups and chloro groups in a non-aqueous solvent, after immersing an apparel member containing a hydroxyl group, an imino group or a carboxyl group on the surface, When the apparel member is taken out and dried in an atmosphere containing almost no water to remove the non-aqueous solvent, the apparel part is removed.
A coating film of the silane-based chemisorbed substance is formed on the surface of the material . Then, when the coating film is further taken out into the air, the coating film is depolymerized with water in the air to undergo a dehydrochlorination reaction to be polymerized. At this time,
Since the coating film also undergoes a dehydrochlorination reaction with the surface of the apparel member to form a covalent bond, a very water- and oil-repellent ultrathin film containing a large number of fluorine bonded to the surface of the apparel member via a chemical bond can be formed. Hereinafter, specific examples will be described.

[0020]

【Example】

Example 1 First, a glass substrate (metal, ceramic,
Any material may be used as long as it 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 of a plastic or fiber. , 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 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 example, CF ₃ (CF ₂ )
₁₀ (CH ₂ ) ₂ SiCl ₃ was dissolved in a 1 wt% solution in a fluorocarbon-based solvent (eg, Asahi Glass: Aflude).
Immersion for about one minute, and then, without washing with an organic solvent, contains almost no water (preferably a relative humidity of 5
% Or less) When the solvent is evaporated and dried in an atmosphere, 200 angstrom (20 nm) of a silane-based chemisorbing substance having a fluorocarbon group and a plurality of chloro groups remaining on the surface is obtained.
The coating film 2 is formed with a film thickness of the order. At this time, some of the silane-based chemisorbed substances undergo a dehydrochlorination reaction with hydroxyl groups 3 on the surface of the base material to form siloxane bonds (-SiO-) 4 and are fixed on the surface of the base material (FIG. 1B). . Then, when the substrate is further moved to an atmosphere containing water (relative humidity of about 30% or more), the chlorosilyl groups remaining in the coating film containing the fixed fluorocarbon group and chlorosilyl group are replaced with moisture in the air. And a dehydrochlorination reaction to form a polymer. Since the coating film thus formed contains a large amount of fluorine and is bonded to the substrate surface by the siloxane bond 4, an ultrathin film 5 having extremely high water / oil repellency is formed on the substrate surface (FIG. 1 (c)). )).

The ultra-thin film was covalently bonded to the substrate via a siloxane bond, and did not peel off even after being rubbed or washed. The angle of wetting with water was about 150 degrees.

Example 2 A processed nylon-ABS resin (polymer alloy) substrate 11 was prepared (FIG. 2A), washed, and then washed with a silane based fluorocarbon group and a plurality of chloro groups. Chemisorbed material, for example, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiC
l ₃ was immersed for about 20 minutes in a hydrocarbon solvent solution of 1 wt% to (normal hexane), then without washing with an organic solvent, as the water contains little (preferably less 5% relative humidity) atmosphere When the solvent is evaporated and dried, a coating film 12 having a thickness of about 100 angstroms (10 nm) is formed with the silane-based chemisorbed substance remaining on the surface. At this time, some of the chlorosilane-based chemisorbed substances undergo a dehydrochlorination reaction with the imino groups 13 on the substrate surface to form siloxane bonds (-SiO-) 14 and are fixed to the substrate surface (FIG. 2 (b) )). Then, when the substrate is further moved to an atmosphere containing water (relative humidity of about 30% or more), the remaining chlorosilyl groups of the coating film and the fixed chlorosilane-based chemically adsorbed substance react with water in the air to undergo a dehydrochlorination reaction. And polymerized. Since the coating film thus formed contains a large amount of fluorine and is bonded to the substrate surface by -SiN <bond 14, a very thin water- and oil-repellent ultrathin film 15 is formed on the substrate surface (FIG. 2 (c)).

The ultra-thin film was covalently bonded to the substrate via a -SiN <bond, and did not peel off even after being rubbed or washed. The wetting angle to water was as high as 130 degrees.

