JP5487429B2 - Water / oil repellent / antifouling treatment liquid, method for producing the same, and water / oil repellent / antifouling treatment using the same - Google Patents

Description

The present invention relates to a water / oil repellent / antifouling treatment liquid, a production method thereof, and a water / oil repellent / antifouling treatment method using the same. More particularly, the present invention relates to a water / oil / oil / repellency treatment solution used for the production of a water / oil / oil / repellency treatment film chemically bonded to the substrate surface, a method for producing the same, and a water / oil / oil / oil repellent treatment method using the same. is there.

In general, a chemical adsorption solution 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 film-like water / oil repellent / antifouling chemical adsorption film. Is already well known (see, for example, 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. 05-193056

However, the conventional water-repellent treatment method using a chlorosilane-based water- and oil-repellent antifouling chemical adsorbent can only use a non-aqueous organic solvent, so the treatment liquid is expensive and the environmental load is highly recommended. It wasn't possible.

Further, since a dehydrochlorination reaction between the active hydrogen group and the chlorosilyl group on the substrate surface is used for film formation, hydrochloric acid is generated and there is a great drawback that it cannot be used in the atmosphere.

The present invention relates to a water / oil repellent / antifouling treatment liquid capable of forming a water / oil repellent / antifouling film excellent in abrasion resistance and water resistance without using a conventional non-aqueous organic solvent, and a method for producing the same An object is to provide a water and oil repellent antifouling treatment method.

It is another object of the present invention to provide a water and oil repellent antifouling treatment liquid that does not generate hydrochloric acid gas during film formation and can be formed in a normal air atmosphere, and a method for producing the same.

In order to achieve the above object, the first invention specifically provided includes at least a substance containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, a substance containing an alkoxysilyl group as a main component, and water. And a composition ratio of a substance containing alcohol and / or a surfactant and containing the fluorocarbon group , hydrocarbon group, and alkoxysilyl group and a substance containing the alkoxysilyl group as a main component is 1: 3 to 3: 1. The total concentration of the substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group and the substance containing the alkoxysilyl group as a main component is 0.01 to 0.0001 mol / L. It is a water / oil repellent antifouling treatment liquid.

A second invention is a water / oil repellent / antifouling treatment liquid characterized in that, in the first invention, alcohol or a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 1) is used as a surfactant. is there.

According to a third invention, in the first or second invention, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si () is a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. OA) ₃ or _{[CF 3 - (CF 2)} n - (CH 2) 2] 2 -Si (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA (n is 0 or an integer of 16 or less, and A is an alkyl group).

A fourth invention is the first to In the third invention of any one of, Si as a substance composed mainly of alkoxysilyl group _{(OA) 4} or _{(AO) 3 Si (OSi (} OA) 2), n OSi (OA) ₃ (n is an integer of 0 or 1, and A is an alkyl group) is a water / oil / oil repellent antifouling treatment liquid.

A fifth invention is the water / oil repellent antifouling treatment liquid according to any one of the first to fourth inventions, wherein the pH of the treatment liquid is 5 to 11.

According to a sixth aspect of the present invention, at least a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, a substance containing an alkoxysilyl group as a main component, water, an alcohol and / or a surfactant are contained in the above-described fluorine. The composition ratio of the substance containing a carbonized carbon group , a hydrocarbon group, and an alkoxysilyl group and the substance containing the alkoxysilyl group as a main component is 1: 3 to 3: 1, and the fluorocarbon group, the hydrocarbon group, and the alkoxy A water / oil repellent / antifouling treatment liquid characterized by mixing and dispersing so that the total concentration of a substance containing a silyl group and a substance containing an alkoxysilyl group as a main component is 0.01 to 0.0001 mol / L It is a manufacturing method.

According to a seventh invention, in the sixth invention, alcohol or a tetraalkylammonium salt represented by the above chemical formula (Chemical Formula 1) is used as a surfactant and dispersed using a homogenizer or an ultrasonic disperser. This is a method for producing a water / oil repellent antifouling treatment liquid.

