JPH089510B2 - Antifouling ceramic product and manufacturing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a ceramic product (made of ceramics,
Products made of glass, ceramics or enamel)
The present invention relates to an antifouling ceramic product having an antifouling coating formed on the surface of.

[0002]

2. Description of the Related Art The surface of ceramic products is treated to prevent stains.
These characteristics are required in various fields including the ceramic product industry in order to keep the ceramic products clean and maintain high hygiene and aesthetics.

Conventionally, in order to prevent stains on ceramic products, there has been no method other than smoothing the surface as much as possible or coating the surface with a fluorine resin or the like. In this case, the fluorine resin was thinly applied fluorine enamel, hand stage is taken you baking finish. In addition to its other resin
As a method of applying, a method of applying a coating material dissolved or suspended in a solvent and drying the solvent, baking and curing, or the like is adopted.

[0004]

However, in the method of applying the fluororesin described above, the adhesion to the surface of the ceramic product is poor and a highly durable product cannot be obtained. There is also a problem that the thickness of the coating film cannot be reduced. In addition, the adhesion strength is weak similarly in the method of applying another resin,
There was a problem that there was a problem in durability. This is because the adhesive force with the ceramic product base material is due to physical adsorption.

In order to solve the above-mentioned problems of the prior art, the present invention chemically bonds an antifouling coating composed of a monomolecular film and a ceramic product base material to obtain an adhesive film having an extremely thin film. It provides high-performance ceramic products with high anti-fouling effect, which is highly resistant to dirt and can be easily removed even if it adheres.

[0006]

Means for Solving the Problems] To achieve the above object, antifouling ceramic product of the present invention is a ceramic product coating <br/> is formed on the surface of the ceramic product, said coating characterized in that it is formed by a chemical bond and is a substrate surface a chemically adsorbed monomolecular film containing fluorine.

In the above structure, it is preferable that the chemisorption monomolecular film containing fluorine is formed at least via the siloxane monomolecular film.

In the above construction, the ceramic product may be a ceramic product, a glass product, a ceramic product or an enamel product.

[0009] The first method of the present invention, after washing prepared ceramic products, Kurorushi Lil group (SiCl _n X at one end
_3-n group, n = 1, 2, 3, X is a functional group) and the other end of the ceramic product in a non-aqueous organic solvent in which a chlorosilane-based surfactant having a fluorocarbon group is dissolved. The method is characterized by including a step of immersing and forming a chemisorption monomolecular film made of the activator over the entire surface of the ceramic product.

The second method of the present invention is to prepare a ceramic product, wash it , and then mix a silyl compound containing a plurality of chloro groups.
The combined hydroxyl group on the surface of the ceramic product and the chloro group of the compound are subjected to dehydrochlorination reaction by contact with the combined non-aqueous solvent to form the compound.
A step of precipitating a substance on the surface of the ceramic product, and washing and removing the unreacted silyl compound remaining on the ceramic product using a non-aqueous organic solvent , and then reacting with water to form a residue on the ceramic product. forming a monomolecular film made of material containing a plurality of silanol groups, to one end black Roshiriru group (SiCl _n X _3-n
Group, n = 1, 2, 3, and X is a functional group), and a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end is chemically adsorbed on the ceramic product to accumulate a monomolecular adsorption film. And a step of performing.

[0011] Before SL in the structure of the second method, SiCl ₄ or Si as a substance comprising a plurality of chlorosilyl groups
HCl ₃ , SiH ₂ Cl ₂ , Cl- (SiCl ₂ O) _n
It is preferable to use —SiCl ₃ (n is an integer).

[0012] In the above configuration of the first or second method, CF ₃ to the other end has a black Roshiriru group at one end as a chlorosilane-based surface active agent containing a linear fluorocarbon group
_{- (CF 2) n -R-} SiX p Cl 3-p (n is 0 or an integer, R represents an alkyl group, an ethylene group, an acetylene group, S
It is not necessary to represent i or a substituent containing an oxygen atom, X is preferably a substituent such as H or an alkyl group, and p is preferably 0 or 1 or 2).

