JP2005206455A - Stain-proof ceramic product and its producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ceramic water repellent, oil repellent and stain-proof product excellent in abrasion resistance, weather resistance and a water droplet releasing property at a ceramic product where water repellent, oil repellent and stain-proof functions are required and to provide its producing method hardly generating hydrochloric acid. <P>SOLUTION: When the ceramic product is produced, an alkoxysilane surfactant is used and then a water repellent, oil repellent and stain-proof film with high durability is formed by a dealcohlization reaction on the surface of the ceramic product. The film at the ceramic product involves at least one layer of composite films containing a substance whose main components are at least a fluorocarbon group, a hydrocarbon group and a silyl group and a substance whose main component is a siloxane group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a ceramic product having a highly durable water- and oil-repellent antifouling film formed on the surface thereof. Specifically, the present invention relates to ceramic products such as tableware, flower vases, sanitary ware, insulators, tiles, etc. that require water / oil / oil repellent functions.

It is already well known that a chemisorbed liquid consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular water-repellent chemisorbed film. (For example, refer to Patent Document 1).

The principle of production of a chemisorbed monolayer in such a solution is to form a monolayer using a dehydrochlorination reaction between active hydrogen such as hydroxyl groups on the substrate surface and chlorosilyl groups of chlorosilane-based adsorbents. It is in.
Japanese Patent Laid-Open No. 02-258032

However, since the conventional chemical adsorption film uses only a chemical bond between the adsorbent and the substrate surface, there is a problem that the wear resistance is poor. In addition, in the method using a chlorosilane-based surfactant, a large amount of hydrochloric acid is generated during film formation, so that the production has to be performed in an isolated place equipped with a special dehydrochlorination facility.

The present invention is a ceramic product such as tableware, flower vase, sanitary ware, insulators, tiles, etc. that require water / oil / oil repellent antifouling function, durability such as wear resistance and weather resistance, water droplet separation (also referred to as water slidability). ), To improve antifouling properties. In addition, when forming a water- and oil-repellent and antifouling film on ceramic products, without generating hydrochloric acid (or by generating only a small amount of hydrochloric acid), durability such as wear resistance and weather resistance, and water-dropping water-removability An object is to form a film having excellent antifouling properties (also referred to as water slidability). The ceramic products referred to in the present invention include ceramic products, glass products, ceramic products, or enamel products. Specifically, sanitary ceramics (for example, toilet bowls, washbasins, baths, etc.), tableware (for example, tea bowls, dishes, bowls, cups, bottles, coffee-boiled containers, pots, mortars, cups, etc.), vases ( Flowerpots, single-feeders, etc.), water tanks (aquaculture tanks, viewing tanks, etc.), chemical laboratory equipment (beakers, reaction vessels, test tubes, flasks, petri dishes, cooling tubes, stirring rods, stirrers, mortars, bats, syringes), Includes building materials (tiles, tiles, various concrete products), enamel products (tableware, washbasins, pans, kettles), ceramic top plates for electromagnetic cookers, etc.

In order to achieve the object, the antifouling ceramic product of the first invention is a ceramic product on which a highly durable water / oil repellent / antifouling coating is formed, wherein the water / oil repellent / antifouling coating is formed. The gist of the present invention is to include at least one composite film containing at least a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group.

According to the antifouling ceramic product of the first aspect of the present invention, it is possible to improve the defect that it is weak against abrasion of a conventional chemical adsorption film, and to provide a coating excellent in wear resistance, durability such as weather resistance, and water separation Can provide antifouling ceramic products. At this time, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group is converted into the silica film and / or the silica film and / or the silica film composed of the substance mainly composed of a siloxane group via the silyl group. Bonding and fixing to the ceramic product surface is convenient for improving durability.

Furthermore, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group are bonded to each other or individually to the ceramic product surface via the silyl group and the siloxane group, respectively. If fixed, it is convenient for greatly improving the durability. Further, the molecular composition ratio of the substance mainly containing a fluorocarbon group, a hydrocarbon group and a silyl group and the substance mainly containing a siloxane group contained in the composite film is 1:10 to 10: 1, more preferably When it is set to 1: 3 to 5: 1, it is convenient for greatly improving the durability.

  Further, controlling the contact angle of the composite membrane with water to 95 ± 10 degrees is advantageous in improving water separation.

Furthermore, it is convenient to increase durability when the underlying ceramic product is a ceramic product having an alkali barrier film formed on the surface.

In order to achieve the above object, the antifouling ceramic product of the second invention is a ceramic product on which a highly durable water / oil repellent antifouling coating is formed, and the coating is at least a fluorocarbon Lower layer composite film containing a substance mainly composed of a group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group, and an upper layer containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group The gist is to have a two-layer structure with the film.

According to the antifouling ceramic product of the second invention described above, the initial water droplet contact angle of the ceramic product of the first invention can be made larger, and the durability performance is further improved as compared with the ceramic product of the first invention. Providing improved antifouling ceramic products.

  At this time, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group constituting the lower layer composite film passes through the silyl group in a silica film composed of a substance mainly composed of a siloxane group. A substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, which is bonded and fixed to the surface of the silica film and / or ceramic product and constitutes the upper layer film, is contained in the lower layer composite film via the silyl group. Bonding and fixing to the siloxane group is advantageous in improving durability.

  In addition, the fluorocarbon group, the hydrocarbon group, and the silyl group as a main component and the siloxane group as a main component constituting the lower layer composite film may be mutually or individually via a silyl group and a siloxane group, respectively. A substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group constituting the upper layer film is bonded to and fixed on the surface of the ceramic product, or on the surface of the ceramic product formed with an alkali barrier film individually or individually. Bonding and fixing to the siloxane group contained in the lower composite film via a group is more convenient for improving durability.

  Furthermore, the molecular composition ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and the substance mainly composed of a siloxane group contained in the lower layer composite film is preferably 1:10 to 10: 1. When the ratio is set to 1: 3 to 5: 1, it is convenient for greatly improving the durability.

  Further, it is convenient to improve the formation density of the upper layer film by controlling the contact angle of the base composite film with water to 95 ± 10 degrees.

  Furthermore, controlling the contact angle of the upper layer film with water to be 105 ± 10 degrees is advantageous in improving the durability.

Furthermore, it is preferable that the base ceramic product is a ceramic product such as tableware, flower vases, sanitary ware, insulators, tiles, ceramic top plates for electromagnetic cookers, etc., in order to impart an antifouling function. In particular, in the case of an electric insulator, it is convenient because it is possible to prevent electric leakage on the surface. Further, in the case of a ceramic top plate for an electromagnetic cooker, when the antifouling film of the present invention is formed after a plurality of fine protrusions (about 0.5 to 2 mm) are provided on the surface in advance, Since it does not directly contact the bottom of the pan, it is convenient for improving durability.

According to a third aspect of the present invention, there is provided a method for producing an antifouling ceramic product, wherein a substance containing a fluorocarbon group, a hydrocarbon group and a chlorosilyl group as a main component and a substance containing a chlorosilyl group as a main component are non-aqueous in a dry atmosphere. A step of bringing a composite film-forming solution prepared by mixing and diluting an organic solvent into contact with the surface of a ceramic product to react to form a coating, and a step of firing the ceramic product with the coating formed in an atmosphere substantially free of oxygen And including at least.

According to the method for producing an antifouling ceramic product of the third aspect of the invention, it is possible to improve the defect of being weak against abrasion of a conventional chemical adsorption film, and to have excellent durability and water separation (the falling angle with respect to water is extremely high). It is possible to provide a method for producing an antifouling ceramic product having a low coating.

At this time, as an atmosphere that does not substantially contain oxygen, using nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit and firing at 300 to 450 ° C., the film does not oxidize and wear resistance. Convenient for improving

Further, the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and the substance mainly composed of the chlorosilyl group is 1:10 to 10: 1 (more preferably 1: 1 to 1). 6: 1) is advantageous because it is possible to produce an antifouling ceramic product having excellent durability and water separation.

Furthermore, it is convenient that the ceramic surface is not damaged, if the ceramic product is stood or hung in the standing state, or is fired while holding the film forming surface up.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and the chlorosilyl group is a main component. As a substance, SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si instead of a substance mainly composed of a chlorosilyl group (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ or (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is 1: 1 to 6 : 1 for high durability and high water separation It is convenient in terms of retention.

Furthermore, if a ceramic product having an alkali barrier film formed on the surface is used as the underlying ceramic product, it is advantageous in increasing durability.

According to a fourth aspect of the present invention, there is provided a method for producing an antifouling ceramic product, wherein a substance containing a fluorocarbon group, a hydrocarbon group and a chlorosilyl group as a main component and a substance containing a chlorosilyl group as a main component are non-aqueous in a dry atmosphere. A step of bringing a composite film-forming solution prepared by mixing and diluting with an organic solvent into contact with the surface of the ceramic product and reacting to form a coating; and a step of removing or wiping off the excess solution on the surface of the ceramic product using an organic solvent And at least a step of firing in an atmosphere substantially free of oxygen.

According to the manufacturing method of the antifouling ceramic product of the fourth invention described above, it is possible to improve the drawback of being weak against abrasion of the conventional chemical adsorption film, durability such as wear resistance and weather resistance, and water separation It is possible to provide a method for producing an antifouling ceramic product having an excellent coating (high sliding property, that is, a very low water drop falling angle).

At this time, as an atmosphere substantially free of oxygen, using nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit and firing at 300 to 450 ° C. (more preferably 400 ± 20 ° C.), This is convenient for improving the wear resistance of the coating.

Further, the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and the substance mainly composed of the chlorosilyl group is 1:10 to 10: 1 (more preferably 1: 1 to 1). If it is set to 6: 1), an antifouling ceramic product having excellent durability and water separation can be produced, which is convenient.

Furthermore, it is convenient that the ceramic product is not damaged during firing, if the ceramic product is raised, suspended in a standing state, or held and fired with the film-forming surface facing up.

Furthermore, using a method of washing with a detergent and water instead of washing with an organic solvent is advantageous in that it can reduce environmental pollution in terms of waste liquid treatment.

Further, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and a substance mainly composed of a chlorosilyl group. As SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si ( OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is 1: 1 to 6: 1. To ensure high durability and high water separation. Convenient.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the underlying ceramic product, it is advantageous in increasing the durability of the water / oil repellent / antifouling film.

According to a fifth aspect of the present invention, there is provided a method for producing a ceramic product comprising a non-aqueous organic solvent containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group in a dry atmosphere. The lower layer composite film forming solution prepared by mixing and diluting is brought into contact with the ceramic product surface and reacted to form the lower layer composite film, and the main components are fluorocarbon groups, hydrocarbon groups and chlorosilyl groups in a dry atmosphere. A step of mixing and diluting a substance with a non-aqueous organic solvent to create an upper layer film forming solution, and a step of bringing the upper layer film forming solution into contact with the surface of the ceramic product on which the lower layer composite film is formed and reacting to form an upper layer film And at least a step of firing the ceramic product formed with the lower composite film and the upper film in an atmosphere substantially free of oxygen.

  According to the method for manufacturing a ceramic product of the fifth aspect of the invention, the antifouling ceramic product in which a film having a higher wear resistance and weather resistance is formed than the method of manufacturing the ceramic product of the second aspect of the invention. Can be provided.

  At this time, if the atmosphere is substantially oxygen-free and nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit is used and firing is performed at 300 to 450 ° C., durability is improved without oxidizing the coating. Convenient for improvement.

  Further, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group to the substance mainly composed of chlorosilyl group is 1:10 to 10: 1, more preferably 1: 3. When it is set to ˜5: 1, it is convenient to produce a water and oil repellent antifouling ceramic product excellent in wear resistance and weather resistance.

Furthermore, it is convenient to raise or suspend ceramic products during firing, or to hold and fire with the film forming surface facing upward, since there is little risk of damaging the surface of the film.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and the chlorosilyl group is a main component. As a substance, SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si instead of a substance mainly composed of a chlorosilyl group (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is from 1: 3 to 5: If it is set to 1, it is necessary to secure high durability. Good.

Furthermore, if a ceramic product having an alkali barrier film formed on the surface is used as the underlying ceramic product, it is advantageous in increasing durability.

According to a sixth aspect of the present invention, there is provided a method for producing a ceramic product comprising a non-aqueous organic solvent containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group in a dry atmosphere. The step of forming a lower layer composite film by contacting and reacting the composite film forming solution prepared by mixing and dilution with the surface of the ceramic product, and using an organic solvent for the excess solution on the surface of the ceramic product on which the lower layer composite film is formed An upper film forming solution prepared by mixing and diluting a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group in a dry atmosphere with a non-aqueous organic solvent in a dry atmosphere; The step of contacting and reacting with the ceramic product surface on which the composite film is formed to form an upper layer film, and the excess solution on the ceramic product surface on which the upper layer film is formed are removed by washing or wiping with an organic solvent. And that step, a step of firing in an atmosphere containing substantially no oxygen and summarized in that at least include.

  According to the method for manufacturing a ceramic product of the sixth aspect of the invention, compared with the method for manufacturing a ceramic product of the third aspect of the invention, a method for manufacturing an antifouling ceramic product superior in wear resistance and weather resistance is provided. Can be provided.

  At this time, if the atmosphere is substantially free of oxygen, using nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit and firing at 300 to 450 ° C., the wear resistance and weather resistance of the coating are improved. Convenient for improvement.

  Further, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group to the substance mainly composed of chlorosilyl group is 1:10 to 10: 1, more preferably 1: 3 to 3. If it is set to 5: 1, a water and oil repellent antifouling ceramic product excellent in abrasion resistance and weather resistance can be produced, which is convenient.

Furthermore, it is convenient to raise or suspend ceramic products during firing, or to hold and fire with the film forming surface facing upward, since there is little risk of damaging the surface of the film.

In addition, using a method of washing with a detergent and water instead of washing with an organic solvent is advantageous because it can reduce environmental pollution in terms of waste liquid treatment.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and the chlorosilyl group is a main component. As a substance, SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si instead of a substance mainly composed of a chlorosilyl group (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is from 1: 3 to 5: If it is set to 1, it is necessary to secure high durability. Good.

Furthermore, if a ceramic product having an alkali barrier film formed on the surface is used as the underlying ceramic product, it is advantageous in increasing durability.

According to a seventh aspect of the present invention, there is provided a method for producing a ceramic product, wherein at least the surface of the ceramic product has a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as a main component, a substance having an alkoxysilyl group as a main component, and a silanol condensation catalyst. Forming a film by contact reaction of a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent, and firing the ceramic product on which the film is formed in an atmosphere substantially free of oxygen It is made to include.