The eighth invention includes at least a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, a substance containing an alkoxysilyl group as a main component, water, an alcohol and / or a surfactant, A water repellent composition having a composition ratio (referring to the ratio of the number of silicon atoms) of a substance containing a fluorocarbon group , a hydrocarbon group, and an alkoxysilyl group and a substance containing the alkoxysilyl group as a main component is 1: 3 to 3: 1. A water / oil repellent / antifouling treatment method characterized by forming a water / oil repellent / antifouling coating film covalently bonded to the surface of the substrate by bringing the oil repellent / antifouling treatment liquid into contact with the substrate. is there.
A ninth invention includes a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, a substance containing an alkoxysilyl group as a main component, water, an alcohol and / or a surfactant, A water / oil repellent having a composition ratio (referring to the ratio of the number of silicon atoms) of a substance containing a carbon group , a hydrocarbon group and an alkoxysilyl group and a substance containing the alkoxysilyl group as a main component (referred to a ratio of the number of silicon atoms). An article characterized in that an antifouling treatment solution is contacted to form a water / oil repellent antifouling film covalently bonded to the surface.

More specifically, the present invention includes at least a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, a substance containing an alkoxysilyl group as a main component, water, alcohol, and / or an interface. The activator is mixed so that the total concentration of the substance containing the fluorocarbon group, the hydrocarbon group, and the alkoxysilyl group and the substance mainly composed of the alkoxysilyl group is 0.01 to 0.0001 mol / L. The dispersion step includes at least a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, a substance containing an alkoxysilyl group as a main component, water, an alcohol and / or a surfactant, the composition ratio of the substance as a main component material and the alkoxysilyl group containing a carbon hydrocarbon group and an alkoxysilyl group is 1: 3 to 3: 1 is water-repellent, oil-repellent, There is provided a processing solution.

Here, as alcohols, so-called alcohols are all possible, but in particular, ethanol, propyl alcohol, butanol, ethylene glycol is a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, or alkoxysilyl. A substance containing a group as a main component is preferable because it can be efficiently dispersed in water. On the other hand, when a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 1) is used as the surfactant, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group or an alkoxysilyl group is mainly used. Conveniently, the component substances can be dispersed efficiently in water.

Further, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [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, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA (n is 0 or 16 an integer, a is an alkyl group) When is used, it is convenient in improving the water / oil repellent / antifouling effect.

On the other hand, Si (OA) ₄ or (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (n is an integer of 0 or 1, ₂ ) When an alkyl group is used, it is convenient because durability such as abrasion resistance of the water / oil repellent / antifouling film can be improved.

Further, controlling the pH of the treatment liquid to 5 to 11 is convenient for forming a coating film with high density.

At this time, an alcohol as the alcohol, using a tetraalkylammonium salt represented by the above Symbol Chemical formula (Formula 1) as a surfactant and dispersed with a homogenizer or an ultrasonic dispersing machine, a treatment liquid Convenient for achieving uniformity and stability.

Furthermore, it is not necessarily performed after the treatment liquid and the substrate are brought into contact with each other. However, when the excess treatment liquid is washed with an organic solvent, the substrate surface is repelled with a uniform thickness covalently bonded to the substrate surface. It is convenient to form a water / oil repellent antifouling film.

As described above, according to the present invention, there is provided a water / oil repellent / antifouling treatment liquid capable of forming a water / oil repellent / antifouling film excellent in abrasion resistance and water resistance without using an organic solvent. There is an effect that can be done.

In addition, there is an effect that it is possible to provide a water / oil repellent / antifouling treatment method that does not generate hydrochloric acid gas during the formation of a film and can be formed in a normal air atmosphere.

The present invention provides a water / oil repellent / antifouling treatment liquid having high durability and high water / oil repellent / antifouling function, a production method thereof, and a water / oil repellent / antifouling treatment method using the same.