[0013]

According to the constitution of the antifouling ceramic product of the present invention,
An extremely thin nanometer (nm) level fluorocarbon monolayer is chemically bonded to the surface of the ceramic product base material, resulting in high adhesion strength and no dirt or easy adhesion. A high-performance ceramic product with a high antifouling effect that can be removed.

Further, the method of the present invention can produce the coating film reasonably efficiently.

[0015]

Examples: Ceramic products of the present invention, such as ceramics, glass, ceramics, and ceramics containing enamels, include sanitary ware (eg, gold concealed, toilet bowl, washbasin, etc.), tableware (eg, bowl, plate, bowl, teacup) , Cups, bottles, coffee brewing containers, pots, mortars, cups, etc.), vases (basins, flowerpots, vase etc.), aquariums (culture tanks, water tanks for appreciation), chemical laboratory equipment (beakers, reaction vessels, tests) Tube, flask, petri dish, cooling tube, stirring rod, stirrer, mortar, vat, syringe), roof tile, tile, enamel tableware,
The present invention relates to high-performance ceramic products with high antifouling effect, which are represented by enamel washbasins and enamel pots.

[0016] A general ceramic product is a mixture of oxides.
It has a hydroxyl group on its surface. Therefore, one end <br/> black Roshiriru group (SiCl _n X _3-n group, n = 1, 2,
3, X is the molecular, for example, chlorosilane-based surface active agent into contact with the non-aqueous solvent obtained by mixing in the ceramic product surface hydroxyl groups containing a fluorocarbon group and Kuroroshi Lil groups containing straight chain having a functional group) And a chlorosilyl group of a substance containing a plurality of chlorosilyl groups are reacted to deposit a monolayer of the substance on the surface of the ceramic product, or contact with a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups. a step of depositing said material by reacting a chlorosilyl groups of matter comprising a plurality of hydroxyl groups and the chlorosilyl groups of the ceramic product surface on the ceramic product surface, unreacted remaining on the ceramic product surface using a non-aqueous organic solvent extra material was washed away, including a plurality of chlorosilyl groups, a siloxane-based monomolecular consisting material containing a plurality of chlorosilyl groups on the ceramic product Forming a next similar to the above
Proof of the the steps of a silane-based surfactant comprising linear carbon chains having black Roshiriru group at one end and chemisorbed on ceramic products accumulating monomolecular adsorption film by methods ceramic product surface
It can produce fouling properties of fluorocarbon chemisorption single component child film.

In the present invention, since the fluorocarbon-based monomolecular film having an extremely thin nanometer level film thickness is formed on the surface of the ceramic product, the original luster of the ceramic product is not impaired. In addition, this film is a fluorocarbon-based monomolecular film that is also excellent in water and oil repellency, and can enhance the antifouling effect on the surface. Therefore, a high-performance ceramic product having a high antifouling effect can be provided.

As a ceramic product related to the present invention, a toilet bowl, a bowl, and a enamel container will be described in order, as typical examples of ceramics.

[0019] Example 1 First, a finished toilet or bowl baking (hereinafter referred to as ceramic), washed with an organic solvent, nonaqueous solvent mixed with material containing a fluorocarbon group and Kuroroshi Lil group,
For example, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ is used, and 80% n-hexadecane (toluene, xylene, dicyclohexyl) dissolved at a concentration of about 1% by weight (hereinafter, % by weight is simply abbreviated as%) is also used. Good), 12% carbon tetrachloride, 8% chloroform solution was prepared, and when the ceramic was immersed for about 2 hours, a natural oxide film was formed on the surface of (Al ₂ O ₃ ceramic ceramic). since the oxide film surface contains many hydroxyl groups, and the hydroxyl group react with SiCl groups of substances containing a fluorocarbon group and Kuroroshi Lil groups arising it is dehydrochlorination reaction. Then the non-aqueous
Unreacted surfactant with organic solvent such as chloroform
If removed by washing, CF ₃ (CF
₂ ) ₇ (CH ₂ ) ₂ Si (O) ₃ − bond is generated,
As shown in FIG. 1, the monomolecular film 2 containing fluorine could be formed with a film thickness of about 15 angstroms in a state of being chemically bonded to the surface of the ceramic. Since the monomolecular film was extremely strongly chemically bonded, it never peeled off.

