JPH0786149B2 - Water repellent / fouling resistant building material manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the modification of materials used for building materials or their coated surfaces. In particular, it relates to a method for producing a building material having water repellency and antifouling property.

[0002]

2. Description of the Related Art Conventionally, many materials have been used as building materials. Building materials are roughly classified into roofing materials, outer wall materials, and interior materials. Kiln roof tiles, slate roof tiles, galvanized iron (galvanized iron plate), etc. are mainly used as roofing materials. As the outer wall material, wood (including processed wood), mortar, concrete, ceramic sizing, metal sizing, brick, stone material, plastic material, and metal material such as aluminum are used. As interior materials, wood (including processed wood),
Metal materials such as aluminum, plastic materials, paper, and fibers are used. Many of these building materials are also painted.

What is generally desired for these building materials is antifouling property. That is, the building material is exposed to the outside air and dust in the air is easily attached thereto, or dust in the room is easily attached thereto. Also, there is a problem that building materials are easily soiled, and once soiled, it is difficult to remove the soil. In addition, roofing materials and outer wall materials may be required to have antifouling property and water repellency in order to be exposed to acid rain and to make it easier for snow on the roof to fall in a snowy country.

[0004]

However, conventional building materials have a problem that they are easily soiled, and once soiled, they are difficult to remove. Fluorocarbon resins such as polytetrafluoroethylene are known as antifouling materials.While fluorocarbon resins have excellent water repellency and antifouling properties, they require baking coating and have very high mechanical properties. There is a problem that it is neither expensive nor expensive. In addition,
JP-A-60-40254 and JP-A-2-248480.
In the publication, a fluorine-based molecule is chemically bonded to the substrate surface.
Although it is proposed that it is thin, it is thin and has water repellency and stain resistance.
It is the current situation that excellent coatings have not yet been realized.

In order to solve the problems of the prior art, the present invention provides
An object of the present invention is to provide a method for producing a building material having excellent water repellency and antifouling property.

[0006]

[Means for Solving the Problems]
Therefore,FirstWater repellent and antifouling building materialManufacturing method
Is-CF at the end of the alkyl group ₃ Group present, other end
Non-Aqueous Solution Containing Chemisorbed Molecule Having Chlorosilyl Group
By contacting the base material surface of the building material or the painted surface
And then wash with a non-aqueous solution to remove the siloxane.
-CF at the terminal of the alkyl group through a bond ₃ Arranged
Characterized by forming a chemisorption film consisting of a monomolecular film
It Next, the second method for producing a water-repellent / antifouling building material of the present invention
Method has multiple chloro groups Silane compound
Contact the material surface or painted surface to cause an adsorption reaction to form the inner layer film.
And then -CF at the end of the alkyl group ₃ Group exists
The chemisorption molecule with a chlorosilyl group at the other end.
Contact the non-aqueous solution containing
Adsorption reaction and then washing with a non-aqueous solution.
At the end of the alkyl group via a siloxane bond
₃ Form a chemisorption film consisting of monolayers with groups arranged
It is characterized by

[0007]

According to the configuration of the first method of the present invention,
A -CF ₃ group is present at the end of the alkyl group, click on the other end
Construction of non-aqueous solution containing chemisorption molecule having lorosilyl group
Contact the base material surface or coated surface of the material to cause an adsorption reaction,
Then, by washing with a non-aqueous solution, the siloxane bond
-CF ₃ is arranged at the terminal of the alkyl group via
By forming a chemisorption film composed of a child film, the water repellency and antifouling property are excellent, and the characteristics such as mechanical strength of the base material can be utilized as they are, and an inexpensive building material can be obtained. That is, Al is the surface layer of the chemically adsorbed film
Because it is arranged to -CF ₃ at the end of kill groups, and is excellent in water repellency, antifouling property. In addition, since the base of the chemisorption film is formed by chemically bonding via a siloxane bond, it is possible to form a film having excellent durability, and even if the surface is repeatedly washed, the chemisorption film is formed into a base material. Does not easily peel from the material surface. Furthermore, since the chemical adsorption film of the present invention is an ultrathin film of nanometer to angstrom unit, it does not impair the characteristics such as mechanical strength of the substrate. Even if the base material is color-coated, the appearance of the coated surface is not impaired. The chemical adsorption film since a monomolecular film can be a thin film of uniform thickness, excellent transparency, it is not impairing the appearance of the substrate surface and painted surfaces.