Substances mainly composed of at least fluorocarbon group, hydrocarbon group and alkoxysilyl group and water and alcohol and / or surfactant, or at least composed mainly of fluorocarbon group, hydrocarbon group and alkoxysilyl group At least a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group are mainly formed by mixing a substance, a substance mainly composed of an alkoxysilyl group, water, an alcohol and / or a surfactant and dispersing the mixture with an ultrasonic disperser. Water- and oil-repellent antifouling treatment liquid containing components and water, alcohol and / or surfactant, or a substance mainly composed of at least a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and an alkoxysilyl group Provided is a water / oil repellent / antifouling treatment liquid comprising a substance mainly composed of water, water, alcohol and / or a surfactant.

In addition, a water / oil repellent / antifouling treatment liquid capable of forming a water / oil repellent / antifouling film excellent in wear resistance and water resistance without using a non-aqueous organic solvent is provided. There is an action that can be done.

Furthermore, there is an effect that it is possible to provide a water and oil repellent and antifouling treatment method that does not generate hydrochloric acid gas during the formation of a film and can form a film in a normal air atmosphere.

Hereinafter, specific examples of the present invention will be described. In the following examples, the molecular composition ratio means a molar ratio unless otherwise specified. Moreover,% means weight%.

First, as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, for example, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (Si (OCH ₃ ) ₃ ) and an alkoxysilyl group are included. Si (OCH ₃ ) ₄ as a main component is weighed so as to have a molecular composition ratio of 2: 1, and mixed in an aqueous solvent containing 10% ethanol by volume so as to be 0.01 mol / L. When treated with an ultrasonic disperser (so-called homogenizer) for about 10 minutes, a part of each —Si (OCH ₃ ) ₃ group is hydrolyzed to —Si (OH) ₃ group, ═Si (OH ) A completely transparent composite film forming solution containing a substance converted into _two groups or ≡SiOH groups could be prepared.

It should be noted that the simple stirring with a stirrer only yielded a slightly turbid liquid, and if left to stand, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group would be immediately separated and stable. The treated liquid was not obtained.

Next, a well-cleaned and dried porcelain dish 1 was prepared, and this composite film forming solution was used in the air (relative humidity 57%, 70% in another experiment was no problem). It was applied to the dish surface and left for about 1 hour. At this time, most of the water-alcohol solvent evaporates, but since the porcelain dish surface contains a large number of hydroxyl groups, a substance or alkoxy containing the fluorocarbon group, hydrocarbon group and alkoxysilyl group as main components is used. The portion converted to ≡SiOH group of the substance mainly composed of silyl group and the hydroxyl group on the surface of the porcelain dish are dehydrated, and the fluorocarbon group and carbonized chemically bonded to the surface over the entire surface of the porcelain dish. A composite film containing the substance 2 containing hydrogen groups and silyl groups as main components and the substance 3 containing siloxane groups as main components can be formed on the surface of the porcelain dish. (Fig. 1 (a))

Therefore, before the aqueous ethanol solvent of the composite film forming solution remaining on the surface completely evaporates, that is, before the film is completely cured, excess fluorocarbon groups and hydrocarbons that have not reacted with ethanol. When a substance mainly composed of a group and an alkoxysilyl group or a substance mainly composed of an alkoxysilyl group is washed and removed, the substance 2 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group having a thickness of about 5 nm. And a composite film containing a substance 3 mainly composed of a siloxane group could be formed on the surface of the porcelain dish. In addition, when it wiped off with the waste containing ethanol, it became about 15 nm thickness.

At this time, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group or a substance mainly composed of an alkoxysilyl group in the composite film forming solution is an alkoxysilyl group in a mixed solvent of water and alcohol. Is converted into —Si (OH) ₃ groups, and the surface of the ceramic product dish 1 contains a large number of hydroxyl groups, that is, active hydrogens (the same applies to glass products). (OH) ₃ groups and the hydroxyl group on the porcelain dish surface are dehydrated to mix the substance 2 mainly composed of fluorocarbon group, hydrocarbon group and silyl group with the substance 3 mainly composed of siloxane group. In this state, they are bonded to the surface of the porcelain dish 1 through -SiO- bonds.