An attempt was made to actually use this toilet bowl, but it was possible to significantly reduce the adhesion of dirt compared to the untreated toilet bowl, and even if it did, it could be easily cleaned by rubbing it with a cleaning brush. At this time, no scratches were formed. In addition, in the case of a bowl, the oil and fat and the rice grains could be removed only by washing with water. Also, little tea astringent was attached.

[0021] Example 2 a small percentage ceramics {glassware containing hydroxyl groups albeit at hydrophilic or Al and Cu, <br/> may be metallic such as stainless steel. }, A silyl compound containing a plurality of chloro groups (eg, SiCl ₄ , or SiHCl ₃ , SiH _{2
Cl 2, Cl- (SiCl 2 O} ) n -SiCl 3 (n is an integer). In particular, if SiCl ₄ is used, it has a small molecule and a large activity on hydroxyl groups, so it has a great effect of uniformly hydrophilizing the surface of the ceramics).
After soaking for about a minute, the surface 11 of the ceramic is hydrophilic OH.
Since there are some groups 12 (FIG. 2), a dehydrochlorination reaction occurs on the surface and a chlorosilane monomolecular film of a silyl compound containing a plurality of chloro groups is formed.

For example, a silyl compound containing a plurality of chloro groups
If SiCl ₄ is used as a substance , since a small amount of hydrophilic OH groups are exposed on the surface of the ceramics 11, a dehydrochlorination reaction occurs on the surface, and Si (Cl) ₃ O− or —OSi (C
l) Molecules, such as ₂ O-, are immobilized on the surface via -SiO- bonds.

After that, when washed with a non-aqueous solvent such as chloroform and further washed with water, SiCl ₄ molecules which have not reacted with the ceramics are removed, and Si on the surface of the ceramics is removed.
A siloxane monomolecular film 13 of (OH) ₃ O- or -OSi (OH) ₂ O- is obtained (Fig. 3).

Since the monomolecular film 13 formed at this time is completely bonded to the surface of the vessel through a chemical bond of -SiO-, it is never peeled off. The obtained monomolecular film has many SiOH bonds on the surface. About three times as many as the initial hydroxyl groups are generated.

[0025] Thus addition, the non-aqueous solvent obtained by mixing a substance containing the same fluorinated carbon groups and Kuroroshi Lil groups as in Example 1, for _{example, CF 3 (CF 2) 7} (CH 2) 2 SiCl
80% n-hexadecane, 12% carbon tetrachloride, 8% chloroform solution dissolved at a concentration of about 1% was prepared using ₃ , and a ceramic having a monomolecular film having many SiOH bonds on the surface was prepared as 1 After soaking for about an hour, on the substrate surface
Dehydrochlorination reaction occurs. Then, a non-aqueous organic solvent, such as
For example, wash off unreacted surfactant with chloroform.
And CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si on the ceramic surface
Monolayer 1 containing (O-) ₃ bond and containing fluorine
In the state where 4 is chemically bonded to the lower layer siloxane monomolecular film, a film thickness of about 20 Å is accumulated over the entire surface of the ceramic.
A product was formed (Fig. 4). The monomolecular film was not peeled at all even after the peeling test.

Furthermore, in the above embodiment, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S is used as the fluorocarbon surfactant.
Although iCl ₃ was used, by adding or incorporating an ethylene group or an acetylene group in the alkyl chain portion, it is possible to crosslink by electron beam irradiation of about 5 megarads after forming the monomolecular film, so that the hardness of the monomolecular film is further improved. It is also possible.

In addition to the above-mentioned fluorocarbon surfactants, CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiC is used.
l ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₁₅ SiCl ₃ , F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH
₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ , CF ₃ COO (C
H ₂ ) ₁₅ SiCl ₃ or the like can be used.

Example 3 An enamel container having a glassy surface baked on a metal was washed with an organic solvent, and then the same treatment as in Examples 1 and 2 was performed.
went. Monomolecular film 2 also containing fluorine as well at this time, its
About the surface and a state where chemically combined in respectively enamel 15-2
The film thickness was 0 angstrom. Further, this monomolecular film or the monomolecular accumulated film was extremely strongly chemically bonded and was not peeled off.