According to the method for producing a ceramic product of the seventh aspect of the invention, the conventional chemical adsorption film is weak against abrasion, and has excellent durability and water separation without generation of hydrochloric acid (water drop falling angle). Can provide a method for producing antifouling ceramic products.

At this time, it is convenient to wash with a detergent and water instead of washing with an organic solvent because environmental pollution can be reduced.

In addition, if an atmosphere containing substantially no oxygen is used as a nitrogen gas or a nitrogen gas containing hydrogen below the explosion limit, baking at 300 to 450 ° C. is advantageous in preventing oxidation of the film and improving the film strength. .

Furthermore, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group to the substance mainly composed of alkoxysilyl group is 1:10 to 10: 1, more preferably 1: When it is set to 3 to 5: 1, it is convenient for controlling water separation.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n − ( CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and the main component is an alkoxysilyl group. Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group) , Short chain alkyl groups such as propyl group), or substances having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is It is convenient to ensure high durability and high water separation when the molecular composition ratio during mixing is 1:10 to 10: 1.

In addition, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, it is convenient to increase durability.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst It is convenient that antifouling ceramic products can be produced in a shorter period of time than in the case of using.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 is used. The film formation time can be further shortened compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. Convenient.

According to an eighth aspect of the present invention, there is provided a method for producing a ceramic product comprising: a material comprising a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as a main component; a substance comprising an alkoxysilyl group as a main component; a silanol condensation catalyst; A step of forming a film by contact reaction of a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent, and removing or wiping off excess composite film forming solution on the ceramic product surface using an organic solvent The gist is to include a step and a step of firing in an atmosphere substantially free of oxygen.

According to the method for manufacturing a ceramic product of the eighth aspect of the invention, a method for manufacturing an antifouling ceramic product having higher gloss than the method of the second aspect of the invention can be provided.

At this time, it is convenient to wash with a detergent and water instead of washing with an organic solvent because environmental pollution can be reduced.

Further, it is convenient to improve the film strength by baking at 300 to 450 ° C. using nitrogen gas or nitrogen gas containing hydrogen below the explosion limit as an atmosphere substantially free of oxygen.

Furthermore, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group to the substance mainly composed of alkoxysilyl group is 1:10 to 10: 1, more preferably 1: When it is set to 3 to 5: 1, it is convenient for controlling the water separation.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n − ( CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and the main component is an alkoxysilyl group. Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group) , Short chain alkyl groups such as propyl group), or substances having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is It is convenient to ensure high durability and high water separation when the molecular composition ratio during mixing is 1:10 to 10: 1.

Moreover, it is convenient to increase the durability when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst It is convenient that antifouling ceramic products can be produced in a shorter period of time than in the case of using.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film formation time can be further shortened compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. Convenient.

In order to achieve the above object, a ceramic product manufacturing method according to a ninth aspect of the present invention has a ceramic product surface comprising a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components and an alkoxysilyl group as a main component. A step of forming a lower layer composite film by contact reaction of a composite film forming solution prepared by mixing and diluting a substance and a silanol condensation catalyst with a non-aqueous organic solvent, and a surface of the ceramic product on which the lower layer composite film is formed is fluorocarbon. Forming an upper film by contacting and reacting an upper film forming solution prepared by mixing and diluting a group mainly composed of a group, a hydrocarbon group and an alkoxysilyl group and a silanol condensation catalyst with a non-aqueous organic solvent; The gist is to include a step of firing the ceramic product on which the film and the upper layer film are formed in an atmosphere substantially free of oxygen.

  According to the method for manufacturing a ceramic product of the ninth invention, compared with the method for manufacturing a ceramic product of the seventh invention, there is provided a method for manufacturing an antifouling ceramic product having more wear resistance and weather resistance. Can be provided.

  At this time, instead of washing with an organic solvent, washing with a detergent and water is advantageous because it can reduce the burden on the environment.

Furthermore, when using nitrogen gas or nitrogen gas containing hydrogen below the explosion limit as an atmosphere substantially free of oxygen and firing at 300 to 450 ° C., the water and oil repellent and antifouling properties are excellent in abrasion resistance and weather resistance. It is convenient to be able to manufacture ceramic products.

  Further, the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and the substance mainly composed of the alkoxysilyl group is 1:10 to 10: 1, more preferably 1: When it is set to 3 to 5: 1, it is convenient to produce a water and oil repellent antifouling ceramic product excellent in wear resistance and weather resistance.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₂ Si (OA) ₂ , or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and a substance mainly composed of an alkoxysilyl group Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group, In place of a compound represented by a short-chain alkyl group such as a propyl group) or a substance mainly composed of an alkoxysilyl group, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (However, m is an integer. Using (number) is convenient in securing high durability.

  Even when only the step of forming the lower layer composite film is repeated a plurality of times and the upper layer film forming step is omitted, there is no practical problem in ensuring excellent water separation and high durability.

  Further, when the upper layer film forming step is performed after the step of forming the lower layer composite film is repeated a plurality of times, it is convenient to ensure excellent initial water repellency and high durability.

  Furthermore, when a ceramic product having an alkali barrier film formed on the surface in advance is used as the base ceramic product, it is convenient for ensuring weather resistance.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst It is convenient that antifouling ceramic products can be produced in a shorter period of time than in the case of using.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film formation time can be further shortened compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. Convenient.

According to a tenth aspect of the present invention, there is provided a method for producing a ceramic product comprising: a material having a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as a main component; a substance having an alkoxysilyl group as a main component; and a silanol condensation catalyst on the ceramic product surface. A step of forming a lower layer composite film by contact reaction of a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent, and an extra solution on the ceramic product surface on which the lower layer composite film is formed using an organic solvent A step of washing or wiping off, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and a silanol condensation catalyst on the surface of the ceramic product on which the lower layer composite film is formed with a non-aqueous organic solvent The upper layer film forming solution prepared by mixing and dilution is contact-reacted to form an upper layer film, and the excess solution on the ceramic product surface on which the upper layer film is formed is removed by washing with an organic solvent. A step of wiping removed, and summarized in that comprising the step of calcining in an atmosphere substantially free of oxygen ceramic products lower composite film and an upper film is formed.

  According to the method for manufacturing a ceramic product of the tenth aspect of the present invention, there is provided a method for manufacturing an antifouling ceramic product that is more excellent in wear resistance and weather resistance than the method of manufacturing the ceramic product of the eighth aspect. Can be provided.

  At this time, instead of washing with an organic solvent, washing with a detergent and water is advantageous because it can reduce the burden on the environment.

Further, when an atmosphere containing substantially no oxygen is used as a nitrogen gas or a nitrogen gas containing hydrogen below the explosive limit and baked at 300 to 450 ° C., the water and oil repellency is excellent in wear resistance and weather resistance on the coating surface. Convenient to manufacture antifouling ceramic products.

  In addition, when the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group and the substance mainly composed of the alkoxysilyl group is 1:10 to 10: 1, It is convenient to manufacture water and oil repellent antifouling ceramic products with excellent wear and weather resistance.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n − ( CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and the main component is an alkoxysilyl group. Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group) , Short chain alkyl groups such as propyl group), or substances having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is Use of (integer) is convenient for ensuring high durability.

  Even if only the step of forming the lower layer composite film is repeated a plurality of times and the upper layer film forming step is omitted, it is convenient for ensuring excellent water separation and high durability.

  In addition, when the upper layer film forming step is performed after repeating the step of forming the lower layer composite film a plurality of times, there is no problem in securing excellent water repellency and high durability.

  Furthermore, when a ceramic product having an alkali barrier film formed on the surface in advance is used as the base ceramic product, it is convenient for ensuring weather resistance.

  In addition, if ceramic products such as tableware, flower vases, sanitary ware, insulators, tiles, etc. are used as the base ceramic products, it is convenient for exerting the function of the water-repellent antifouling film.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst It is convenient that antifouling ceramic products can be produced in a shorter period of time than in the case of using.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film formation time can be further shortened compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. Convenient.

As described above, in the antifouling ceramic product of the present invention, the surface of the ceramic product has at least a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group (silica). ) Anti-fouling ceramic products such as tableware, flower vases, sanitary ware, insulators and tiles that have extremely high weather resistance and abrasion resistance and show high-performance water separation and antifouling properties. There is an effect that can provide.

Furthermore, in the case of insulators, there is an effect that it is possible to prevent deterioration of electrical insulation performance due to surface contamination, salt damage, or the like. Further, in the case of a ceramic top plate for an electromagnetic cooker, when the antifouling film of the present invention is formed after a plurality of fine protrusions (about 0.5 to 2 mm) are provided on the surface in advance, Is not directly in contact with the bottom of the pan, and has the effect of improving durability.

Further, in the water / oil repellent / antifouling ceramic product of the present invention, an alkoxysilane-based surfactant, a silanol condensation catalyst, and a non-aqueous organic solvent are used, and at least a fluorocarbon group and a hydrocarbon group are formed on the surface of the ceramic product. By forming an antifouling film comprising at least one composite film containing a silyl group-based material and a siloxane group-based material (silica), the weather resistance and wear resistance are extremely high, There is an effect that it is possible to manufacture and provide a water and oil repellent antifouling ceramic product exhibiting water separation characteristics of performance without generating hydrochloric acid at all.

The present invention provides ceramic products such as tableware, flower vases, sanitary ware, insulators, tiles, etc. that are highly durable and have high water separation (small water drop falling angle).

The antifouling ceramic product of the first invention is a ceramic product in which a highly durable water and oil repellent and antifouling coating is formed, and the water and oil repellent and antifouling coating is at least a fluorocarbon group. And a ceramic product in which at least one composite film containing a substance mainly composed of hydrocarbon group and silyl group and a substance mainly composed of siloxane group is formed.

In the antifouling ceramic product of the first invention, the conventional chemical adsorption film is weak against abrasion and forms a film having excellent wear resistance, durability such as weather resistance, and water separation. Can provide antifouling ceramic products. At this time, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group is converted into the silica film and / or the silica film and / or the silica film composed of the substance mainly composed of a siloxane group via the silyl group. By bonding and fixing to the ceramic product surface, there is an effect that the durability such as abrasion resistance and weather resistance of the coating can be greatly improved.

Furthermore, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group are bonded to each other or individually to the ceramic product surface via the silyl group and the siloxane group, respectively. If fixed, it is convenient for greatly improving the durability. Further, the molecular composition ratio of the substance mainly containing a fluorocarbon group, a hydrocarbon group and a silyl group and the substance mainly containing a siloxane group contained in the composite film is 1:10 to 10: 1, more preferably When it is set to 1: 3 to 5: 1, there is an effect that durability can be further improved.

  Further, when the contact angle of the composite film with respect to water is controlled to 95 ± 10 degrees, there is an effect that water separation such as water drop falling property can be improved while water droplet water repellency is maintained.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the underlying ceramic product, the weather resistance can be improved. On the other hand, in the case of a ceramic top plate for an electromagnetic cooker, if a plurality of fine protrusions (about 0.5 to 2 mm) are provided on the surface in advance, the coating does not directly contact the bottom of the pan. There exists an effect | action which can improve the durability of a dirty film.

The antifouling ceramic product of the second invention is a ceramic product on which a highly durable water and oil repellent and antifouling coating is formed, wherein the water and oil repellent and antifouling coating is at least carbon fluoride. Lower layer composite film containing a substance mainly composed of a group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group, and an upper layer containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group A ceramic product with a film.

According to the antifouling ceramic product of the second invention, the initial water droplet contact angle of the ceramic product of the first invention can be made larger, and the durability performance is further improved compared to the ceramic product of the first invention. There is an action that can be done.

  At this time, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group constituting the lower layer composite film is passed through the silyl group in a silica film composed of a substance mainly composed of a siloxane group. The lower layer composite film contains a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, which is bonded and fixed to the surface of the silica film and / or ceramic product and constitutes the upper layer film through the silyl group. When bonded and fixed to the siloxane group, the durability can be improved.

  In addition, the fluorocarbon group, the hydrocarbon group, and the silyl group as a main component and the siloxane group as a main component constituting the lower layer composite film may be mutually and / or individually via a silyl group and a siloxane group, respectively. Bonded and fixed to the ceramic product surface, and the substance mainly composed of fluorocarbon group, hydrocarbon group and silyl group constituting the upper layer film is bonded and fixed to the siloxane group contained in the lower layer composite film through the silyl group If this is done, the durability can be improved.

  Furthermore, the molecular composition ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and silyl group and the substance mainly composed of siloxane group contained in the lower layer composite film is preferably 1:10 to 10: 1. If 1: 3 to 5: 1, the durability can be greatly improved.

  Further, if the contact angle of the base composite film with respect to water is controlled to 95 ± 10 degrees, there is an effect that the formation density of the upper layer film can be improved.

  Furthermore, when the contact angle of the upper layer film with respect to water is controlled to be 105 ± 10 degrees, there is an effect that the initial water repellency and durability can be improved.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the weather resistance can be improved.

According to a third aspect of the present invention, there is provided a method for producing an antifouling ceramic product comprising a non-aqueous system comprising a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group in a dry atmosphere. A step of bringing a composite film-forming solution prepared by mixing and diluting an organic solvent into contact with the surface of a ceramic product to react to form a coating, and a step of firing the ceramic product with the coating formed in an atmosphere substantially free of oxygen And at least.

According to the method for producing an antifouling ceramic product of the third aspect of the present invention, the disadvantage of being weak against abrasion of a conventional chemical adsorption film is improved, and durability and water separation are excellent (the falling angle with respect to water is extremely low). ) It has the effect of being able to manufacture and provide antifouling ceramic products with coatings formed.

At this time, as an atmosphere that does not substantially contain oxygen, using nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit and firing at 300 to 450 ° C., the film does not oxidize and wear resistance. Has the effect of improving.

Further, the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and the substance mainly composed of the chlorosilyl group is 1:10 to 10: 1 (more preferably 1: 1 to 1). 6: 1) has an effect of improving the production of antifouling ceramic products having excellent durability and water separation.

Furthermore, when firing, when a ceramic product is stood or hung in an upright state or held and fired with the film-forming surface up, there is an effect that the film surface can be fired without damaging it.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and the chlorosilyl group is a main component. As a substance, SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si instead of a substance mainly composed of a chlorosilyl group (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is 1: 1 to 6: When set to 1, both high durability and high water separation are improved. Kill there is action.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

According to a fourth aspect of the present invention, there is provided a method for producing an antifouling ceramic product, wherein a substance containing a fluorocarbon group, a hydrocarbon group and a chlorosilyl group as a main component and a substance containing a chlorosilyl group as a main component are non-aqueous in a dry atmosphere. A step of bringing a composite film-forming solution prepared by mixing and diluting with an organic solvent into contact with the surface of the ceramic product and reacting to form a coating; and a step of removing or wiping off the excess solution on the surface of the ceramic product using an organic solvent And a step of firing in an atmosphere substantially free of oxygen.