However, in this state, a part 4 of the —SiOH group remains in the film without causing a dehydration reaction. (FIG. 1 (a)) Then, when each porcelain dish 5 on which a composite film is formed is heated in air at 120 to 300 ° C. for about 30 minutes, unreacted —SiOH groups are completely removed. A dehydration reaction forms a polysiloxane bond and changes to a mesh-like silica film 6, which has a fluorocarbon group, a hydrocarbon group, and a silyl group that are excellent in wear resistance and water separation (also referred to as water slidability). A porcelain dish covered with a water-repellent / oil-repellent / anti-fouling composite film 7 having a water droplet contact angle of 116 degrees made of the substance 2 having the main component and the substance 3 having the siloxane group as the main component could be manufactured. (Fig. 1 (b))

Here, when a heat treatment at 300 to 400 ° C. for about 30 minutes is performed in a nitrogen gas atmosphere that is an inert gas, the coating is not oxidized, and the water and oil and oil repellents are excellent in wear resistance. A porcelain dish covered with a dirty composite film could be produced.

In Example 1, a step of washing away or wiping off an unreacted extra fluorocarbon group, hydrocarbon group, and alkoxysilyl group as a main component or a substance having an alkoxysilyl group as a main component As a result, a film having a surface water droplet contact angle of approximately 113 degrees and a film thickness of several tens of nanometers was obtained. Even under these conditions, the transparency was not so much impaired, and when the base was opaque such as a porcelain dish, there was no problem in terms of gloss in practice.

In Examples 1 and 2, the molecular 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 preferably 1: When the ratio was 10: 1: 0 (more preferably 1: 3-3: 1), the surface energy of the coating could be controlled between 20-5 mN / m.

In addition, since the water droplet contact angle of the antifouling porcelain dish at this time depends on the composition of the substances 2 and 3, for example, if the composition is changed in the range of 1:10 to 1: 0, the critical surface energy The water droplet contact angle could be controlled in the range of 105 ± 13 degrees. Moreover, in the case of 1: 3-3: 1, the falling angle with respect to a 0.02 mL water droplet was controllable to 25-12 degrees, and the draining at the time of washing | cleaning improved.
Furthermore, a similar film was obtained even when the total concentration of the substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group and the substance containing the alkoxysilyl group as a main component was 0.05 mol / L. When prepared so as to be -0.0001 mol / L, gelation of the treatment liquid could be prevented, and the lifetime could be secured up to about 1 month.

In Example 1, a dish made of water and oil repellent and antifouling porcelain was produced under the same conditions except for the substance Si (OCH ₃ ) ₄ having an alkoxysilyl group as a main component. The contact angle with water, which is the basic performance of the coating film obtained in this case, was 118 degrees. In addition, drainage characteristic ability and high durability are slightly inferior to those of Example 1, but other physical property values are almost the same as those of Example 1, and antifouling porcelain dishes that can be put to practical use are manufactured. did it.

On the other hand, in Example 1, a water-alcohol solvent was prepared so that the tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 2), which is a cationic surfactant, was 0.0005 mol / L. A similar experiment was conducted in place of the surfactant solvent, but almost the same film could be formed.

Further, in the embodiment 1, the water - was added to tetraalkylammonium salts represented by the above Symbol formula is more cationic surfactants in an alcohol solvent (Formula 2) is 0.005 mol / L A similar experiment was performed, but almost the same film could be formed.

In Examples 1, 2, 3, and 5, all so-called alcohols could be used as the alcohol, but good results were obtained with ethanol, propyl alcohol, butanol, and ethylene glycol.

As the surfactant, any neutral or weakly alkaline surfactant can be used. However, a high-performance film could not be formed unless the pH of the preparation treatment liquid was 5 to 11. When the pH was less than 5, a high-density film could not be formed. On the other hand, when the pH exceeded 12, a part of the coating was destroyed.
Of the tetraalkyl ammonium salt represented by the above Symbol Chemical formula (Formula 1), particularly preferred are the number of carbon atoms in R ¹ was 12 to 16.