In the above embodiment, the chlorosilane-based chemical
CF as an adsorbent_Three(CF_Two) ₇(CH_Two)_TwoSi
Cl_Three, CF_Three(CF_Two)_Five(CH_Two)_TwoSiCl_ThreeTo
Used, but in addition to this, CF_ThreeCH_TwoO (CH_Two)_FifteenS
iCl_Three, CF_Three(CH_Two) _TwoSi (CH_Three)_Two(CH
_Two)_FifteenSiCl_Three, F (CF_Two)_Four(CH_Two)_TwoSi
(CH_Three)_Two(CH_Two)₉SiCl_Three, CF_ThreeCOO
(CH_Two)_FifteenSiCl_ThreeEtc. were available.

When a substrate whose surface has been roughened by about 10 to 0.1 μm in advance is used,
And the water repellent angles were about 160 degrees and 1 respectively.
70 ° was obtained.

Example 3 First, a cotton fabric for raincoat which has been processed (if the surface contains a functional group capable of causing a dehydrochlorination reaction with a chlorosilyl group such as a hydroxyl group, an imino group or a carboxyl group on the surface of the fiber or the like, fur) Or 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 silicon or an 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). In the treatment, it is used by diluting it in a non-aqueous solvent.

As a specific compound of the silane-based chemisorbed substance represented by the above general formula, for example, CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ SiCl ₃ . 1% by weight of this compound in a fluorocarbon solvent (for example, Asahi Glass: Aflud)
After immersion in the dissolved solution for about 10 minutes, and without drying with an organic solvent, the solvent is evaporated and dried in an atmosphere containing almost no water (preferably 5% or less in relative humidity). The coating film 2 is formed with a film thickness of about 200 angstroms (20 nm) using the remaining silane-based chemisorbed substance. At this time, some of the silane-based chemisorbed substances undergo a dehydrochlorination reaction with the hydroxyl group 3 on the surface of the cotton fiber to form a siloxane bond (-SiO-) 4 and are fixed on the fiber surface (FIG. 1 (b)). . Then, when the cotton cloth is further moved to an atmosphere containing moisture (relative humidity of about 30% or more), the chlorosilyl groups remaining on the fiber surface and the silane-based chemisorbed substance fixed on the surface of the fiber are converted into moisture in the air. And a dehydrochlorination reaction to form a polymer. Since the coating film thus formed contains a large amount of fluorine and is bonded to the surface of the cotton fiber by the siloxane bond 4, an ultra-thin film 5 having extremely high water / oil repellency is formed on the surface of the cotton fiber (FIG. 1 ( c)).

Note that 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 the solution in which iCl ₃ is dissolved in the fluid, it can be processed without deteriorating the cotton cloth. Was. The reason is that the hydroxyl group (—OH group) or carboxyl group of the cotton fiber and the CF
The reaction of ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl _{3 with} a chlorosilyl group (—Cl group) causes dehydrochlorination, and it is considered that the hydrochloric acid causes acid degradation of cotton. However, if a significant amount of pyridine is added, the dehydrochlorination may be neutralized by pyridine and may not damage the cotton fibers.

The ultra-thin film containing fluorine thus obtained was covalently bonded to the cotton fiber via a siloxane bond, and did not peel off even when rubbed or washed. The wetting angle of the cotton cloth thus treated with water and oil repellency to water was about 170 degrees.