In the method for producing an antifouling ceramic product according to the fourth aspect of the invention, the wear resistance and durability such as weather resistance, and water separation are excellent (the water sliding property is high, that is, the water drop falling angle is extremely low). It has the effect of producing antifouling ceramic products with a coating formed.

At this time, as an atmosphere substantially free of oxygen, using nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit and firing at 300 to 450 ° C. (more preferably 400 ± 20 ° C.), There exists an effect | action which can improve the abrasion resistance of a film significantly.

Further, the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and the substance mainly composed of the chlorosilyl group is 1:10 to 10: 1 (more preferably 1: 1 to 1). 6: 1) has the effect of producing an antifouling ceramic product having excellent durability and water separation.

Further, when firing, when a ceramic product is raised, suspended in a standing state, or held and fired with the film forming surface facing upward, there is an effect that the film can be fired without damaging the film.

Furthermore, using a method of washing with a detergent and water instead of washing with an organic solvent has the effect of reducing environmental pollution in terms of waste liquid treatment.

Further, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and a substance mainly composed of a chlorosilyl group. As SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si ( OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is 1: 1 to 6: 1. Can improve high durability and high water separation. There is a use.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

According to a fifth aspect of the present invention, there is provided a method for producing a ceramic product comprising a non-aqueous organic solvent containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group in a dry atmosphere. A process of forming a lower composite film by bringing the composite film forming solution prepared by mixing and dilution into contact with the ceramic product surface and reacting with it, and having a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group as main components in a dry atmosphere A step of mixing and diluting a substance with a non-aqueous organic solvent to create an upper layer film forming solution, and a step of bringing the upper layer film forming solution into contact with the surface of the ceramic product on which the lower layer composite film is formed and reacting to form an upper layer film And firing at least a ceramic product on which the lower composite film and the upper film are formed in an atmosphere substantially free of oxygen.

  If the method for producing a ceramic product according to the fifth invention is used, the antifouling ceramic product having a film having a more excellent wear resistance and weather resistance than the method for producing a ceramic product according to the third invention is formed. There is an effect that can be manufactured.

  At this time, if the atmosphere is substantially oxygen-free and nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit is used and firing is performed at 300 to 450 ° C., durability is improved without oxidizing the coating. There is an action that can be improved.

  Further, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group to the substance mainly composed of chlorosilyl group is 1:10 to 10: 1, more preferably 1: 3 to 3. If it is set to 5: 1, it has the effect | action which can manufacture the water-repellent | oil-repellent | oil-repellent antifouling ceramic products excellent in abrasion resistance and a weather resistance.

Further, when firing, when a ceramic product is raised, suspended in a standing state, or held and fired with the film forming surface facing upward, there is an effect that the film can be fired without damaging the film.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and the chlorosilyl group is a main component. As a substance, SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si instead of a substance mainly composed of a chlorosilyl group (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is from 1: 3 to 5: When set to 1, it can improve high durability. A.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

According to a sixth aspect of the present invention, there is provided a method for producing a ceramic product comprising a non-aqueous organic solvent containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group in a dry atmosphere. A step of forming a lower layer composite film by contacting and reacting the lower layer composite film forming solution prepared by mixing and dilution with the surface of the ceramic product, and using an organic solvent for the excess solution on the ceramic product surface on which the lower layer composite film is formed Cleaning and wiping and removing, and mixing and diluting a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group with a non-aqueous organic solvent in a dry atmosphere; A step of bringing the upper layer film-forming solution into contact with the surface of the ceramic product on which the lower layer composite film is formed and reacting to form an upper layer film; and an extra solvent on the surface of the ceramic product on which the upper layer film is formed using an organic solvent. for A step of washing off or wiping removed Te, and calcining in an atmosphere substantially free of oxygen and summarized in that at least include.

  According to the method for manufacturing a ceramic product of the sixth aspect of the present invention, the method for manufacturing an antifouling ceramic product that is more excellent in wear resistance and weather resistance than the method of manufacturing the ceramic product of the fourth aspect of the invention is provided. Can be provided.

  At this time, if the atmosphere is substantially free of oxygen, using nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit and firing at 300 to 450 ° C., the wear resistance and weather resistance of the coating are improved. There is an action that can be improved.

  Further, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group to the substance mainly composed of chlorosilyl group is 1:10 to 10: 1, more preferably 1: 3. When it is set to ˜5: 1, there is an effect of further improving the wear resistance and weather resistance.

Furthermore, when firing, when a ceramic product is set up, suspended, or held and fired with the film forming surface facing upward, there is an effect that the film surface can be fired without damaging it.

In addition, using a method of washing with a detergent and water instead of washing with an organic solvent has the effect of reducing environmental pollution in terms of waste liquid treatment.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, and the chlorosilyl group is a main component. As a substance, SiCl ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si instead of a substance mainly composed of a chlorosilyl group (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is from 1: 3 to 5: When set to 1, it can improve high durability. A.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

According to a seventh aspect of the present invention, there is provided a method for producing a ceramic product, wherein at least the surface of the ceramic product has a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as a main component, a substance having an alkoxysilyl group as a main component, and a silanol condensation catalyst. Forming a film by contact reaction of a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent, and firing the ceramic product on which the film is formed in an atmosphere substantially free of oxygen It is made to include.

According to the method for producing a ceramic product of the seventh aspect of the invention, the conventional chemical adsorption film is weak against abrasion, and has excellent durability and water separation without generation of hydrochloric acid (water drop falling angle). Can provide a method for producing antifouling ceramic products.

At this time, instead of washing with an organic solvent, washing with a detergent and water has the effect of reducing environmental pollution.

Further, when nitrogen gas containing nitrogen gas or hydrogen below the explosion limit is used as an atmosphere substantially free of oxygen and baking is performed at 300 to 450 ° C., it has an effect of preventing film oxidation and improving film strength.

Furthermore, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group to the substance mainly composed of alkoxysilyl group is 1:10 to 10: 1, more preferably 1: When it is set to 3 to 5: 1, there is an effect that water separation can be further improved.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n − ( CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and the main component is an alkoxysilyl group. Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group) , Short chain alkyl groups such as propyl group), or substances having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is When the molecular composition ratio at the time of mixing is 1:10 to 10: 1, the durability and water separation can be improved.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst Compared to the use of, antifouling ceramic products can be produced in a shorter time.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film-forming time can be further reduced compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. There is an effect.

According to an eighth aspect of the present invention, there is provided a method for producing a ceramic product comprising: a material comprising a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as a main component; a substance comprising an alkoxysilyl group as a main component; a silanol condensation catalyst; A step of forming a film by contact reaction of a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent, and removing or wiping off excess composite film forming solution on the ceramic product surface using an organic solvent And firing in an atmosphere substantially free of oxygen.

If the method for producing a ceramic product of the eighth invention is used, it is possible to produce and provide an antifouling ceramic product having superior surface gloss compared to the method of the seventh invention.

At this time, instead of washing with an organic solvent, washing with a detergent and water has the effect of reducing environmental pollution.

Further, when an atmosphere containing substantially no oxygen is used as a nitrogen gas or a nitrogen gas containing hydrogen below the explosion limit and baked at 300 to 450 ° C., the film strength can be improved.

Furthermore, the molecular mixing ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group to the substance mainly composed of alkoxysilyl group is 1:10 to 10: 1, more preferably 1: Setting 3 to 5: 1 has an effect of easily controlling water separation.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n − ( CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and the main component is an alkoxysilyl group. Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group) , Short chain alkyl groups such as propyl group), or substances having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is When the molecular composition ratio at the time of mixing is 1:10 to 10: 1, the durability and water separation can be improved at the same time.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst Compared to the use of, the antifouling ceramic product can be produced in a shorter time.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film-forming time can be further reduced compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. There is an effect.

According to a ninth aspect of the present invention, there is provided a ceramic product manufacturing method comprising: a material having a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as a main component; a substance having an alkoxysilyl group as a main component; and a silanol condensation catalyst on the ceramic product surface. A step of forming a lower layer composite film by contacting and reacting a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent to a ceramic product, and a fluorocarbon group and a hydrocarbon on the surface of the ceramic product on which the lower layer composite film is formed Forming an upper film by contacting and reacting an upper film forming solution prepared by mixing and diluting a group mainly composed of an alkoxysilyl group and a silanol condensation catalyst with a non-aqueous organic solvent, and a lower composite film and an upper film And a step of firing the ceramic product formed with an atmosphere substantially free of oxygen.

  According to the method for manufacturing a ceramic product of the ninth invention, it is possible to manufacture and provide an antifouling ceramic product that is more excellent in wear resistance and weather resistance than the method of manufacturing a ceramic product of the seventh invention. There is an effect.

  At this time, instead of washing with an organic solvent, washing with a detergent and water has an effect of reducing the burden on the environment.

Furthermore, when using nitrogen gas or nitrogen gas containing hydrogen below the explosion limit as an atmosphere substantially free of oxygen and firing at 300 to 450 ° C., the water and oil repellent and antifouling properties are excellent in abrasion resistance and weather resistance. It has the effect of producing ceramic products.

  Further, the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and the substance mainly composed of the alkoxysilyl group is 1:10 to 10: 1, more preferably 1: When it is set to 3 to 5: 1, there is an action capable of producing a water and oil repellent antifouling ceramic product excellent in wear resistance and weather resistance.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₂ Si (OA) ₂ , or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and a substance mainly composed of an alkoxysilyl group Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group, In place of a compound represented by a short-chain alkyl group such as a propyl group) or a substance mainly composed of an alkoxysilyl group, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (However, m is an integer. When the number is used, there is an effect that high durability can be improved.

  Even when only the step of forming the lower layer composite film is repeated a plurality of times and the upper layer film forming step is omitted, there is no practical problem in securing excellent water separation and high durability.

  Further, when the upper layer film forming step is performed after repeating the step of forming the lower layer composite film a plurality of times, there is an effect that the initial water repellency is excellent and the high durability can be improved.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst Compared to the use of, the antifouling ceramic product can be produced in a shorter time.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film-forming time can be further reduced compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. There is an effect.

According to a tenth aspect of the present invention, there is provided a method for producing a ceramic product comprising: a material having a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as a main component; a substance having an alkoxysilyl group as a main component; and a silanol condensation catalyst on the ceramic product surface. A step of forming a lower layer composite film by contacting and reacting a composite film forming solution prepared by mixing and diluting with a non-aqueous organic solvent on the surface of the ceramic product, and an extra solution on the surface of the ceramic product on which the lower layer composite film is formed. The step of washing or wiping off using a solvent, and the surface of the ceramic product on which the lower layer composite film is formed, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, and a silanol condensation catalyst are removed. Using an organic solvent, the step of forming an upper layer film by contact reaction of the upper layer film-forming solution prepared by mixing and diluting with an aqueous organic solvent, and an extra solvent on the ceramic product surface on which the upper layer film has been formed And a step of washing off or wiping off and the step of firing in an atmosphere containing substantially no oxygen ceramic products lower composite film and an upper film is formed.

  The method for producing a ceramic product according to the tenth aspect of the present invention has the effect of producing and providing an antifouling ceramic product having superior wear resistance and weather resistance as compared with the method for producing a ceramic product of the eighth aspect. is there. .

  At this time, instead of washing with an organic solvent, washing with a detergent and water has an effect of reducing the burden on the environment.

Further, when an atmosphere containing substantially no oxygen is used as a nitrogen gas or a nitrogen gas containing hydrogen below the explosive limit and baked at 300 to 450 ° C., the water and oil repellency is excellent in wear resistance and weather resistance on the coating surface. It has the effect of producing antifouling ceramic products.

  In addition, when the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group and the substance mainly composed of the alkoxysilyl group is 1:10 to 10: 1, Water and oil repellent antifouling ceramic products with excellent wear and weather resistance can be produced.

Furthermore, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n − ( CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and the main component is an alkoxysilyl group. Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl group or an ethyl group) , Short chain alkyl groups such as propyl group), or substances having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is Use of an integer) has an effect of improving high durability.

  Even if only the step of forming the lower layer composite film is repeated a plurality of times and the upper layer film forming step is omitted, there is no problem in ensuring excellent water separation and high durability.

  Further, when the upper layer film forming step is performed after repeating the step of forming the lower layer composite film a plurality of times, there is an effect that the initial water repellency is excellent and the high durability can be improved.

Furthermore, when a ceramic product having an alkali barrier film formed on the surface is used as the base ceramic product, the durability can be improved.

Here, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate during film formation can be improved, and the silanol condensation catalyst Compared to the use of, the antifouling ceramic product can be produced in a shorter time.

Also, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed (usually 1: 9 to 9: 1, but about 1: 1 When used, the film-forming time can be further reduced compared to the case where only a silanol condensation catalyst or a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound or an aminoalkylalkoxysilane compound is used alone. There is an effect.

Hereinafter, embodiments of the present invention will be described in detail.
(Embodiment 1)

First, the antifouling ceramic products such as tableware, flower vases, sanitary ware, insulators, tiles and the like, which are the first invention, will be described together with the manufacturing methods (third and fourth inventions).

For example, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group in a dry atmosphere (humidity of 35% or less is good) Is a positive number) and a substance having a chlorosilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or a chlorosilyloxy group as a main component Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC _{2 H 5) 3, SiH 2} (OC 2 H 5) 2 or _{(C 2 H 5 O) 3} Si (OSi (OC 2 H 5,) 2) m OC 2 H 5 (but, m is an integer), Yes, contains almost no non-aqueous water Solvents (e.g., hexadecane) each dissolved to a concentration of 0.01 M / L (in this case, the former and the latter molecular composition ratio 1: 1) to create a composite film-forming solution.

  Next, ceramic products (for example, tile 3) such as tableware, flower vases, sanitary ware, insulators, and tiles are thoroughly washed and dried, and then the composite film forming solution is applied to the surface and allowed to react for 1 to 2 hours.

At this time, since the surface of the tile 3 contains a large number of hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, the SiCl ₃ groups of the two substances and the hydroxyl group or adsorbed water undergo a dehydrochlorination reaction on the surface of the tile 3. In addition, a substance having a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group as main components and a substance having a chlorosilyl group as main components are mixed and reacted with each other and bonded to the surface of the tile 3 through a —SiO— bond.

That is, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group is changed to the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and is changed through the -SiO- bond. Thus, the surface of the tile 3 and the substance 2 having a siloxane group as a main component are combined, while the substance having a chlorosilyl group as a main component is changed to the substance 2 having a siloxane group as a main component before the -SiO- bond. Through this, it binds to the surface of the tile 3 and the substance 1 whose main component is a fluorocarbon group, a hydrocarbon group, and a silyl group.