Furthermore, as a substance mainly composed of only a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, the following substances are generally exemplified.
_{CF 3 - (CF 2) n} - (R) m SiX p (OA) 3-p
(Where n is an integer of 0 or 16 or less, 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, an alkyl group or an alkoxy group. , A fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2, A is an alkyl group such as CH ₃ , C ₂ H ₅ , C ₃ H ₇ )

Specifically, the general formula _{CF 3 - (CF 2) n} - (CH 2) 2 -Si (OA) 3 or _{[CF 3 - (CF 2)} n - (CH 2) 2] 2 -Si (OA) ₂ , [CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ ] ₃ —SiOA (n is an integer of 0 or 16 or less, A is an alkyl group).

More specifically, the following substances (1) to (18) can be 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 ) ₃ (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 (OCH ₃ ) 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 ] ₃ SiOCH ₃
(17) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OC ₂ H ₅ ) ₂
(18) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOC ₂ H ₅
Further, as a substance mainly composed of an alkoxysilyl group, generally, Si (OA) ₄ or (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (n is 0 or 1, An integer of 2 and A is an alkyl group).

More specifically, the following substances (1) to (8) can be mentioned.
(1) Si (OCH ₃ ) ₄
(2) SiH (OCH ₃ ) ₃
(3) SiH ₂ (OCH ₃ ) ₂
(4) (CH ₃ O) ₃ SiOSi (OCH ₃ ) ₂ OCH ₃
(5) Si (OC ₂ H ₅ ) ₄
(6) SiH (OC ₂ H ₅ ) ₃
(7) SiH ₂ (OC ₂ H ₅ ) _{2
(8) (H 5 C 2} O) 3 SiOSi (OC 2 H 5) 2 OC 2 H 5

In addition, the process liquid of this invention is not limited to a base material at all. In general, water- and oil-repellent and antifouling of materials whose surfaces get wet with water (surfaces may be painted with paint, etc.) such as metals, ceramics, wood, stone, fiber, fur, or leather. Applicable to processing. Furthermore, a material whose surface does not wet with water, such as a painted surface or plastics that repels water, can be similarly applied if the surface is processed to be hydrophilic by plasma treatment or corona treatment.

More specifically,
(A) Examples of blades:
Kitchen knife, scissors, knife, cutter, carving knife, razor, clipper, saw, canna, chisel, cone, awl, cutting tool, drill blade, mixer blade, juicer blade, flour mill blade, lawn mower blade, Punch, press cut, staple blade, can open blade, or surgical knife.

(B) Examples of needles:
Acupuncture needles, sewing needles, sewing needles, tatami needles, injection needles, surgical needles, safety pins, etc.

(C) Examples of ceramic products:
Products made of ceramic, glass, ceramics or enamel. For example, sanitary ceramics (for example, toilet bowls, washbasins, baths, etc.), tableware (for example, tea bowls, dishes, bowls, cups, cups, bottles, coffee-boiled containers, pots, mortars, cups, etc.) Etc.), aquarium (aquaculture tank, appreciation aquarium, etc.), chemical laboratory equipment (beaker, reaction vessel, test tube, flask, petri dish, cooling tube, stir bar, stirrer, mortar, vat, syringe), tile, tile, Enamel tableware, enamel basin, enamel pan.

(D) Example of mirror:
Hand mirrors, sight mirrors, bathroom mirrors, bathroom mirrors, automotive mirrors (back mirrors, side mirrors), half mirrors, show window mirrors, department store product mirrors, etc.

(E) Examples of molding members:
Press mold, cast mold, injection mold, transfer mold, vacuum mold, blow mold, extrusion mold, inflation mold, fiber spinning Base, calendar processing roll, etc.

(F) Examples of ornaments:
Jewelry such as watches, eyeglass frames and pearls, pearls, pearls, rubies, emeralds, garnets, cat's eyes, diamonds, topaz, bloodstone, aquamarine, sardonyx, turquoise, jade, marble, amethyst, cameo, opal, crystal, glass, etc. Furthermore, platinum, gold, silver, copper, aluminum, titanium, tin or their alloys and stainless steel rings, bracelets, brooches, tie pins, earrings, necklaces and other precious metal decoration products.