Next, according to the configuration of the second method of the present invention.
For example, silane compounds with multiple chloro groups are used as building material base materials.
The inner layer film is formed by contacting the surface or painted surface and causing an adsorption reaction.
Form, followed by a -CF ₃ group is present at the end of the alkyl group,
Includes chemisorption molecule with chlorosilyl group at other end
The nonaqueous solution is brought into contact with the substrate surface or the coated surface of the building material intake
The reaction is then followed by washing with a non-aqueous solution.
-CF ₃ group is added to the end of the alkyl group via a roxane bond.
Forming a chemisorption film consisting of aligned monolayers
Allows for high-density silanol bonding on the surface of building materials.
Given possible, chemical absorption with a -CF ₃ group at the terminal of the alkyl group
The deposition film can be formed with higher density.

[0009]

EXAMPLES The present invention will be described more specifically below with reference to examples.
In the following examples, a plastic material, which is a typical example of a building material, is used for convenience of explanation. In the method for producing a water-repellent / antifouling building material of the present invention, the surface of the material or the coated surface
The monomolecular consisting film chemically adsorbed film in which are arranged a -CF ₃ at the end is formed by chemical bonds via a siloxane bond. That is, the ultra thin film containing fluorine is formed on the plastic surface. Therefore, the surface is unlikely to get dirty. Alternatively, it can be easily wiped off if it becomes dirty. Further, even if the surface is repeatedly washed, the chemical adsorption film does not peel off from the surface, and the water repellency and antifouling property are maintained.

As shown in FIG. 1, the building material obtained by the method of the present invention comprises a monomolecular film 3 containing a fluorinated alkyl group on the surface of a substrate 1 such as a plastic via a siloxane bond 2.
Is used. Examples of the plastic material include phenol resin, melamine resin, vinyl chloride resin, glass fiber-containing unsaturated polyester, and the like. Among building materials, wall material, door material, phenol resin,
Melamine resin is used. Polyvinyl chloride resin is used for flooring materials and toys, and unsaturated polyester containing glass fiber is used for the corrugated sheet of eaves. In addition, unsaturated polyester and PMMA resin mixed with glass fiber and marble powder are used in the bathtub.

The chemical adsorption film provided on the surface of the plastic material used in the building material article of the present invention is composed of a chlorosilane-based surfactant having a fluorinated alkyl group. Examples of the chlorosilane-based surfactant having a fluorinated alkyl group include CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl
₃ , CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ , CF
₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl
₃ , F (CF ₂ ) ₄ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (C
H ₂ ) ₉ SiCl ₃ , F (CF ₂ ) ₈ (CH ₂ ) ₂ Si
(CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ , CF ₃ COO
(CH ₂ ) ₁₅ SiCl ₃ , CF ₃ (CF ₂ ) ₅ (C
H _{2) 2} SiCl ₃ including trichlorosilane-based surface active agents such as, for example, _{CF 3 (CF 2) 7 (} C
_{H 2) 2 SiCl n (CH} 3) 3-n, CF 3 (CF 2)
_{7 (CH 2) 2 SiCl n} (C 2 H 5) 3-n, CF 3 C
_{H 2 O (CH 2) 15} SiCl n (CH 3) 3-n, CF 3
^{_{CH 2 O (CH 2) 15}} SiCl n (C 2 H 5) 3-n, C
F ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiC
l _n (CH ₃ ) _3-n , F (CF ₂ ) ₄ (CH ₂ ) ₂ Si
(CH ₃ ) ₂ (CH ₂ ) ₉ SiCl _n (C
₂ H ₅ ) _3-n , F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH
₃ ) ₂ (CH ₂ ) ₉ SiCl _n (CH ₃ ) _3-n , CF ₃
COO (CH ₂ ) ₁₅ SiCl _n (CH ₃ ) _3-n , CF _{3
(CF 2) 5 (CH 2} ) 2 SiCl n (CH 3)
Examples thereof include lower alkyl group-substituted monochlorosilane-based or dichlorosilane-based surfactants such as _3-n (where n is 1 or 2 in the formula). Among these, especially chlorosilyl bonds other than the chlorosilyl bond bonded to the hydrophilic group of the trichlorosilane-based surfactant form an intermolecular bond with the adjacent chlorosilane group and the siloxane bond, resulting in a stronger chemisorption film. Is preferred. Further, CF ₃ (CF ₂ ) _n CH ₂ CH ₂ SiCl ₃ (where n in the formula is an integer, and about 3 to 25 is the easiest to handle) has a solvent solubility, a chemical adsorption property, and water repellency and antifouling property. It is preferable because it is balanced with functionality such as sex. Furthermore,
If an ethylene group or an acetylene group is incorporated in the fluorinated alkyl chain portion, it can be crosslinked by electron beam irradiation of about 5 megarads after the formation of the chemisorption film, so that the hardness of the chemisorption film itself can be further improved.