Thereafter, the excess composite film forming solution on the surface is removed by washing (fourth invention, may be wiped off using an organic solvent). When the fluorocarbon group and hydrocarbon group are several nanometers thick, A composite film 5 containing a substance 1 having a silyl group as a main component and a substance 2 having a siloxane group as a main component, and having a large number of exposed hydroxyl groups 4 and internal hydroxyl groups 4 '(transmittance to visible light is 99 % Or more) can be formed on the surface of the tile 3. (Fig. 1 (a))

If the non-aqueous organic solvent is evaporated (third invention) or wiped off with a cloth or the like without the washing step, a fluorocarbon group, hydrocarbon group and silyl group having a thickness of several tens of nanometers are formed. A composite film containing a substance 1 having a main component and a substance 2 having a siloxane group as a main component and containing many hydroxyl groups (transmittance to visible light of 98% or more) could be formed on the tile surface. In this case, the thickness is thicker than that obtained by washing, and the surface gloss is inferior to that obtained by washing, but the advantage is that durability can be further improved.

Thereafter, each tile on which the composite film (which has been washed, or the solvent has been evaporated or wiped off) is formed is subjected to heat treatment at 300 to 450 ° C. for about 30 to 120 minutes. Then, the hydroxyl group 4 remaining in the film undergoes a dehydration reaction to form a polysiloxane bond and change to a network-like silica film 6. As a result, the water- and oil-repellent composite film 7 having high wear resistance and high weather resistance, comprising the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and the substance 2 mainly composed of a siloxane group. Thus, a highly durable antifouling tile can be produced (FIG. 1 (b)).

When using nitrogen gas containing 3% hydrogen (explosion limit is 4%) as the atmosphere gas when firing at 300 to 450 ° C., the coating film is formed even if some oxygen is mixed into the furnace when the furnace door is opened and closed. It can be fired without oxidation.

The contact angle of the antifouling tile 3 with respect to water at this time depends on the composition of the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and the substance 2 mainly composed of a siloxane group. If the composition is changed, it can be controlled to 95 ± 10 degrees. Moreover, the falling angle for 0.02 ml water droplets can be controlled to 35 degrees or less.

When forming a film by evaporating the solvent of the composite film forming solution, the lower the boiling point of the non-aqueous solvent used in the composite film forming solution is, the more convenient it is because it can be removed by evaporation earlier. About 50-150 degreeC is good.

On the other hand, when washing with a non-aqueous organic solvent, the higher the boiling point of the non-aqueous solvent used in the composite film-forming solution is, the more stable it is.

In addition, the fluorocarbon group contained in the composite film can be changed by changing the molecular composition ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and rosilyl group and substance mainly composed of chlorosilyl group in the composite film forming solution. And the molecular composition ratio of the substance 1 mainly composed of hydrocarbon group and silyl group and the substance 2 mainly composed of siloxane group is preferably 1:10 to 10: 1 (more preferably 1: 1 to 6: 1). ), The wear resistance can be greatly improved as compared with the case of a film made of 100% of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group.

As a reference, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group is CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , and a substance mainly composed of a chlorosilyl group is SiCl _4. 100% of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group (Comparative Example 1), and a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group. The results of contact angle change in the abrasion resistance test of the coating on the surface of the tile 3 (Example 1) when the composition of the substance and the substance mainly composed of chlorosilyl groups is 2: 1 are shown in FIG.
On the other hand, the molecular composition ratio of the substance 1 mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group and the substance 2 mainly composed of chlorosilyl group in the composite film forming solution is 1:10 to 10: 1 (more preferably Is 1: 1-6: 1), the contact angle with water can be controlled to 95 ± 10 degrees (in the case of 1: 1-6: 1, 100 ± 5 degrees). Compared with the case of a film (contact angle is about 110 degrees) made of 100% of a substance mainly composed of hydrogen groups and chlorosilyl groups, the water-drop separation performance can be greatly improved (the water drop falling angle is reduced).

As a reference, FIG. 3 shows the relationship between the contact angle for water droplets obtained in various experiments (including data obtained using other substances) and the falling angle (related to water separation performance).

In general, examples of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group include the following substances.
CF ₃ (CF ₂ ) _n (R) _m SiX _p Cl _3-p
(Where n is 0 or an integer, preferably an integer of 1 to 22, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or an oxygen atom, m is 0 or 1, X is H, alkyl Group, alkoxyl group, fluorine-containing alkyl group or substituent of fluorine-containing alkoxy group, p is 0, 1 or 2)

More specifically, the following (1) to (7) are mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ SiCl ₃

In addition, as a substance having a chlorosilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or a substance having a chlorosilyl group as a main component Instead, a compound represented by Si (OCH ₃ ) ₄ or Si (OC ₂ H ₅ ) ₄ can be used.

Furthermore, instead of Si (OCH ₃ ) ₄ or Si (OC ₂ H ₅ ) ₄ , SiH (OCH ₃ ) ₃ , SiH ₂ (OCH ₃ ) ₂ , or (CH ₃ O) ₃ Si (OSi (OCH ₃ )) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , or (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H _{5) 2} ) _m OC ₂ H ₅ (where m is an integer) can also be used.

At this time, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , or (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H _5, where m is an integer Although no dehydrochlorination reaction is performed, hydrochloric acid generated by the reaction of a chemical adsorbent containing a fluorocarbon group and a chlorosilyl group serves as a catalyst to form a siloxane bond with the substrate surface.

Further, instead of the chlorosilane-based chemical adsorbent, isocyanate-based chemical adsorbents in which all chlorosilyl groups are replaced with isocyanate groups, for example, (1) to (5) shown below can be mentioned.

(1) CF ₃ (CH ₂ ) _r SiX _p (NCO) _3-p
(2) CF ₃ (CH ₂ ) _r SiX _p (NCO) _3-p
(3) CF ₃ (CH ₂ ) _s O (CH ₂ ) _t SiX _p (NCO) _3-p
(4) CF ₃ (CH ₂ ) _u Si (CH ₃ ) ₂ (CH ₂ ) _v SiX _p (NCO) _3-p
(5) CF ₃ COO (CH ₂ ) _w SiX _p (NCO) _3-p
(However, as a preferable range, r is 1 to 25, s is 0 to 12, t is 1 to 20, u is 0 to 12, v is 1 to 20, and w is 1 to 25.)

Furthermore, in addition to the adsorbents described above, the following specific adsorbing compounds (1) to (7) can be mentioned, and any of them can be used in the second embodiment as well.

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (NCO) ₃
In this case, there is an advantage that hydrochloric acid is not generated.

Further, as the non-aqueous solvent, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent, and those having a boiling point of 50 to 300 ° C. are particularly suitable for use. Yes.

Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, nonane, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, etc. Can be mentioned.

Fluorocarbon solvents include chlorofluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added.

Furthermore, in the first embodiment, a silica film or a titanium oxide film formed using a sol-gel method, a CVD method, or a silicon nitride film formed using polysilazane or the like is used as an alkali barrier film instead of a tile. When tiles formed with a thickness of several nanometers to several tens of microns are used, elution of alkali components from the underlying tile can be reduced, and weather resistance and water resistance can be further improved. (The same applies to general ceramic products. Furthermore, in the case of a ceramic top plate for an electromagnetic cooker, if a plurality of fine protrusions (about 0.5 to 2 mm) are provided on the surface in advance, the coating directly contacts the pan bottom. Therefore, the durability of the antifouling film of the present invention can be further improved.)

Here, when firing, an atmosphere that does not contain oxygen, for example, nitrogen gas mixed with hydrogen below the explosion limit, is used. It can be removed with hydrogen, and oxidation of the film can be completely prevented.

In addition to tiles, the surface energy may be appropriately adjusted according to the required wear resistance or antifouling property.
(Embodiment 2)

Next, the antifouling ceramic product (for example, tile) which is the second invention will be described together with the manufacturing method (the fifth and sixth inventions).

In Embodiment 1, excess composite film forming solution on the surface is removed by washing (middle of the fourth invention), or the washing step is omitted and the non-aqueous organic solvent is evaporated, or with a cloth or the like After wiping off (in the middle of the third invention) to form a composite film (which is a lower layer composite film in the second embodiment), another layer is composed of a fluorocarbon group, a hydrocarbon group, and a silyl group as main components. An upper layer film containing the material 1 to be formed is formed (fifth and sixth inventions).

For example, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group in a dry atmosphere (humidity of 35% or less is good) Is a positive number) and dissolved in an organic solvent containing almost no non-aqueous water (for example, hexadecane) to a concentration of 0.01 M / L to prepare an upper layer film-forming solution.

  Next, the upper layer film-forming solution is applied to the surface of the tile 3 on which the lower layer composite film is formed, and reacted for 1 to 2 hours.

At this time, the surface of the tile 3 on which the lower composite film 5 is formed has a large number of hydroxyl groups 4, 4 ′, that is, active hydrogen, as shown in FIG. Therefore, a chlorosilyl group (—SiCl ₃ ) group of a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group on the surface of the tile 3 and a hydroxyl group 4 exposed on the surface undergo a dehydrochlorination reaction, thereby A substance 1 ′ mainly composed of a carbonized carbon group, a hydrocarbon group, and a silyl group is bonded to the surface of the tile 3 through a —SiO— bond.

That is, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group is changed to a substance 1 ′ mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and the —SiO— bond is changed. Thus, the film is bonded to the hydroxyl group 4 exposed on the surface of the tile 3 to form a coating film containing the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group.

Thereafter, the excess upper layer film-forming solution on the surface is washed away (sixth invention, may be wiped off using an organic solvent), and a fluorocarbon group and a hydrocarbon group having a thickness of several nanometers A lower layer composite film composed of a substance 1 having a silyl group as a main component and a substance 2 having a siloxane group as a main component, and a fluorocarbon group, a hydrocarbon group and a silyl group bonded to the surface of the lower layer composite film as main components A film having a two-layer structure made of the upper film 8 made of the substance 1 can be formed on the surface of the tile 3.

Thereafter, each tile 3 on which the two-layer coating film (which has been washed, or evaporated or wiped) may be further subjected to heat treatment at 300 to 450 ° C. for about 30 to 120 minutes. Then, the hydroxyl group 4 ′ of the SiOH group remaining inside the film undergoes a dehydration reaction to form a polysiloxane bond and change to a network-like silica film 6 ′. As a result, the lower layer composite film 7 ′ made of the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and the substance 2 mainly composed of a siloxane group, the fluorocarbon group, the hydrocarbon group and the silyl group. The upper layer film 8 made of the substance 1 containing as a main component becomes a water- and oil-repellent two-layer film 9 with high wear resistance and weather resistance, and a highly durable antifouling tile with a water droplet contact angle of approximately 110 degrees. 3 can be manufactured (FIG. 1 (c)). Even if this film has a two-layer structure, the transmittance for visible light is approximately 99% or more, so the surface gloss of the underlying tile is not lost.

If the non-aqueous organic solvent is evaporated or wiped off with a cloth (fifth invention) without the washing and removing step, a tens of nanometer-thick fluorine having a thickness larger than that of the washing is obtained. An upper layer film (substance of 98% or more with respect to visible light even in a two-layer structure) made of the substance 1 mainly composed of carbonized carbon group, hydrocarbon group and silyl group can be formed on the surface of the tile 3. In this case, the film thickness of the coating is increased, and the surface gloss is inferior to that obtained by washing and removal, but there is no problem in practical use and the durability can be further improved.

The initial contact angle with respect to water of the antifouling tile at this time is determined by the physical properties of the uppermost film on the outermost surface, and as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, for example, CF ₃ (CF ₂ ) When _n (CH ₂ ) ₂ SiCl ₃ (n is a positive number) is used, it can be controlled to approximately 105 ± 10 degrees. Moreover, the falling angle with respect to 0.02 ml of water droplets can be controlled to about 45 degrees or less.

When the upper layer film is formed by evaporating the solvent of the upper layer film forming solution, the lower the boiling point of the non-aqueous solvent used in the composite film forming solution is, the more convenient it is. Then, about 50-150 degreeC is good.

On the other hand, when washing with a non-aqueous organic solvent, the higher the boiling point of the non-aqueous solvent used in the composite film-forming solution is, the more stable it is.

As a reference, a film having a two-layer structure when CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group (Example) The result of contact angle change in the wear resistance test of 2) is shown in comparison with FIG.

In addition, the drop angle of the water droplet is about 45 degrees in the case of a 20 microliter water droplet, which is larger than the first embodiment as the contact angle increases (see FIG. 3). The sex can be further greatly improved.

In general, examples of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group for forming the upper layer film include the following substances.
CF ₃ (CF ₂ ) _n (R) _m SiX _p Cl _3-p
(Where n is 0 or an integer, preferably an integer of 1 to 22, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or an oxygen atom, m is 0 or 1, X is H, alkyl Group, alkoxyl group, fluorine-containing alkyl group or substituent of fluorine-containing alkoxy group, p is 0, 1 or 2)

More specifically, the following (1) to (7) are mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ SiCl ₃

Further, instead of the chlorosilane-based chemical adsorbent, isocyanate-based chemical adsorbents in which all chlorosilyl groups are replaced with isocyanate groups, for example, (1) to (5) shown below can be mentioned.

(1) CF ₃ (CH ₂ ) _r SiX _p (NCO) _3-p
(2) CF ₃ (CH ₂ ) _r SiX _p (NCO) _3-p
(3) CF ₃ (CH ₂ ) _s O (CH ₂ ) _t SiX _p (NCO) _3-p
(4) CF ₃ (CH ₂ ) _u Si (CH ₃ ) ₂ (CH ₂ ) _v SiX _p (NCO) _3-p
(5) CF ₃ COO (CH ₂ ) _w SiX _p (NCO) _3-p
(However, as a preferable range, r is 1 to 25, s is 0 to 12, t is 1 to 20, u is 0 to 12, v is 1 to 20, and w is 1 to 25.)

Furthermore, in addition to the above adsorbents, the following specific adsorbing compounds (1) to (7) can be mentioned.

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (NCO) ₃
In this case, there is an advantage that hydrochloric acid is not generated.

Further, as the non-aqueous solvent, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent, and those having a boiling point of 50 to 300 ° C. are particularly suitable for use. Yes.

Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, nonane, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, etc. Can be mentioned.

Fluorocarbon solvents include chlorofluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added.