(G) Examples of food molds:
Cake baking mold, cookie baking mold, bread baking mold, chocolate molding mold, jelly molding mold, ice cream molding mold, oven dish, ice tray, etc.

(H) Examples of cookware:
Pots, kettles, kettles, pots, frying pans, hot plates, grilled nets, oil drainers, octopus grilled plates, etc.

(I) Examples of paper: gravure paper, water / oil repellent paper, poster paper, high-grade brochure paper, etc.

(J) Examples of resins:
Polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyamideimide, polyester, aramid, polystyrene, polysulfone, polyethersulfone, polyphenylene sulfide, phenol resin, furan resin, urea resin, epoxy resin, polyurethane , Silicon resin, ABS resin, methacrylic resin, acrylate resin, polyacetal, polyphenylene oxide and the like.

(K) Examples of home appliances:
Television, radio, tape recorder, audio, CD, refrigeration equipment refrigerators, freezers, air conditioners, juicers, mixers, fan blades, lighting equipment, dials, permanent hair dryers, etc.

(L) Examples of sports equipment:
Skis, fishing rods, pole vaulting poles, boats, yachts, jet skis, surfboards, golf balls, bowling balls, fishing lines, fishnets, fishing floats, etc.

(M) Examples applied to vehicle parts:
(1) ABS resin: lamp cover, instrument panel, interior parts, motorcycle protector, (2) Cellulose plastic: car mark, handle (3) FRP (fiber reinforced resin): outer bumper, engine cover, (4 ) Phenolic resin: Brake (5) Polyacetal: Wiper gear, gas valve, carburetor parts (6) Polyamide: Radiator fan (7) Polyarylate: Direction indicator lens, instrument panel lens, relay housing (8) Polybutylene terephthalate: Rear end, front Fender (9) Polyamino bismaleimide: Engine parts, gearbox, wheel, suspension drive system (10) Methacrylic resin: Lamp cover lens, instrument panel and cover, Center mark (11) Polypropylene: Bumper (12) Polyphenylene oxide: Radiator Guriru, wheel cap (13) polyurethane: a bumper, fender, instrument panel, a fan (14) Unsaturated polyester resin: body, fuel tank, heater housing, instrument panels and the like.

(N) Examples of office supplies:
Fountain pens, ballpoint pens, sharp pencils, brush holders, binders, desks, chairs, bookshelves, racks, telephone stands, rulers, drafting tools, etc.

(O) Examples of building materials:
Roofing materials, outer wall materials, interior materials. Roof tiles include kiln tiles, slate tiles, and tin (galvanized iron plate). Outer wall materials include wood (including processed wood), mortar, concrete, ceramic sizing, metal sizing, bricks, stones, plastic materials, aluminum and other metal materials. Interior materials include wood (including processed wood), metal materials such as aluminum, plastic materials, paper, cloth and fur.

(P) Examples of stone:
Flower kite, marble, granite, etc. For example, buildings, construction materials, works of art, figurines, baths, tombstones, monuments, gateposts, stone walls, paving stones, etc.

(Q) Examples of musical instruments and audio equipment:
Percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and other acoustic equipment such as microphones and speakers. Specifically, drums, cymbals, violins, cellos, guitars, kotos, pianos, flutes, clarinets, shakuhachi, horns and other percussion instruments, stringed instruments, keyboard instruments, woodwind instruments, brass instruments, etc., microphones, speakers, Sound equipment such as earphones.

(R) Other:
The present invention can be applied to a substrate made of a high voltage-resistant insulator such as a thermos, a vacuum device, a power transmission insulator or a spark plug, which has a high water and oil repellent and antifouling effect.