The chlorosilane-based surfactant that can be used in the present invention is not only linear as described above, but also has a branched fluorinated alkyl group or hydrocarbon group, or has a fluorinated alkyl group at the terminal silicon. Group substituted with a group or a hydrocarbon group (that is, R, R ¹ , R ² and R ³ are substituted with a fluoroalkyl group or a hydrocarbon group and represented by the general formula R ₂ SiCl ₂ , R 3
₃ SiCl, R ¹ R ² SiCl ₂ or R ¹ R ² R ³
SiCl, etc.) may be used, but the linear form is generally preferable in order to increase the adsorption density. In addition, a chloro group
A silane compound that has several silane compounds is used as a building material base material surface or painted surface
It is also possible to form an inner layer film by contacting with
It For example, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl
₂ , Cl- (SiCl ₂ O) _n -SiCl ₃ (where n is a natural number), SiCl _m (CH ₃ ) _4-m , SiCl _m
(C ₂ H ₅ ) _4-m (where m is an integer from 1 to 3), HS
iCl _l (CH ₃ ) _3-l , HSiCl _l (C ₂ H ₅ )
After chemically adsorbing a substance containing a plurality of chlorosilyl bonds such as _3-l (where l is 1 or 2), etc., when it reacts with water, the chlorosilyl bond on the surface changes to a hydrophilic silanol bond and plastic The surface of the molded product becomes hydrophilic.

Among these substances containing a plurality of chlorosilyl groups, tetrachlorosilane (SiCl ₄ ) is preferable since it has a high reactivity and a small molecular weight and can give a silanol bond at a higher density. By making the substrate hydrophilic in this way, the hydrophilicity can be made higher than that of the oxidation treatment of the substrate containing the polymer. For example, a chlorosilane-based surfactant containing a fluorinated alkyl group can be chemically adsorbed thereon, and the chemisorption film thus obtained has a higher density, so that the functions such as water repellency and antifouling property are further enhanced. To be

In the method of the present invention, an alkyl group is attached to the surface of a plastic material used for a building material through a siloxane bond.
How to end forming a chemical adsorption film composed of a monomolecular film in which are arranged a -CF ₃ group, the steps of the hydrophilic by oxidizing the plastic article surface, the oxidation-treated surface of the non-aqueous organic The method includes a step of immersing in a solvent to chemically adsorb a chlorosilane-based surfactant on the surface to form a chemisorption film containing a fluorinated alkyl group through a siloxane bond.

As a method for oxidizing the plastic material, a usual method such as oxygen plasma treatment, corona treatment, or dipping in a mixed solution of concentrated sulfuric acid and potassium dichromate (chromium mixed acid solution treatment) is applied. . The non-aqueous solvent used in the method for producing the polymer composition of the present invention may be an organic solvent that does not dissolve the plastic material forming the chemisorption film and does not have active hydrogen that reacts with the chlorosilane-based surfactant. . For example, 1,1-
Dichloro, 1-fluoroethane, 1,1-dichloro,
2,2,2 -trifluoroethane, 1,1-dichloro,
2,2,3,3,3-pentafluoropropane, 1,3
A fluorine-based solvent such as dichloro, 1,1,2,2,3-heptafluoropropane, a hydrocarbon-based solvent such as hexane, octane, hexadecane or cyclohexane, an ether-based solvent such as dibutyl ether or dibenzyl ether, For example, any of ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and amyl acetate is preferable.

Further, the chemical adsorption film formed on the surface of the plastic material used for the building material of the present invention can sufficiently exhibit its function even if only one monomolecular chemical adsorption film is formed. To form a single molecule chemisorption film, it is sufficient to chemically adsorb a chlorosilane-based surfactant or a substance containing a plurality of chlorosilyl groups, and then wash it with a non-aqueous solvent without contacting with water. It can be done easily without any steps. Further, it goes without saying that the chemical adsorption film may be a monomolecular film accumulated. As described above, when the chemisorption film forms a cumulative film, the imparted functional groups are oriented and the density is improved, so that the chemical adsorption film can exhibit higher functions.

The present invention will be described below with reference to specific examples. Example 1 A wall material using a phenol resin was subjected to oxygen plasma treatment for 10 minutes in a UV dry stripper (oxygen flow rate: 1
(l / min) After the surface is oxidized, it is immersed in a 10 ^-2 mol / l cyclohexane solution of heptadecafluorodecyltrichlorosilane for 60 minutes at room temperature under a nitrogen atmosphere, and then unreacted heptadecafluorodecyltrichlorosilane is removed. It was washed with cyclohexane and then with pure water to form a chemisorption monomolecular film via a siloxane bond containing a fluoroalkyl group on the surface of the phenol resin.