Furthermore, in the second embodiment, as in the first embodiment, instead of tiles, silicon nitride formed using a silica film, a titanium oxide film, or polysilazane formed using a sol-gel method, a CVD method, or the like. When a tile formed with a thickness of several nanometers to several tens of microns using a film or the like as an alkali barrier film is used, elution of alkali components from the tile can be reduced, and weather resistance and water resistance can be further improved. (The same applies to general ceramic products)

Here, when firing, an atmosphere that does not contain oxygen, for example, nitrogen gas mixed with hydrogen below the explosion limit, is used. It can be removed with hydrogen, and oxidation of the film can be completely prevented.

In this method, the surface energy can be appropriately adjusted and used in accordance with the purpose of the ceramic product to be manufactured.
(Embodiment 3)

Furthermore, the antifouling ceramic product (for example, tile) which is the first invention will be described together with other manufacturing methods (seventh and eighth inventions).

First, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si () is a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group in a dry atmosphere (humidity is preferably 50% or less). OA) ₃ (n is a positive number, A is an alkyl group such as a methyl group or an ethyl group) and Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA ) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a short-chain alkyl group such as a methyl group, an ethyl group, or a propyl group), or alkoxy Instead of a substance containing silyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer) contains almost non-aqueous water No organic solvent (eg For example, hexadecane) is dissolved to a concentration of 0.01 M / L (in this case, the former and the latter have a molecular composition ratio of 1: 1), and the silanol condensation catalyst is further added to a concentration of 0.0001 M / L. The composite film forming solution is prepared by adding and dissolving so that.

  Next, the underlying tile 13 is thoroughly cleaned, and the composite film forming solution is applied to the surface and reacted for 1 to 2 hours.

At this time, since the surface of the tile 13 contains a large number of hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, the -Si (OA) ₃ group of the two substances and the hydroxyl groups and adsorbed water on the surface of the tile 13 In a state where a dealcoholization reaction is carried out in the presence of a silanol condensation catalyst, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and a substance mainly composed of an alkoxysilyl group are mixed and reacted with —SiO—. It couple | bonds with the said tile 13 surface through coupling | bonding.

That is, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group is changed to the substance 11 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and the —SiO— bond is changed. And the surface of the tile 13 and the substance 12 having a siloxane group as a main component, while the substance having an alkoxysilyl group as a main component is changed to the substance 12 having a siloxane group as a main component before the -SiO 2 -Bonded with the surface of the tile 13 and the substance 11 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group through the bond.

Thereafter, the excess composite film forming solution on the surface is washed away (8th invention, may be wiped off using an organic solvent). When the fluorocarbon group and the hydrocarbon group are several nanometers thick, A composite film 15 containing a substance 11 mainly containing a silyl group and a substance 12 containing a siloxane group as a main component and containing many exposed hydroxyl groups 14 and internal hydroxyl groups 14 '(transmittance to visible light is 99 % Or more) can be formed on the surface of the tile 13. (Fig. 4 (a))

The step of washing and removing is omitted and the non-aqueous organic solvent is evaporated or wiped off with a cloth (seventh invention) to obtain a tens of nanometer-thick fluorocarbon group, hydrocarbon group and silyl group. A composite film 15 containing a substance 11 having a group as a main component and a substance 12 having a siloxane group as a main component and containing a large number of hydroxyl groups (the transmittance for visible light is 98% or more) could be formed on the surface of the tile 13. . In this case, the thickness is thicker than that obtained by washing, and the surface gloss is inferior to that obtained by washing, but the advantage is that durability can be further improved.

Thereafter, each tile on which the composite film (washed, or the solvent has been evaporated or wiped off) is formed is subjected to heat treatment at 300 to 450 ° C. for about 30 to 120 minutes. Then, the hydroxyl groups 14 and 14 ′ remaining in the film undergo a dehydration reaction to form a polysiloxane bond and change to a network-like silica film 16. As a result, the water- and oil-repellent composite film 17 having high wear resistance and high weather resistance is composed of the substance 11 mainly composed of fluorocarbon group, hydrocarbon group and silyl group, and the substance 12 mainly composed of siloxane group. Thus, a highly durable water / oil repellent antifouling tile 13 can be produced (FIG. 4B).

The contact angle of the water-repellent / oil-repellent antifouling tile with respect to water depends on the composition of the substances 11 and 12, and can be controlled to approximately 95 ± 10 degrees by changing the composition. Moreover, the falling angle for 0.02 ml water droplets can be controlled to 35 degrees or less.

When forming a film by evaporating the solvent of the composite film forming solution, the lower the boiling point of the non-aqueous solvent used in the composite film forming solution is, the more convenient it is because it can be removed by evaporation earlier. About 40-300 degreeC is good.

On the other hand, in the case of washing with a non-aqueous organic solvent, the boiling point of the non-aqueous solvent used in the composite film forming solution is more stable as it is higher, but is preferably about 300 to 350 ° C. in terms of handling.

In addition, in place of washing with an organic solvent instead of washing with the two manufacturing methods, the environmental load in production can be reduced.

Further, when the molecular mixing ratio of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group and the substance mainly composed of the alkoxysilyl group is set to 1:10 to 10: 1, durability is maintained. Property and water separation can be improved at the same time.

Furthermore, the fluorination contained in the composite film can be changed by changing the molecular composition ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and rosilyl group and the substance mainly composed of alkoxysilyl group in the composite film forming solution. The molecular composition ratio of the substance 11 mainly composed of carbon group, hydrocarbon group and silyl group to the substance 12 mainly composed of siloxane group is preferably 1:10 to 10: 1 (more preferably 1: 1 to 6). 1), the wear resistance can be greatly improved as compared with the case of a film made of 100% of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group.

As a reference, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group is CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OA) ₃ , and the alkoxysilyl group is a main component. When the substance to be used is Si (OA) ₄ and dibutyltin diacetylacetonate is used as the silanol catalyst, the substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, and the alkoxysilyl group as a main component The tile surface coating (Example 3) in the case of the composition of the material to be 2: 1 and the (100%) tile surface of the material mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group The result of the contact angle change in the abrasion resistance test with the coating (Comparative Example 2) is shown in comparison with FIG.

Note that the molecular composition ratio of the substance 11 mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group and substance 12 mainly composed of alkoxysilyl group in the composite film forming solution is 1:10 to 10: 1 ( More preferably, the contact angle with respect to water can be controlled to 95 ± 10 degrees (in the case of 1: 1 to 6: 1, 100 ± 5 degrees). Compared with the case of a film (contact angle is about 110 degrees) made of 100% of a substance mainly composed of a hydrocarbon group and an alkoxysilyl group, the water-drop water separation performance can be greatly improved (the water drop falling angle is reduced).

In general, examples of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group include the following substances.
CF ₃ (CF ₂ ) _n (R) _m SiX _p (OA) _3-p
(Where n is 0 or an integer, preferably an integer of 1 to 22, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or an oxygen atom, m is 0 or 1, X is H, alkyl Group, alkoxyl group, fluorine-containing alkyl group or substituent of fluorine-containing alkoxy group, A is a short-chain alkyl group such as methyl group, ethyl group or propyl group, p is 0, 1 or 2)

More specifically, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. ) _N (CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is a short group such as a methyl group, an ethyl group, or a propyl group) Chain alkyl group).

More specifically, the following (1) to (18) are mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OCH ₃ ) ₃
(8) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(9) CF 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{(10) CF 3 (CH 2} ) 6 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(13) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(14) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OC ₂ H ₅ ) ₃
(15) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OCH ₃ ) ₂
(16) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OC ₂ H ₅ ) ₂
(17) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOCH ₃
(18) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOC ₂ H ₅
Is raised.

Moreover, Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (provided that the alkoxysilyl group is a main component) m is an integer, and A is a short chain alkyl group such as a methyl group, an ethyl group, or a propyl group).

Further, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer) can be used in place of the substance having an alkoxysilyl group as a main component. If these substances are added, a small amount of hydrochloric acid is generated by dehydrochlorination reaction with the surface of the base material, so that it substantially acts as a promoter and further has an effect of increasing the film forming speed.

Furthermore, carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates can be used as silanol condensation catalysts. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate can be used.

If a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the reaction time can be shortened by about twice and the film formation time can be halved. It can be shortened to the extent.

Moreover, when a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed and used (1: 9 to 9: 1), the reaction time is several times longer. The film formation time can be shortened to a fraction.

Further, as the non-aqueous solvent, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent, and those having a boiling point of 40 to 300 ° C. are particularly suitable for use. Yes.

Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, nonane, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, etc. Can be mentioned.

In addition, fluorocarbon solvents include fluorocarbon solvents 365 LIVE (Daiwa Chemical Industry Co., Ltd. product), Fluorinert (3M product), Afludo (Asahi Glass product), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, a small amount of an organic chlorine-based solvent such as chloroform may be added.

Furthermore, in the first embodiment, a silica film or a titanium oxide film formed using a sol-gel method, a CVD method, or a silicon nitride film formed using polysilazane or the like is used as an alkali barrier film instead of a tile. When tiles formed with a thickness of several nanometers to several tens of microns are used, elution of alkali components from the underlying tile can be reduced, and weather resistance and water resistance can be further improved. (The same applies to general ceramic products.)

Here, when firing, an atmosphere that does not contain oxygen, for example, nitrogen gas mixed with hydrogen below the explosion limit, is used. It can be removed with hydrogen, and oxidation of the film can be completely prevented.

Even in this method, the surface energy can be appropriately adjusted and used in accordance with the purpose of the ceramic product to be manufactured.
(Embodiment 4)

The ceramic product according to the second invention will be described together with another manufacturing method (the ninth and tenth inventions).

In Embodiment 3, excess composite film forming solution on the surface of the underlying tile is removed by washing (middle of the tenth invention), or the washing step is omitted to evaporate the non-aqueous organic solvent, or cloth Or the like (in the middle of the ninth invention) to form a composite film (lower layer composite film in the fourth embodiment), and then another layer, a fluorocarbon group, a hydrocarbon group, and a silyl group. An upper layer film containing the substance 11 containing as a main component is formed.

For example, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group in a dry atmosphere (humidity is preferably 50% or less). ) ₃ (n is a positive number), dissolved in an organic solvent containing almost no non-aqueous water (for example, hexadecane) to a concentration of 0.01 M / L, and further a silanol condensation catalyst was added to 0.0001 M / L. An upper layer film-forming solution is prepared by adding and dissolving to a concentration of L.

  Next, the upper layer film-forming solution is applied to the surface of the tile 13 formed by the same method as in the third embodiment and formed with the lower layer composite film that has not been fired yet, and is reacted for 1 to 2 hours.

At this time, as shown in FIG. 4A, the surface of the tile 13 on which the lower layer composite film 15 is formed has a large number of hydroxyl groups 14, 14 ′, that is, active hydrogen. Therefore, silanol condensation occurs between the alkoxysilyl group (—Si (OA) ₃ ) group of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group on the surface of the tile 13 and the hydroxyl group 14 exposed on the surface. A dealcoholization reaction is performed in the presence of a catalyst, and a substance 11 ′ mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group is bonded to the surface of the tile 13 through a —SiO— bond.

That is, the substance having a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as main components is changed to a substance 11 ′ having a fluorocarbon group, a hydrocarbon group, and a silyl group as main components, and the —SiO— bond is changed. Thus, a film containing the substance 11 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group is formed by bonding with the hydroxyl group 14 exposed on the surface of the tile 13.

Thereafter, the excess upper layer film-forming solution on the surface is washed away (it may be removed by wiping with an organic solvent. The tenth invention), and a fluorocarbon group and a hydrocarbon group having a thickness of several nanometers A lower layer composite film composed of a substance 11 mainly containing a silyl group and a substance 12 mainly containing a siloxane group, and a fluorocarbon group, a hydrocarbon group and a silyl group bonded to the surface of the lower layer composite film. A coating 19 having a two-layer structure made of the upper film 18 made of the substance 11 can be manufactured.

Thereafter, each tile 13 on which the two-layered film (washed or evaporated or wiped) may be formed is preferably 300 to 450 ° C. (more preferably 400 ± 20 ° C.). When the heat treatment is performed for about 30 to 120 minutes, the hydroxyl group 14 'of the SiOH group remaining inside the film undergoes a dehydration reaction to form a polysiloxane bond and change to a network-like silica film 16'. As a result, the lower layer composite film 17 ′ composed of the substance 11 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and the substance 12 mainly composed of a siloxane group, the fluorocarbon group, the hydrocarbon group, and the silyl group. The upper layer film 18 made of the substance 11 having the main component is a water- and oil-repellent two-layer film 19 having high wear resistance and weather resistance, and a highly durable water-repellent water contact angle of approximately 105 ± 5 degrees. An oil-repellent antifouling tile can be produced (FIG. 4C). Even if this film has a two-layer structure, the visible light transmittance is approximately 98% or more, so the gloss of the underlying surface is not impaired.

If the non-aqueous organic solvent is evaporated or wiped off with a cloth or the like (the ninth invention) without the washing and removing step, a fluorine film having a thickness of several tens of nanometers is obtained as compared with the case of washing. An upper film (having a transmittance of 98% or more with respect to visible light even in a two-layer structure) made of the substance 11 mainly composed of a carbonized carbon group, a hydrocarbon group, and a silyl group can be formed on the tile surface. In this case, the film thickness of the coating is increased, and the surface gloss is inferior to that obtained by washing and removal, but there is no problem in practical use and the durability can be further improved.

The initial contact angle with respect to the water of the water / oil / oil repellent antifouling tile at this time is determined by the physical properties of the uppermost film on the outermost surface, and as a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, When CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ (n is a positive number) is used, it can be controlled to approximately 105 ± 10 degrees. Moreover, the falling angle with respect to 0.02 ml of water droplets can be controlled to about 45 degrees or less.

When the upper layer film is formed by evaporating the solvent of the upper layer film forming solution, the lower the boiling point of the non-aqueous solvent used in the composite film forming solution is, the more convenient it is. Then, about 40-300 degreeC is good.

On the other hand, in the case of washing with a non-aqueous organic solvent, the boiling point of the non-aqueous solvent used in the composite film forming solution is more stable as it is higher, but is preferably about 300 to 350 ° C. in terms of handling.

In addition, in place of washing with an organic solvent instead of washing with the two manufacturing methods, the environmental load in production can be reduced.

As a reference, the tile surface of a two-layer structure when CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OA) ₃ is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group FIG. 5 shows the results of contact angle change in the wear resistance test of (Example 4) of this film together with the results of Example 3 and Comparative Example 2.

In addition, the drop angle of the water droplet is about 45 degrees in the case of a 20 microliter water drop, and there is a drawback that the drop angle of the water drop becomes larger as the contact angle becomes larger than the result of Example 4 (see FIG. 3). However, the wear resistance can be further greatly improved.