The manufacturing process of the water-repellent / oil-repellent antifouling porcelain dish using the water / oil repellent / antifouling treatment liquid of the present invention is shown. (A) is a porcelain made after the formation of the composite coating in Example 1. (B) is a conceptual cross-sectional view in which the surface of the antifouling porcelain dish on which the composite film after firing in Example 1 is formed is enlarged to the molecular level.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Porcelain dish 2 Substance which has fluorocarbon group, hydrocarbon group, and silyl group as main component 3 Substance which has siloxane group as main component 4 Hydroxyl group 5 Composite film containing many hydroxyl groups 4 Reticulated silica film 7 Water / oil repellent antifouling composite film

Claims (9)

At least, a material containing a fluorocarbon hydrocarbon group and an alkoxysilyl group, a substance mainly containing alkoxysilyl group, and water, wherein the alcohol and / or surfactant, and the fluorocarbon group carbonized The composition ratio of a substance containing a hydrogen group and an alkoxysilyl group and a substance containing the alkoxysilyl group as a main component is 1: 3 to 3: 1, and a substance containing the fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group And a water / oil repellent / antifouling treatment liquid, wherein the total concentration of the substance mainly composed of alkoxysilyl groups is 0.01 to 0.0001 mol / L. The water / oil / oil repellent according to claim 1, wherein ethanol, propyl alcohol, butanol, ethylene glycol, or a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 1) is used as a surfactant. Soil treatment liquid.

As a substance containing a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ ] ₂ -Si (OA) ₂ , [CF _3- (CF ₂ ) _n — (CH ₂ ) ₂ ] ₃ —SiOA (n is an integer of 0 or 16 or less, A is an alkyl group) The water and oil repellent antifouling treatment liquid according to claim 1 or 2. Si (OA) ₄ or (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (n is an integer of 0, 1 or 2; A is alkyl) The water / oil repellent / antifouling treatment liquid according to any one of claims 1 to 3, wherein a base) is used. The water / oil repellent / antifouling treatment solution according to any one of claims 1 to 4, wherein the pH of the treatment solution is 5 to 11. Even without low, a material containing a hydrocarbon group and an alkoxysilyl group and fluorocarbon group, a material mainly containing alkoxysilyl group, and water, an alcohol and / or surfactant, and the fluorocarbon group The composition ratio of the substance containing a hydrocarbon group and an alkoxysilyl group and the substance containing the alkoxysilyl group as a main component is 1: 3 to 3: 1 and contains the fluorocarbon group, the hydrocarbon group, and the alkoxysilyl group. A method for producing a water / oil repellent / antifouling treatment liquid, characterized in that a substance and a substance mainly composed of alkoxysilyl groups are mixed and dispersed so that a total concentration of the substance is 0.01 to 0.0001 mol / L. The water / oil / oil repellent according to claim 6, wherein alcohol or a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 2) is used as a surfactant and dispersed using a homogenizer or an ultrasonic disperser. A method for producing a soil treatment liquid.

At least, a material containing a fluorocarbon hydrocarbon group and an alkoxysilyl group, a substance mainly containing alkoxysilyl group, and water, wherein the alcohol and / or surfactant, and the fluorocarbon group carbonized Water / oil repellent / antifouling treatment liquid having a composition ratio (referred to as a ratio of the number of silicon atoms) of a substance containing a hydrogen group and an alkoxysilyl group and a substance mainly composed of the alkoxysilyl group of 1: 3 to 3: 1. A water and oil repellent and antifouling treatment method comprising forming a water and oil repellent and antifouling coating film covalently bonded to the substrate surface on the surface of the substrate. At least, a material containing a fluorocarbon hydrocarbon group and an alkoxysilyl group, a substance mainly containing alkoxysilyl group, and water, wherein the alcohol and / or surfactant, and the fluorocarbon group carbonized Water / oil repellent / antifouling treatment liquid having a composition ratio (referred to as a ratio of the number of silicon atoms) of a substance containing a hydrogen group and an alkoxysilyl group and a substance mainly composed of the alkoxysilyl group of 1: 3 to 3: 1. To form a water- and oil-repellent and antifouling film covalently bonded to the surface.

Images