When this basin was used, an attempt was made to actually use it, but the adhesion of dirt could be greatly reduced compared to the case without treatment, and even if it did, it could be easily cleaned by rubbing it with a cleaning brush. . At this time, no scratches were formed. The oil and fat content could be removed only by washing with water.

[0030]

As described above, according to the present invention,
Since the antifouling fluorocarbon-based monomolecular film having an extremely thin nanometer level film thickness is formed on the surface of the ceramic product, the original luster of the ceramic product is not impaired. In addition, this film is a fluorocarbon-based monomolecular film that is also excellent in water and oil repellency, and can enhance the antifouling effect on the surface. Therefore, it is possible to provide a high-performance ceramic product having an extremely high antifouling effect. In addition, this also reduces the amount of detergent used conventionally and has a great effect of reducing environmental pollution.

[Brief description of drawings]

FIG. 1 is a conceptual cross-sectional view in which the surface of the ceramic of the present invention is enlarged to a molecular level.

FIG. 2 is a conceptual view showing an enlarged cross section of the surface of the ceramics of the present invention.

FIG. 3 is a conceptual diagram of an intermediate step of a cross-section in which the surface of the base material of the ceramic is enlarged to the molecular level for explaining the second embodiment of the present invention.

FIG. 4 is a conceptual cross-sectional process diagram in which the surface of the base material of the ceramics is enlarged to the molecular level for explaining the second embodiment of the present invention.

[Explanation of symbols]

 1,11 Ceramic substrate 2,14 Monolayer 12 Hydroxyl group 13 Siloxane monolayer

Claims (7)

[Claims] 1. A ceramic product in which a coating is formed on the surface of a ceramic product, the coating being a chemisorption monomolecular film containing fluorine, which is formed by a chemical bond on the surface of the base material. Antifouling ceramic products. 2. The antifouling ceramic product according to claim 1 , wherein the chemisorption monomolecular film containing fluorine is formed via at least a siloxane-based monomolecular film. 3. The antifouling ceramic product according to claim 1 or 2 , wherein the ceramic product is a product made of ceramics, glass, ceramics or enamel. 4. After providing a ceramic ware washing, click <br/> Rorushi drill group at one end (SiCl _n X _3-n group, n = 1, 2, 3,
X is immersing the ceramic product in an organic solvent non-aqueous dissolved chlorosilane-based surface active agent having a fluorocarbon group on the other end has a functional group), consisting of the surfactant chemically adsorbed monomolecular A method for producing an antifouling ceramic product, comprising the step of forming a film over the entire surface of the ceramic product. 5. A chloro group after preparing and cleaning a ceramic product.
And a chloro compound of the compound by contacting with a non-aqueous solvent mixed with a silyl compound containing a plurality of
A step of dehydrochlorinating with a group to deposit the compound on the surface of the ceramic product , and washing and removing an unreacted silyl compound remaining on the ceramic product using a non-aqueous organic solvent, followed by reaction with water , The process of forming a monolayer made of a substance containing multiple silanol groups on a ceramic product, and the black film at one end
Rosilyl group (SiCl _n X _3-n group, n = 1, 2, 3, X
Is a functional group) and the other end has a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end of which is chemically adsorbed on the ceramic product to accumulate a monomolecular adsorption film. Manufacturing method of dirty ceramic products. 6. The substance containing a plurality of chlorosilyl groups is SiCl ₄ , or SiHCl ₃ , SiH ₂ Cl ₂ , C.
The method for producing an antifouling ceramic product according to claim 5, wherein l- (SiCl ₂ O) _n -SiCl ₃ (n is an integer) is used. 7. CF ₃ in the other end has a black Roshiriru group at one end as a chlorosilane-based surface active agent containing a linear fluorocarbon group _{- (CF 2) n -R-} SiX p Cl 3-p ( n
Is 0 or an integer, R is an alkyl group, an ethylene group, an acetylene group, Si or a substituent containing an oxygen atom, but is not necessary, X is a substituent such as H or an alkyl group, and p is 0 or 1 or 2). The method for producing an antifouling ceramic product according to claim 4 or 5, which uses.