In general, examples of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group for forming the upper layer film include the following substances.
CF ₃ (CF ₂ ) _n (R) _m SiX _p (OA) _3-p
(Where n is 0 or an integer, preferably an integer of 1 to 22, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or an oxygen atom, m is 0 or 1, X is H, alkyl Group, alkoxyl group, fluorine-containing alkyl group or substituent of fluorine-containing alkoxy group, A is a short-chain alkyl group such as methyl group, ethyl group or propyl group, p is 0, 1 or 2)

More specifically, CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. ) _N (CH ₂ ) ₂ ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is a short group such as a methyl group, an ethyl group, or a propyl group) Chain alkyl group).

More specifically, the following (1) to (18) are raised.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OCH ₃ ) ₃
(8) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(9) CF 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{(10) CF 3 (CH 2} ) 6 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(13) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(14) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OC ₂ H ₅ ) ₃
(15) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OCH ₃ ) ₂
(16) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OC ₂ H ₅ ) ₂
(17) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOCH ₃
(18) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOC ₂ H ₅
Is raised.

Moreover, Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (provided that the alkoxysilyl group is a main component) m is an integer, and A is a short chain alkyl group such as a methyl group, an ethyl group, or a propyl group).

Further, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer) can be used in place of the substance having an alkoxysilyl group as a main component. If these substances are added, a small amount of hydrochloric acid is generated by dehydrochlorination reaction with the surface of the base material, so that it substantially acts as a promoter and further has an effect of increasing the film forming speed.

Furthermore, carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates can be used as silanol condensation catalysts. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate can be used.

If a ketimine compound, or an organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the reaction time can be shortened by about twice and the film forming time can be shortened. it can.

Moreover, when a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed and used (1: 9 to 9: 1), the reaction time is several times longer. It can be done quickly and the film formation time can be reduced to a fraction of that.

Further, as the non-aqueous solvent, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent, and those having a boiling point of 50 to 300 ° C. are particularly suitable for use. Yes.

Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, nonane, isoparaffin, normal paraffin, decalin, industrial gasoline, octane, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone. And polyether silicone.

In addition, fluorocarbon solvents include fluorocarbon solvents 365 LIVE (Daiwa Chemical Industry Co., Ltd. product), Fluorinert (3M product), Afludo (Asahi Glass product), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, a small amount of an organic chlorine-based solvent such as chloroform may be added.

Further, it is possible to provide a ceramic product having high durability and considerably excellent water and oil repellency characteristics without repeating the upper layer film forming step by repeating only the step of forming the lower layer composite film a plurality of times.

Furthermore, in the first embodiment, a silica film or a titanium oxide film formed using a sol-gel method, a CVD method, or a silicon nitride film formed using polysilazane or the like is used as an alkali barrier film instead of a tile. When tiles formed with a thickness of several nanometers to several tens of microns are used, elution of alkali components from the underlying tile can be reduced, and weather resistance and water resistance can be further improved. (The same applies to general ceramic products)

Here, when firing, an atmosphere that does not contain oxygen, for example, nitrogen gas mixed with hydrogen below the explosion limit, is used. It can be removed with hydrogen, and oxidation of the film can be completely prevented.

Even in this method, the surface energy can be appropriately adjusted and used in accordance with the purpose of the ceramic product to be manufactured.

Hereinafter, specific examples of the present invention will be described together with comparative examples. In the following examples, the molecular composition ratio means a molar ratio unless otherwise specified.

CF as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group in a dry atmosphere (humidity of 35% or less is preferable. ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , SiCl ₄ as a substance mainly composed of a chlorosilyl group, and 0% each in a 5% chloroform-containing dimethyl silicone solution containing almost no water as a non-aqueous organic solvent. A composite film forming solution was prepared by dissolving to a concentration (2: 1) of 0.02 M / L and 0.01 M / L.

  Next, ceramic tiles, which are typical examples of ceramic products, are thoroughly washed, dried, and then in a dry atmosphere (humidity is 35% or less. When the temperature is higher than this, the film-forming substance is hydrolyzed and the film becomes cloudy. .) Was applied to the surface and allowed to react at room temperature for 1-2 hours.

At this time, since the tile surface contains many hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, the ≡SiCl group of the two substances and the hydroxyl group or adsorbed water react with each other on the tile surface to cause dehydrochlorination reaction. Bonded to the tile surface in a mixed state of a substance mainly composed of carbonized carbon group, hydrocarbon group and silyl group and a substance mainly composed of siloxane group.

A substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group is bonded to a tile surface or a substance mainly composed of a siloxane group via the silyl group. Bonded with the surface of the tile or a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group via a siloxane group.

Thereafter, when the excess composite film forming solution on the surface is washed away with ethanol, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a substance mainly composed of a siloxane group having a thickness of about 5 nm are obtained. A composite film containing it could be formed on the tile surface.

Note that the non-aqueous organic solvent is evaporated without washing (in this case, when the tile is heated at 60 to 100 ° C., the evaporation of the solvent can be accelerated and the evaporation time can be shortened). A composite film containing a material mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a material mainly composed of a siloxane group having a thickness of 30 nm could be formed on the tile surface. When wiped off, the thickness was approximately 10 nm.

After that, when each tile on which the composite film is formed is subjected to heat treatment at 400 ° C. for about 30 minutes in an atmosphere substantially free of oxygen, for example, nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit, Most of the ≡SiOH groups produced by the reaction of SiCl ₃ groups with adsorbed water undergo a dehydration reaction to form polysiloxane bonds and change to a mesh-like silica film, resulting in high wear resistance and high weather resistance. It becomes a water- and oil-repellent composite film composed of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a substance mainly composed of a siloxane group, and is approximately three times as much as when fired at 250 ° C. or less. A highly durable water and oil repellent antifouling tile could be manufactured.

When nitrogen gas containing 3% hydrogen (explosion limit is 4%) is used as the atmosphere gas during firing at 400 ° C. for 30 minutes, the coating film is formed even if some oxygen is mixed into the furnace when the furnace door is opened and closed. Firing was possible without oxidation.

At this time, the contact angle of the antifouling tile with respect to water was approximately 103 degrees regardless of whether or not cleaning was performed.

Further, the falling angle of 0.02 ml water droplets was about 30 degrees. Furthermore, in the abrasion test, the contact angle with respect to water was able to maintain 95 degrees or more with respect to the reciprocating 6000 times of rubbing on the conditions of a load of 500 g / 4cm < ² >. Furthermore, if a tile having an alkali barrier film previously formed on the tile surface was used, the water resistance could be further improved.

Furthermore, instead of the tile, a silica film (such as a titanium oxide film or a silicon nitride film formed using polysilazane) formed by using a sol-gel method or a CVD method may be used as an alkali barrier film, and about 10 microns. When a tile formed with a thickness of 5 mm was used, the elution of alkali components from the tile could be considerably reduced, and the weather resistance and water resistance could be further improved. (The same applies to general ceramic products)

Here, in place of SiCl ₄ which is a substance mainly composed of a chlorosilyl group, a similar result can be obtained even if a compound represented by Si (OCH ₃ ) ₄ or Si (OC ₂ H ₅ ) ₄ is used. It was.
At this time, Si (OCH ₃ ) ₄ and Si (OC ₂ H ₅ ) ₄ do not undergo a dehydrochlorination reaction, but hydrochloric acid generated by reaction of a chemical adsorbent containing a fluorocarbon group and a chlorosilyl group is a catalyst. Thus, a siloxane bond is formed with the substrate surface.
Further, instead of SiCl ₄ , SiH (OCH ₃ ) ₃ , SiH ₂ (OCH ₃ ) ₂ , or (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), , SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , or (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is Integer) could also be used.
(Comparative Example 1)

In Example 1, an antifouling tile was prototyped under the same conditions except for the material SiCl ₄ having a chlorosilyl group as a main component. When the contact angle with water, which is the basic performance, was measured, it was 112 degrees.

The drop angle of the water droplet was 0.02 ml, and was about 50 degrees initially. In addition, a wear test was performed. The wear resistance evaluation results under the conditions of weighting 500 g / 4 cm ^2, shown in FIG. 2 with Example 1.

In view of practicality, the contact angle of 95 degrees (see FIG. 3) with the most favorable water separation performance was able to withstand only up to 2800 round trips. Further, as apparent from FIG. 2, when compared with the point that the contact angle becomes 95 degrees, only wear resistance of 1/2 or less was obtained as compared with the tile of Example 1.

From the above experiment, the antifouling tile manufactured by the conventional technique has a higher contact angle with water of 110 degrees or more than the antifouling tile manufactured by using the manufacturing method of the present invention, and therefore the water separation performance is inferior. It has been confirmed that there is a drawback. It was also confirmed that the wear resistance was inferior.

In Example 1, an excessive composite film forming solution on the tile surface was removed by washing with ethanol, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group having a thickness of about 5 nm and a siloxane group were mainly used. After the formation of the lower layer composite film containing the substance as a component, the following steps were subsequently added to form a water / oil repellent film having a two-layer structure.

The added process is shown below.
That is, in a dry atmosphere (humidity of 35% or less is good. If the humidity is higher than this, the film-forming substance is hydrolyzed and the film becomes cloudy), and the main component is a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group. CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ is used as the substance to be used, and a concentration of 0.01 M / L is added to a 5% chloroform-containing dimethyl silicone solution containing almost no water, which is a non-aqueous organic solvent. An upper layer film-forming solution was prepared by dissolving in

  Next, a tile on which a lower composite film is formed is prepared, and the composite film forming solution is dried on the surface in a dry atmosphere (humidity is 35% or less. If the temperature is higher than this, the film forming substance is hydrolyzed and the film becomes cloudy. And allowed to react at room temperature for 1-2 hours.

At this time, the lower layer composite film on the tile surface is exposed to hydroxyl groups, that is, active hydrogen, to some extent. Therefore, the ≡SiCl group and the hydroxyl group of a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group on the tile surface. As a result of dehydrochlorination reaction, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group was bonded to the tile surface via the silyl group.

Thereafter, the excess upper layer film forming solution on the surface is removed by washing with ethanol, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a substance mainly composed of a siloxane group, having a thickness of about 7 nm. It was possible to form a coating having a two-layer structure on the surface of the tile, with the composite film including the lower layer as the upper layer and the coating containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group as the upper layer film.

Note that the non-aqueous organic solvent is evaporated without washing (in this case, when the tile is heated at 60 to 100 ° C., the evaporation of the solvent can be accelerated and the evaporation time can be shortened). A 50 nm thick two-layer coating could be formed on the tile surface.
When wiped off, the thickness was approximately 20 nm.

Hereinafter, in the same manner as in Example 1, each tile on which a coating having a two-layer structure is formed has an oxygen-free atmosphere, for example, nitrogen gas or nitrogen gas mixed with hydrogen below the explosion limit at 400 ° C. 30. When heat treatment is performed for about a minute, most of the ≡SiOH groups remaining in the film undergo a dehydration reaction to form a polysiloxane bond and change to a network-like silica film. An underlayer composite film containing a fluorocarbon group, a hydrocarbon group, a silyl group as a main component, and a siloxane group as a main component, and a fluorocarbon group, which has high water repellency and high wear resistance and weather resistance; A highly durable antifouling tile having a two-layer coating film comprising an upper layer film containing a substance mainly composed of a hydrocarbon group and a silyl group could be produced. In this case as well, a highly durable water / oil / oil repellent and antifouling tile 5 times or more than that when fired at 250 ° C. or lower could be produced. However, when heated at 470 ° C. or higher, the film was decomposed even in an atmosphere containing no oxygen.

Also at this time, the contact angle of the antifouling tile with respect to water was within about 110 ± 3 degrees regardless of whether or not cleaning was performed.

Further, the falling angle of 0.02 ml water droplets was about 45 degrees. Furthermore, in the abrasion test, the contact angle with water was able to maintain 95 degrees or more with respect to 9000 times of rubbing under conditions of a load of 500 g / 4 cm ² . FIG. 2 shows the results of evaluation of wear resistance under the condition of a weight of 500 g / 4 cm ² together with Example 1 and Comparative Example 1.
Furthermore, if a tile having an alkali barrier film previously formed on the tile surface was used, the water resistance could be further improved.

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OA) ₃ as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group in a dry atmosphere (humidity is preferably 50% or less) , Si (OA) ₄ (A represents an alkyl group) as a substance having an alkoxysilyl group as a main component is added to a 5% chloroform-containing dimethylsilicone solution containing almost no water as a non-aqueous organic solvent. Dissolve to a concentration of 02M / L and 0.01M / L (2: 1), and add and dissolve dibutyltin diacetylacetonate as a silanol condensation catalyst to a concentration of 0.0001M / L. A composite film forming solution was prepared.

  Next, the tile was thoroughly washed and dried, and then the composite film forming solution was applied to the surface in a dry atmosphere (humidity of 50% or less), and allowed to react at room temperature for 1 to 2 hours.

At this time, since the tile surface contains many hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, the ≡SiOA group of the two substances on the tile surface and the hydroxyl group or adsorbed water are dealcoholized under a silanol condensation catalyst. It reacted and bonded to the tile surface in a state where a substance mainly composed of fluorocarbon group, hydrocarbon group and silyl group and a substance mainly composed of siloxane group were mixed.

At this time, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group is bonded to the tile surface or a substance mainly composed of a siloxane group via the silyl group, and the siloxane group is mainly composed. The substance to be bonded to the tile surface or a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group via a siloxane group.

Thereafter, when the excess composite film forming solution on the surface is washed away with ethanol, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a substance mainly composed of a siloxane group having a thickness of about 5 nm are obtained. A composite film containing it could be formed on the tile surface.

The non-aqueous organic solvent is evaporated without washing (in this case, heating the tile at 60 to 100 ° C. can accelerate the evaporation of the solvent and shorten the evaporation time). A composite film containing a material mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a material mainly composed of a siloxane group having a thickness of 30 nm could be formed on the tile surface. Moreover, when it wiped off only with the cloth, it became about 10 nm thickness.

Thereafter, when each tile formed with the composite film is subjected to a heat treatment at 400 ° C. for about 20 minutes in an atmosphere substantially free of oxygen, for example, nitrogen gas or nitrogen gas containing hydrogen below the explosion limit, ≡ Most of the ≡SiOH groups produced by the reaction of SiOA groups with adsorbed water undergo a dehydration reaction to form polysiloxane bonds and change into a mesh-like silica film, which is a highly wear-resistant and weather-resistant fluoride. It becomes a water- and oil-repellent composite film composed of a substance mainly composed of carbonated hydrocarbon group, hydrocarbon group and silyl group and a substance mainly composed of siloxane group, and is approximately three times as durable as when fired at 250 ° C. And water- and oil-repellent and antifouling tiles could be produced.