Example 4 A nylon fiber 11 which has been processed is prepared (FIG. 2).
(A)) After washing, a silane-based chemisorbing substance having a plurality of fluorocarbon groups and chloro groups, for example, CF ₃ (CF ₂ )
₅ (CH ₂ ) ₂ SiCl ₃ immersed in a solution of 1 wt% in a fluorocarbon solvent (normal hexane) for about 20 minutes,
After that, without washing with an organic solvent, the solvent is evaporated and dried in an atmosphere containing almost no water (preferably, 5% or less in relative humidity). As a result, 100 angstrom (10 n
The coating film 12 is formed with a thickness of about m 2 ). At this time, a part of the substance containing a fluorocarbon group and a chlorosilyl group reacts with the imino group 13 on the fiber surface by a dehydrochlorination reaction to obtain -SiN <bond 1
4 and is fixed to the surface of the fiber substrate (FIG. 2 (b)).
Then, when the fiber is further transferred to an air atmosphere containing water (relative humidity of about 30% or more), the chlorosilyl group remaining in the coating film and the fixed substance containing a fluorocarbon group and a chlorosilyl group is combined with the moisture in the air. It is polymerized by a dehydrochlorination reaction. Since the coating film thus formed contains a large amount of fluorine and is bonded to the fiber surface by -SiN <bond 14,
An ultra-thin film 15 having extremely high water and oil repellency is formed on the fiber surface (FIG. 2C).

The ultra-thin film was covalently bonded to the fiber via a -SiN <bond, and did not peel off even after being rubbed or washed. After weaving the water- and oil-repellent treated nylon fibers on a cloth, the wetting angle to water was measured to be as high as about 170 degrees.

In the above embodiment, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ are used as substances containing a fluorocarbon group and a chlorosilyl group. Was used, but the following substances and the like 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

[0034]

As described above, when the method of the present invention is used, a solution in which a silane-based chemisorbing substance containing a fluorocarbon group is dissolved in a non-aqueous solvent is coated on the surface with a functional group such as a hydroxyl group or an imino group. After immersing the base material containing, 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 chemisorbed substance is formed on the base material surface. Is done. Then, when the coating film is further exposed to the air, the coating film undergoes a dehydrochlorination reaction with moisture in the air to be polymerized. At this time, the coating film contains a large amount of fluorine, reacts with moisture in the air, hydroxyl groups, imino groups, or carboxyl groups on the surface of the base material, and chemically bonds to the base material surface via -SiO- or -SiN <bonds. It is formed. As a result, an ultra-thin film having an extremely high water- and oil-repellent effect can be formed on the surface of the base material via a chemical bond, so that a highly durable water- and oil-repellent treatment can be performed very easily.

Further, when the present invention is used, an ultra-thin film having an extremely high water- and oil-repellent effect can be formed on the surface of the base material via covalent bonds, so that a highly durable water- and oil-repellent treated apparel member can be manufactured at low cost. There is an effect that can be provided.

[Brief description of the drawings]

FIG. 1 is a process cross-sectional view used for describing a method of treating a substrate for water / oil repellency according to first and third embodiments of the present invention.

FIG. 2 is a process cross-sectional view used for describing a method of treating a substrate for water / oil repellency according to second and fourth embodiments of the present invention.

[Explanation of symbols]

 Reference Signs List 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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B05D 7/24 302 B05D 7/24 302Y B32B 27/00 101 B32B 27/00 101 27/10 27/10 27/12 27/12 C08J 7/04 C08J 7/04 S D06M 13/517 D06M 13/517 (56) References JP-A-63-135435 (JP, A) JP-A-60-40254 (JP, A) JP-A 55-9652 (JP, A) JP-A-4-289273 (JP, A) JP-A-4-288349 (JP, A) The Japan Society of Applied Physics, 1990 (Heisei 2) The 37th Spring Meeting of the Japan Society of Applied Physics Proceedings, Vol. 3 (March 28, 1990), p. 1048 (58) Fields investigated (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 B05D 5/00-7/24 C08J 7/04

Claims (4)

(57) [Claims] 1. A chemically adsorbed polymer film containing a large number of water- and oil-repellent functional groups containing a fluorocarbon group, comprising -Si-
A water- and oil-repellent substrate which is directly bonded to a substrate surface via a covalent bond containing a bond. 2. A sharing bonds repellent substrate according to claim 1, wherein a siloxane bond. 3. The water / 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 substrate according to claim 1, wherein the substrate is a fiber for apparel.
The water- and oil-repellent substrate as described in the above.