Example 2 The same experiment as in Example 1 was carried out by replacing the wall material using the phenol resin of Example 1 with the door material using the melamine resin and replacing cyclohexane with 1,1-dichloro, 1-fluoroethane. did. Example 3 The wall material using the phenol resin of Example 1 was replaced with a floor material using polyvinyl chloride, and after oxygen plasma treatment, a 1 wt% tetrachlorosilane solution (solvent: 1,1-dichloro, 1- 6) at room temperature under a nitrogen atmosphere
Immerse for 0 minutes, then wash the unreacted tetrachlorosilane with 1,1-dichloro, 1-fluoroethane,
After that, the sample was washed with pure water and dried, and cyclohexane was replaced with 1,1-dichloro, 1-fluoroethane, and the same experiment as in Example 1 was performed.

The building materials of Examples 1 to 3 were used for 30 days in a state where they were normally used. As a comparative example, a building material without a chemical adsorption film was used. After 30 days, the soil conditions of both were compared. The building material of the comparative example was extremely dirty. Also, to remove dirt, it was necessary to wipe it off with a cloth containing detergent. On the other hand, the building material of the present invention showed almost no stain. Moreover, even a little dirt could be easily removed by wiping with a cloth containing water.

As is clear from the above, in the building materials of Comparative Examples, the antifouling property was remarkably reduced after 30 days of use, but in the building materials obtained by the method of the present invention, the characteristics were not changed. . As is clear from the above Examples and Comparative Examples, it was confirmed that the building materials obtained by the method of the present invention are excellent in water repellency and antifouling property. It was also confirmed that when used for roofing materials and outer wall materials, it is durable even when exposed to acid rain, and when used for roofs in snowy countries, it is easy to drop snow.

[0021]

As described above, the product obtained by the production method of the present invention
That building materials, monolayers are arranged a -CF ₃ at the end of the alkyl group via a siloxane bond to the substrate surface or painted surfaces
Since the chemical adsorption film made of is provided, the water repellency and antifouling property are excellent, the characteristics such as mechanical strength of the base material can be utilized as they are, and an inexpensive building material can be obtained. The chemical adsorption film since a monomolecular film can be a thin film of uniform thickness, excellent transparency, it is not impairing the appearance of the substrate surface and painted surfaces.

Next, according to the second method of the present invention,
A silane compound having a plurality of loro groups is applied to the surface of a building material substrate.
Or contact the coated surface to cause an adsorption reaction to form an inner layer film,
Then a -CF ₃ group is present at the end of the alkyl group, the end of the other
Water-insoluble containing chemisorbed molecules with chlorosilyl groups at the ends
Adsorption reaction by bringing the liquid into contact with the base material surface or the painted surface of building materials
And then washed with a non-aqueous solution.
-CF ₃ group is arranged at the end of the alkyl group through a silane bond.
By forming a chemisorption film consisting of
By applying high density silanol bonds to the surface of the base material of building materials
It can, chemically adsorbed film with a -CF ₃ group at the terminal of the alkyl group
Can be formed with higher density.

[Brief description of drawings]

FIG. 1 is a conceptual cross-sectional view in which the surface of a plastic material used for a building material obtained by the method of the present invention is enlarged to a molecular level.

[Explanation of symbols]

 1 Building material base material 2 Siloxane bond 3 Chemisorption film

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area E04F 13/18 A 9127-2E

Claims (2)

[Claims] 1. A method of manufacturing a building material, which comprises an alkyl group
-CF ₃ group is present at the terminal and chlorosilyl group at the other terminal
Of non-aqueous solution containing chemisorbed molecules with
Or contact with the painted surface to cause adsorption reaction, and then water-insoluble
By washing with liquid, the siloxane bond
Consisting monolayers are arranged a -CF ₃ at the end of kill groups
Water-repellent and antifouling construction characterized by forming a chemisorption film
Method of manufacturing wood. 2. A method of manufacturing a building material, which comprises adding a chloro group
A silane compound that has several silane compounds is used as a building material base material surface or painted surface
To form an inner layer film by adsorbing and reacting with
A -CF ₃ group is present at the end of kill, chloro other end
Building materials containing non-aqueous solutions containing chemisorbed molecules with silyl groups
Contact the substrate surface or painted surface to cause an adsorption reaction, then
By washing with a non-aqueous solution at
Single molecules are arranged a -CF ₃ group at the terminal of the alkyl group and
Water repellent characterized by forming a chemisorption film composed of a film
-Method of manufacturing antifouling building materials.