In addition, when nitrogen gas containing 3% hydrogen (explosion limit is 4%) is used as an atmospheric gas during firing at 400 ° C. for 30 minutes, the coating does not oxidize even if some oxygen is mixed into the furnace. Baked.

At this time, the light transmittance of the composite film was 99% or more with respect to light having a wavelength of 400 to 700 nm regardless of whether or not cleaning was performed. Moreover, the contact angle with respect to the water of a water-repellent | oil-repellent | oil-repellent antifouling tile was about 103 degree | times irrespective of the presence or absence of washing | cleaning.

Further, the falling angle of 0.02 ml water droplets was about 30 degrees. Furthermore, in the abrasion test, the contact angle with water was able to maintain 96 degrees or more with respect to 6000 rubbing reciprocations under the condition of a load of 500 g / 4 cm ² .

Furthermore, instead of the tile, a silica film (such as a titanium oxide film or a silicon nitride film formed using polysilazane) formed by using a sol-gel method or a CVD method may be used as an alkali barrier film, and about 10 microns. When a tile formed with a thickness of 5 mm was used, the elution of alkali components from the tile could be considerably reduced, and the weather resistance and water resistance could be further improved. (The same applies to general ceramic products)
(Comparative Example 2)

In Example 3, a water and oil repellent and antifouling tile was produced under the same conditions except for the substance Si (OA) ₄ having an alkoxysilyl group as a main component. When the contact angle with water, which is the basic performance, was measured, it was 112 degrees.

The drop angle of the water droplet was 0.02 ml, and was about 50 degrees initially. In addition, a wear test was performed. FIG. 5 shows the results of the evaluation of wear resistance under the condition of a weight of 500 g / 4 cm ² together with the results of Examples 3 and 4.

In view of practicality, the contact angle of 95 degrees (see FIG. 3) with the most favorable water separation performance was able to withstand only up to 2800 round trips. Further, as apparent from the figure, when compared with the point that the contact angle is 95 degrees, only wear resistance of 1/2 or less was obtained compared to the tile of Example 4.

From the above experiments, the water- and oil-repellent antifouling tiles manufactured by excluding the substance Si (OA) ₄ having an alkoxysilyl group as a main component are not practical, but have an alkoxysilyl group as a main component. Compared to the water / oil repellent / antifouling tile produced by adding the substance Si (OA) ₄ , it was confirmed that the water contact performance was high at 105 degrees or more, so that the water separation performance was inferior. It was also confirmed that the wear resistance was inferior.

In Example 3, the excess composite film forming solution on the tile surface was removed by washing with ethanol, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group having a thickness of about 5 nm and a siloxane group were mainly used. After the formation of the lower layer composite film containing the substance as a component, the following steps were subsequently added to form a water / oil repellent film having a two-layer structure.

The added process is shown below.
That is, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group in a dry atmosphere (humidity is preferably 50% or less) in advance. OA) ₃ and dissolved in a 5% chloroform-containing dimethyl silicone solution containing almost no water, which is a non-aqueous organic solvent, so as to have a concentration of 0.01 M / L, and dibutyltin acetate is further added as a silanol condensation catalyst. An upper layer film-forming solution was prepared by adding and dissolving to a concentration of 0.0001 M / L.

  Next, a tile on which a lower composite film is formed is prepared, and further, the composite film forming solution is applied to the lower composite surface in a dry atmosphere (humidity is preferably 50% or less), and at room temperature for 1 to 2 hours. The reaction was allowed to stand.

At this time, since a hydroxyl group, that is, active hydrogen is exposed to some extent on the surface of the lower layer composite film on the tile surface, ≡SiOA of a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group on the tile surface. The group and the hydroxyl group were subjected to dealcoholization reaction in the presence of a silanol catalyst, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group was bonded to the tile surface via the silyl group.

Thereafter, the excess upper layer film forming solution on the surface is removed by washing with ethanol, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a substance mainly composed of a siloxane group, having a thickness of about 7 nm. It was possible to form a coating having a two-layer structure on the surface of the tile, with the composite film including the lower layer as the upper layer and the coating containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group as the upper layer film.

Note that the non-aqueous organic solvent is evaporated without washing (in this case, when the tile is heated at 60 to 100 ° C., the evaporation of the solvent can be accelerated and the evaporation time can be shortened). A 50 nm thick two-layer coating could be formed on the tile surface.
Moreover, when it wiped off with the cloth, it became about 20 nm thickness.

Hereinafter, in the same manner as in Example 3, each tile on which a two-layered film is formed is subjected to 400 ° C. for 20 minutes in nitrogen gas that is an atmosphere that does not substantially contain oxygen, or in nitrogen gas that contains hydrogen below the explosion limit. When heat treatment is performed to the extent, most of the ≡SiOH groups remaining in the film undergo a dehydration reaction to form a polysiloxane bond and change to a network-like silica film. An underlayer composite film containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and a substance mainly composed of a siloxane group, which has a property as high as 1.5 times and excellent in water repellency and weather resistance; A highly durable water- and oil-repellent and antifouling tile having a two-layered film formed of an upper layer film containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group could be produced. In this case as well, a tile having a water repellent, oil repellent and antifouling property 5 times higher than that when fired at 250 ° C. could be produced.

The contact angle of the water / oil / oil repellent antifouling tile with respect to water was within about 105 ± 3 degrees, regardless of whether or not cleaning was performed.

Further, the falling angle of 0.02 ml water droplets was about 45 degrees. Furthermore, in the abrasion test, the contact angle with water was able to maintain 95 degrees or more with respect to 9000 times of rubbing under conditions of a load of 500 g / 4 cm ² . Furthermore, if a tile having an alkali barrier film previously formed on the tile surface was used, the water resistance could be further improved.

In addition, although manufacturing cost becomes high, it goes without saying that if the process of forming the lower layer composite film is repeated a plurality of times and then the process of forming the upper layer film is performed, a tile having further excellent durability can be obtained.

Further, it is needless to say that a tile that is considerably excellent in water and oil repellency can be produced without repeating the step of forming the lower layer composite film a plurality of times and without performing the step of forming the upper layer film.

When nitrogen gas containing 3% hydrogen (explosion limit is 4%) is used as the atmospheric gas during firing at 400 ° C. for 30 minutes, firing is performed without oxidizing the coating even if there is some oxygen in the furnace. did it.

Furthermore, in Examples 3 and 4, a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound could be used instead of the above-mentioned silanol condensation catalyst.
For example, in Examples 3 and 4, a ketimine compound (H3 from Japan Epoxy Resin and Silaace S340 from Chisso was used in place of the silanol condensation catalyst described above, the performance was almost the same). When used at the same concentration, the reaction time could be shortened to 30 minutes.

Furthermore, in Examples 3 and 4, when the above-mentioned silanol condensation catalyst and ketimine compound, or aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound are used in a mixture of 1: 9 to 9: 1, further, The reaction time could be shortened to 20-3 minutes.
For example, in Examples 3 and 4, when the above-mentioned silanol condensation catalyst concentration was halved and the above-mentioned ketimine compound (for example, S340) was equimolarly mixed (1: 1), the reaction time could be shortened to 10 minutes. .

The ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3,10- Tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2, , 4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19 -There is trieicosadiene.

Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

CF as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group in a dry atmosphere (humidity of 35% or less is preferable. _{3 - (CF 2) 7 -} (CH 2) 2 and -SiCl _3, and SiCl ₄ as a material mainly containing chlorosilyl groups, 5% chloroform containing dimethyl silicone solution containing little water which is a non-aqueous organic solvent The composite film forming solution was prepared by dissolving in a concentration of 0.02 M / L and 0.01 M / L (2: 1), respectively.

  Next, the porcelain dish is thoroughly washed, dried, and then dried on the surface in a dry atmosphere (humidity is preferably 35% or less. When the temperature is higher than this, the film-forming substance is hydrolyzed and the film becomes cloudy). A film forming solution was applied and allowed to react at room temperature for 1 to 2 hours.

At this time, since the dish surface contains many hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, the ≡SiCl group of the two substances and the hydroxyl group or adsorbed water undergo a dehydrochlorination reaction on the porcelain dish surface. Then, the substance having the fluorocarbon group, the hydrocarbon group and the silyl group as main components and the substance having the siloxane group as main components were mixed and bonded to the surface of the porcelain dish.

A substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group is bonded to a porcelain dish surface or a substance mainly composed of a siloxane group via the silyl group, and the siloxane group is composed mainly of the siloxane group. The substance to be bonded was bonded to a porcelain dish surface or a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group via a siloxane group.

Thereafter, when the excess composite film forming solution on the surface is washed away with ethanol, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a substance mainly composed of a siloxane group having a thickness of about 5 nm are obtained. A composite film containing it could be formed on the surface of the porcelain dish.

The non-aqueous organic solvent is evaporated without washing (in this case, heating the porcelain dish at 60 to 100 ° C. can accelerate the evaporation of the solvent and shorten the evaporation time). A composite film containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group having a thickness of about 30 nm could be formed on the surface of the porcelain dish. When wiped off, the thickness was approximately 10 nm.

Then, when each porcelain dish on which the composite film is formed is further subjected to a heat treatment at 400 ° C. for about 30 minutes in nitrogen gas as an inert gas, the —SiCl ₃ group in the coating reacts with the adsorbed water. Most of the ≡SiOH groups generated in this way undergo a dehydration reaction to form polysiloxane bonds and change to a network-like silica film, which is a wear-resistant and water-resistant fluorocarbon group and hydrocarbon group. And a water- and oil-repellent composite film composed of a substance 1 containing silyl groups as a main component and a substance 2 containing siloxane groups as a main component, and an antifouling porcelain dish having high durability and excellent drainage characteristics. I was able to manufacture it.

At this time, the light transmittance of the composite film was 98% or more with respect to light having a wavelength of 400 to 700 nm regardless of whether or not the film was washed. There was no. In addition, the water droplet contact angle of the antifouling porcelain dish is approximately 104 degrees (critical surface energy is about 12 mN / m) regardless of whether or not the cleaning process is performed, and the oil repellency is equivalent to or higher than that of a Teflon (registered trademark) coat. Could be granted.

Further, the falling angle of 0.02 ml water droplets was about 30 degrees. This value is a level at which almost all water drops flow down when the tableware is stood, and the draining characteristics are outstanding. Furthermore, in the abrasion test, the contact angle with respect to water was able to maintain 95 degrees or more with respect to the reciprocating 6000 times of rubbing on the conditions of a load of 500 g / 4cm < ² >. This condition corresponds to the condition of wiping the surface hundreds of thousands of times with a cloth.

In addition, before performing heat processing, when the same film-forming process was repeated once and heat processing was performed after that, the antifouling film | membrane of 2 layer structure was able to be formed. In this case, needless to say, the durability of the coating could be further improved.

Furthermore, the outermost surface layer is formed by changing the composition ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group to the substance mainly composed of chlorosilyl group at the time of forming the second layer film. Once formed, the initial contact angle for water was 109 degrees. In the abrasion resistance test, 1.8 times durability was obtained.
(Comparative Example 3)

In Example 7, a dish made of water and oil repellent antifouling porcelain was produced under the same conditions except for the substance SiCl ₄ mainly composed of chlorosilyl groups. That is, it was made of 100% of a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group. In this case, when the contact angle with water, which is the basic performance, was measured, it was 112 degrees.

The drop angle of the water droplet was 0.02 ml, and was about 50 degrees initially.

In view of practicality, the contact angle of 95 degrees, the most favorable water separation performance, could withstand up to 2800 round trips.

Therefore, since the contact angle with respect to water is as extremely high as 110 degrees or more, a good antifouling function can be imparted to the porcelain dish. There was also some durability.

However, it was confirmed that the durability was inferior compared to the case where a composite film containing a substance mainly containing a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly containing a siloxane group was formed. Further, the water repellency was high, the water drop falling angle was high, and the drainage was poor.

On the other hand, in Example 7 and Comparative Example 3, instead of a normal porcelain dish, a porcelain dish having a silica film formed on the surface with a thickness of about 10 microns using a sol-gel method is used. Alkaline component elution from porcelain dishes can be reduced, and weather resistance and water resistance can be improved more than twice. (The same applies to general ceramic products)

First, a porcelain dish was prepared, washed thoroughly and dried. Next, for example, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (Si (OC ₂ H ₅ ) ₃ ) 59 is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. .7% by weight, Si (OC ₂ H ₅ ) ₄ as a substance having an alkoxysilyl group as a main component, 40% by weight, and silanol condensation catalyst as, for example, dibutyltin oxide, 0.3% by weight Adjusted and dissolved in a silicone solvent containing almost no water, such as hexamethyldisiloxane solvent, to a total concentration of about 0.2% by weight (preferably about 0.05 to 1%). A film forming solution was obtained.

The composite film-forming solution was applied to the surface of the porcelain dish in normal air (relative humidity 57%, 70% in another experiment). The solvent was evaporated. At this time, since the porcelain dish surface contains a large number of hydroxyl groups, ≡Si of the substance mainly composed of the fluorocarbon group, the hydrocarbon group and the alkoxysilyl group and the substance mainly composed of the alkoxysilyl group. The (OC ₂ H ₅ ) group reacts with the hydroxyl group and adsorbed water on the surface of the porcelain dish in the presence of a silanol condensation catalyst, and in this case, de-C ₂ H ₅ OH, and further, the porcelain dish The surface of the porcelain dish is also subjected to a dealcoholization reaction between the unreacted fluorocarbon group, hydrocarbon group, alkoxysilyl group-based material, and alkoxysilyl group-based material as well as moisture in the air. A composite film comprising a substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance 2 mainly composed of a siloxane group, which is chemically bonded to the surface over the entire surface, is manufactured by the above porcelain. Was formed on the surface of the dish.

On the other hand, when the excessive composite film forming solution on the surface is removed by washing with ethanol (fifth invention), the substance 1 and siloxane having a fluorocarbon group, a hydrocarbon group, and a silyl group as main components having a thickness of about 5 nm. A composite film containing the substance 2 containing the group as a main component could be formed on the surface of the porcelain dish. When wiped off, the thickness was approximately 15 nm.

Then, when each porcelain dish on which the composite film is formed is subjected to a heat treatment at 400 ° C. for about 30 minutes in an inert gas, nitrogen gas, the —Si (OC ₂ H ₅ ) group reacts with the adsorbed water. Most of the ≡SiOH groups generated in this way undergo a dehydration reaction to form polysiloxane bonds and change to a mesh-like silica film, which is a fluorescein with excellent wear resistance and water separation (also referred to as water slidability). Highly durable having substantially the same physical properties as in Example 7 with a composite film having antifouling properties consisting of a substance 1 mainly composed of carbonized carbon, hydrocarbon and silyl groups and a substance 2 mainly composed of siloxane groups. Moreover, an antifouling porcelain dish excellent in draining characteristics could be produced.

In addition, before performing heat processing, when the same film-forming process was repeated once and heat processing was performed after that, the antifouling film | membrane of 2 layer structure was able to be formed. In this case, needless to say, the durability of the coating could be further improved.

  Furthermore, the composition ratio of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and a substance mainly composed of an alkoxysilyl group is changed at the time of forming the second layer film, for example, 1: 0. That is, when the outermost surface layer was formed only of a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, the initial contact angle with respect to water could be 111 degrees. In the abrasion resistance test, 1.7 times durability was obtained.

In Example 8, a single layer of water / oil repellent / antifouling film was formed under the same conditions except for the substance Si (OC ₂ H ₅ ) ₄ having an alkoxysilyl group as a main component. When the contact angle with water, which is the basic performance, was measured, it was 111 degrees. Further, the drainage characteristic ability and durability are slightly inferior to those of Examples 7 and 8, but other physical property values are almost the same as those of Comparative Example 3, and an antifouling porcelain dish that can be put to practical use is used. I was able to manufacture it.

On the other hand, in place of the porcelain dish in Example 8 and 9, when a porcelain dish having a silica film formed on the surface with a thickness of about 10 microns by using the sol-gel method is used, a base porcelain dish Elution of alkaline components from the water, and improved weather resistance and water resistance more than double. Furthermore, when the base is a ceramic top plate for an electromagnetic cooker, before the antifouling film is formed, if a plurality of fine protrusions (about 0.5 to 2 mm) are provided on the top plate surface in advance, the film is directly applied to the pan bottom. The contact was eliminated and the durability of the coating could be improved.

The manufacturing process of the antifouling tile of this invention is shown, (a) is the tile surface after film formation in Example 1, (b) is the water-repellent and oil-repellent antifouling film after baking in Example 1. (C) is a conceptual cross-sectional view in which the tile surface on which the two-layered water- and oil-repellent and antifouling film of Example 2 is formed is enlarged to the molecular level. The figure which compared and showed the abrasion resistance test result of the antifouling tile manufactured in Example 1 and 2 and the comparative example 1. FIG. The figure which plotted the data obtained by the preliminary experiment in performing this invention, and showed the relationship between the contact angle with respect to water, and a fall angle. The manufacturing process of the water-repellent / oil-repellent antifouling tile of the present invention is shown, (a) is the tile surface after the coating is formed in Example 3, and (b) is the water- and oil-repellent after firing in Example 3. The tile surface on which the antifouling film was formed, (c) is a conceptual cross-sectional view in which the tile surface on which the water- and oil-repellent antifouling film having a two-layer structure after firing in Example 4 is formed is enlarged to the molecular level. The figure which compared and showed the abrasion resistance test result of the water-repellent | oil-repellent | oil-repellent antifouling tile manufactured in Example 3 and 4 and the comparative example 2. FIG.

Explanation of symbols

1, 1 'Substance 2 mainly composed of fluorocarbon group, hydrocarbon group and silyl group 2 Substance 2 mainly composed of siloxane group
3 Porcelain tile 4, 4 'hydroxyl group 5 composite film 6 containing many hydroxyl groups 4 network-like silica film 6' network-like silica film 7 water-repellent / oil-repellent / anti-fouling composite film 7 'lower layer composite film 8 upper layer film 9 Two-layer water / oil repellent / antifouling film 11, 11 ′ Substance 12 mainly composed of fluorocarbon group, hydrocarbon group and silyl group 12 Substance 2 mainly composed of siloxane group
13 Tile 14, 14 'Hydroxyl 15 Composite film 16 containing many hydroxyl groups 4 Reticulated silica film 16' Reticulated silica film 17 Water repellent / oil repellent / antifouling composite film 17 'Lower layer composite film 18 Upper layer film 19 2 layers Structure Water and oil repellent antifouling film

Claims (35)

  A ceramic product on which a highly durable water / oil repellent / antifouling coating is formed, wherein the water / oil repellent / antifouling coating comprises at least a fluorocarbon group, a hydrocarbon group and a silyl group as main components. And an antifouling ceramic product comprising at least one layer of a composite film containing a substance mainly composed of a siloxane group.   A substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group is bonded to the surface of the silica film and / or ceramic product through the silyl group in a silica film composed of a substance mainly composed of a siloxane group. The antifouling ceramic product according to claim 1, wherein the antifouling ceramic product is bonded and fixed.   A substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group are bonded and fixed to the surface of the ceramic product through the silyl group and the siloxane group, respectively, or individually. The antifouling ceramic product according to claim 1, wherein   A ceramic product on which a highly durable water / oil / oil repellent antifouling film is formed, wherein the film is mainly composed of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a siloxane group. An antifouling ceramic product characterized by comprising a two-layer structure film comprising a lower layer composite film containing a substance and an upper layer film containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group.   A substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group constituting the lower layer composite film is a silica film composed of a substance mainly composed of a siloxane group. / Or a siloxane group that is bonded and fixed to the surface of the ceramic product, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group constituting the upper layer film is contained in the lower layer composite film via the silyl group The antifouling ceramic product according to claim 4, wherein the antifouling ceramic product is bonded and fixed to.   A material mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a material mainly composed of a siloxane group constituting the lower layer composite film are ceramic products individually or individually via a silyl group and a siloxane group, respectively. Bonded and fixed on the surface, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group constituting the upper layer film is bonded and fixed to a siloxane group contained in the lower layer composite film via the silyl group. The antifouling ceramic product according to claim 4.   The molecular composition ratio of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group contained in the composite film is 1:10 to 10: 1. The antifouling ceramic product according to any one of claims 1 to 6.   8. The antifouling ceramic product according to claim 1, wherein a contact angle of the composite membrane with respect to water is controlled to 95 ± 10 degrees.   7. The antifouling ceramic product according to claim 4, wherein a contact angle of the upper layer film with water is controlled to 105 ± 10 degrees. 7. The antifouling ceramic product according to claim 1, wherein a ceramic product having an alkali barrier film formed on the surface in advance is used as the ceramic product. 11. The antifouling ceramic product according to claim 1, wherein the ceramic product is a ceramic top plate for tableware, flower vase, sanitary ware, insulator, tile, and electromagnetic cooker. Prepared by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group, and chlorosilyl group and a substance mainly composed of chlorosilyl group in a dry atmosphere with a non-aqueous organic solvent on the surface of at least the base ceramic product. An antifouling ceramic industry comprising a step of forming a film by bringing a composite film-forming solution into contact with each other and a step of firing the ceramic product on which the film is formed in an atmosphere substantially free of oxygen Product manufacturing method.   Prepared by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group, and chlorosilyl group and a substance mainly composed of chlorosilyl group in a dry atmosphere with a non-aqueous organic solvent on the surface of at least the base ceramic product. A step of bringing a composite film-forming solution into contact with each other to form a film; a step of removing or wiping off an excess solution on the surface of the ceramic product using an organic solvent; and a substantially oxygen-free atmosphere. A method for producing an antifouling ceramic product, comprising a step of firing.   The molecular mixing ratio of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group is set to 1:10 to 10: 1. 14. A method for producing an antifouling ceramic product according to 12 and 13. CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group, and SiCl is used as a substance mainly composed of a chlorosilyl group. ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si (OC ₂ ) instead of a substance having a chlorosilyl group as a main component. H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , Or (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is 1:10 to 10: 1 13. A method according to claim 12, wherein Method for producing antifouling ceramic product according to 4. Prepared by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group, and chlorosilyl group and a substance mainly composed of chlorosilyl group in a dry atmosphere with a non-aqueous organic solvent on the surface of at least the base ceramic product. Mixing and diluting a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group in a dry atmosphere with a non-aqueous organic solvent The upper layer film forming solution thus prepared is brought into contact with the ceramic product surface on which the lower layer composite film is formed to react with it, and an upper layer film is formed; and the ceramic product on which the lower layer composite film and the upper layer film are formed is substantially oxygenated. A method for producing an antifouling ceramic product, comprising a step of firing in an atmosphere not containing the antifouling ceramic product.   Prepared by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group, and chlorosilyl group and a substance mainly composed of chlorosilyl group in a dry atmosphere with a non-aqueous organic solvent on the surface of at least the base ceramic product. A step of contacting and reacting the composite film forming solution to form a lower layer composite film; a step of removing or wiping off an excess solution on the ceramic product surface on which the lower layer composite film is formed using an organic solvent; and drying. Contact the surface of the ceramic product on which the lower layer composite film is formed with the upper layer film formation solution prepared by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group with a non-aqueous organic solvent in the atmosphere. A step of forming an upper layer film by reacting, and a step of washing or wiping off an excess solution on the surface of the ceramic product on which the upper layer film is formed using an organic solvent; Method for producing antifouling ceramic product characterized in that it comprises a step of firing in an atmosphere containing no.   The molecular mixing ratio of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group is set to 1:10 to 10: 1. 16. A method for producing an antifouling ceramic product according to 16 and 17. CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer) is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group, and SiCl is used as a substance mainly composed of a chlorosilyl group. ₄ or SiHCl ₃ , SiH ₂ Cl ₂ , Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer), or Si (OCH ₃ ) ₄ or Si (OC ₂ ) instead of a substance having a chlorosilyl group as a main component. H ₅ ) ₄ , (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃ (where m is an integer), SiH (OC ₂ H ₅ ) ₃ , SiH ₂ (OC ₂ H ₅ ) ₂ , Or (C ₂ H ₅ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅ (where m is an integer), and the molecular composition ratio during mixing is 1:10 to 10: 1 17. A device according to claim 16, wherein Method for producing antifouling ceramic product according to 8. At least the surface of the base ceramic product is mixed and diluted with a non-aqueous organic solvent with a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, a substance mainly composed of an alkoxysilyl group and a silanol condensation catalyst. An antifouling property comprising a step of forming a film by contact reaction of the prepared composite film forming solution, and a step of firing the ceramic product on which the film is formed in an atmosphere substantially free of oxygen. Manufacturing method for ceramic products.   Prepared by mixing and diluting at least the surface of the ceramic products with a non-aqueous organic solvent with a substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group, a substance mainly composed of alkoxysilyl group and a silanol condensation catalyst. A step of forming a film by contact-reacting the composite film forming solution, a step of removing or wiping off an excess of the composite film forming solution on the surface of the ceramic product using an organic solvent, and a substantially oxygen-free atmosphere. A method for producing an antifouling ceramic product, comprising a step of baking in the soil.   A molecular mixing ratio of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and a substance mainly composed of an alkoxysilyl group is set to 1:10 to 10: 1. The method for producing an antifouling ceramic product according to claim 20 or 21. CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ as substances mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and Si ( OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl or ethyl group, a propyl group, etc. Instead of a compound represented by a short-chain alkyl group) or a substance having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (provided that m is an integer) The method for producing an antifouling ceramic product according to any one of claims 20 to 22, wherein the molecular composition ratio during mixing is 1:10 to 10: 1. Prepared by mixing and diluting at least the surface of ceramic products with a substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group, substance based on alkoxysilyl group and silanol condensation catalyst with non-aqueous organic solvent. A step of forming a lower layer composite film by contact reaction of the composite film forming solution, and a silanol condensation with a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group on the ceramic product surface on which the lower layer composite film is formed The step of forming an upper layer film by contact reaction of an upper layer film forming solution prepared by mixing and diluting a catalyst with a non-aqueous organic solvent, and the ceramic product formed with the lower layer composite film and the upper layer film are substantially free of oxygen. A method for producing an antifouling ceramic product, comprising a step of firing in an atmosphere. Composite made by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group, substance mainly composed of alkoxysilyl group and silanol condensation catalyst on non-aqueous organic solvent on the surface of ceramic products A step of contacting a film-forming solution to form a lower layer composite film; a step of removing or wiping off an excess solution on the ceramic product surface on which the lower layer composite film is formed using an organic solvent; and the lower layer composite film The upper layer film forming solution prepared by mixing and diluting a substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group and silanol condensation catalyst with non-aqueous organic solvent is contact-reacted A step of forming an upper layer film, a step of washing or wiping off an excess solution on the ceramic product surface on which the upper layer film is formed using an organic solvent, a lower layer composite film and Method for producing antifouling ceramic product characterized in that it comprises a step of firing ceramic products layer film formed in an atmosphere containing substantially no oxygen. A molecular composition ratio at the time of mixing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and a substance mainly composed of an alkoxysilyl group is set to 1:10 to 10: 1. A method for producing an antifouling ceramic product according to claim 24 and 25. CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ Si (OA) ₃ , [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ as substances mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. ] ₂ Si (OA) ₂ or [CF ₃ (CF ₂ ) _n (CH ₂ ) ₂ ] ₃ SiOA (n is an integer, A is an alkyl group), and Si ( OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is an integer, A is a methyl or ethyl group, a propyl group, etc. Instead of a compound represented by a short-chain alkyl group) or a substance having an alkoxysilyl group as a main component, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (provided that m is an integer) The method for producing an antifouling ceramic product according to any one of claims 24 to 26. The method for producing an antifouling ceramic product according to claim 24 and 27, wherein only the step of forming the lower layer composite film is repeated a plurality of times, and the upper layer film forming step is not performed. 28. The method for producing an antifouling ceramic product according to claim 24, wherein an upper layer film forming step is performed after the step of forming the lower layer composite film is repeated a plurality of times. 30. The production of an antifouling ceramic product according to any one of claims 20 to 29, wherein a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used in place of the silanol condensation catalyst. Method. 30. The production of an antifouling ceramic product according to any one of claims 20 to 29, wherein a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed and used. Method.   26. The method for producing an antifouling ceramic product according to claim 13, 17, 21 and 25, wherein the product is washed with a detergent and water instead of washing with an organic solvent.   Baking is performed at 300 to 450 ° C. using nitrogen gas or nitrogen gas containing hydrogen below the explosion limit as an atmosphere substantially free of oxygen. 26. A method for producing an antifouling ceramic product according to 24 or 25. 26. The antifouling ceramic product according to claim 12, 13, 16, 17, 20, 21, 24, and 25, wherein a ceramic product having an alkali barrier film previously formed on the surface is used as the base ceramic product. Manufacturing method. 26. The method for producing an antifouling ceramic product according to claim 12, 13, 16, 17, 20, 21, 24, and 25, wherein the base ceramic product is a tableware, flower vase, sanitary ware, insulator, or tile. .

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