JP4542322B2 - Amorphous coating and anti-fogging amorphous coating - Google Patents

Description

  The present invention relates to an amorphous coating that is formed on the surface of various substrates to make the surface of the substrate hydrophilic.

  It is known that extremely good antifouling properties and antifogging properties can be obtained when the surface of a substrate such as glass, mirror, tile, or metal plate is made hydrophilic with a water contact angle of about 10 ° or less. Yes. Therefore, in order to form the surface of the base material with antifouling and antifogging properties, a hydrophilic film is formed on the surface of the base material.

Various types of hydrophilic coatings have been proposed in the past, but recently, hydrophilic coatings formed of a film supporting a photocatalyst such as titanium oxide have attracted particular attention (for example, Patent Document 1). reference).
Japanese Patent Laid-Open No. 10-314598

  However, photocatalytic activity such as anatase type or rutile type titanium oxide is in the form of particles, and the film supporting the photocatalyst particles has reduced light transmittance and the photocatalyst particles have a high refractive index, so the reflectance of the film As a result, the coating coloration due to the interference effect becomes a problem. In addition, the action of electrons or holes with high energy peculiar to the photocatalytic effect and the action of active oxygen and hydroxyl radicals excited by the photocatalyst particles degrade the binder forming the base material and the film, and the film on the base material It has the problem that the adhesiveness of is easy to fall.

  The present invention has been made in view of the above points, and is an amorphous material that is transparent, has low reflectivity, is less colored by interference, has high adhesion strength to a substrate, and can maintain hydrophilicity over a long period of time. The object is to provide a coating, and further to provide an antifogging amorphous coating capable of maintaining antifogging properties over a long period of time.

The amorphous coating film according to claim 1 of the present invention is a supernatant liquid obtained by precipitating a precipitate of a mixed solution obtained by mixing titanium tetrachloride with water and mixing phosphoric acid and magnesium hydroxide in the mixed solution. Is a film-forming solution (an aqueous solution containing phosphoric acid, titanic acid, and Mg cations), and this film-forming solution is formed into a film.

The anti-fogging amorphous coating according to claim 2 of the present invention is a mixture of titanium tetrachloride with water, and precipitates a precipitate of a mixed solution obtained by mixing phosphoric acid and magnesium hydroxide in this mixed solution. The supernatant liquid is a film-forming liquid (an aqueous solution containing phosphoric acid, titanic acid, and Mg cations), and the film-forming liquid is obtained to form a film. .

  The amorphous coating according to the present invention can exhibit hydrophilicity without having to carry photocatalyst particles, is transparent, has a low reflectance, and can reduce coloring due to interference. The adhesive strength to the material is high, and the hydrophilicity can be maintained for a long time.

  Moreover, according to the anti-fogging amorphous film which concerns on this invention, in addition to said effect, anti-fogging property can be maintained over a long period of time.

  Hereinafter, the best mode for carrying out the present invention will be described.

The amorphous coating film according to the present invention has an element composition of M-Ti-PO ( M is Mg ), and an aqueous solution containing phosphoric acid, titanic acid, and a cation of metal M is used as a film forming liquid. And an amorphous film can be formed by forming a film on the surface of the substrate.

  Further, the aqueous solution containing the phosphoric acid, titanic acid, and the cation of the metal M can further contain silicic acid. The film forming solution having this composition is used to form the surface of the substrate. In the case of forming a film, an amorphous film having an elemental composition of M-Ti-Si-PO can be formed.

In preparing the above film forming liquid, first, titanium tetrachloride is dissolved in water to prepare an aqueous solution of titanium tetrachloride. Titanic acid is generated in the aqueous solution of titanium tetrachloride. Next, a film forming liquid can be obtained by mixing phosphoric acid and a salt of metal M in an aqueous solution of titanium tetrachloride. As salts of metal M, which can be used hydroxide of the metal M, if metals M is magnesium, it is possible to use magnesium hydroxide. In the case of forming an amorphous film having an elemental composition of M-Ti-Si-P-O, silicic acid is further mixed at this time. Silicic acid can be mixed, for example, as sodium silicate.

  And the film forming liquid produced in this way is coated on the surface of a base material. The coating can be performed by a method such as application, spraying, dipping, roll coating, spin coating and the like. After coating in this way, the film can be dried or heat-treated to form an amorphous film on the surface of the substrate. Since this amorphous coating film is highly hydrophilic and the surface of the substrate can be formed hydrophilic, the amorphous coating film can be used for antifouling and antifogging applications.

  In the present invention, the base material that is an object for forming an amorphous coating is not particularly limited. For example, a ship bottom material, an outer wall material, a bathroom material, a bathtub material, an ornamental aquarium material, a circulating water utilization facility, Outdoor building materials, solar cell covers, solar water heater heat collector covers, railings, tunnel inner walls, soundproof walls, sound insulation walls, guard fences, road structures, blinds, glass, wheels, vehicle casings, building window glass , Vehicle window glass, vehicle windshield, vehicle mirror, road mirror, wash mirror, instrument panel cover, eyeglass lens, helmet shield, goggles, heat showcase, heat exchanger fins, glass / tub, wash counter, Amorphous coatings are formed on kitchen counters, roofing materials, roof toys, antennas, power transmission lines, contact lenses, etc. Forming a surface hydrophilic, in which the antifouling property and antifogging can be imparted.

  Next, the present invention will be specifically described with reference to examples.

Example 1
100 parts by mass of titanium tetrachloride was mixed with 1000 parts by mass of ion-exchanged water and stirred for 30 minutes or more. This mixed solution is used as a base solution. The base solution contains a titanium aco complex and its condensate. X-ray diffraction shows that this base liquid is a yellow transparent liquid, and what is obtained by evaporating to dryness is anatase or brookite type ultrafine particles (average particle diameter 10 nm) of titanium oxide (TiO ₂ ). It was confirmed by.

  Further, 4000 parts by mass of ion-exchanged water and 200 parts by mass of this base solution were mixed and stirred for 30 minutes or more. Let the mixed solution obtained in this way be A liquid.

  Next, 1000 mass parts of A liquid, 60 mass parts of phosphoric acid, and 20 mass parts of magnesium hydroxide were mixed and stirred. Then, this was left still to precipitate a precipitate, and the supernatant was used as a film-forming solution.

  And this film formation liquid was coated on the glass plate by dipping, and it formed into a film by heating at 320 degreeC for 30 minutes. When the film thus formed was measured by X-ray diffraction, it was in an amorphous state.

  When the contact angle of the surface of the amorphous coating thus obtained with respect to water was measured, it was 5 ° or less and had high hydrophilicity. Further, when this amorphous film was cooled to a temperature 5 ° C. lower than the dew point temperature and allowed to stand in the air, the occurrence of fogging was not visually recognized, and good antifogging properties were exhibited. In addition, when the surface of this film was written with a rice field with an oil-based ink pen (Terani Chemical Co., Ltd. “Magic Ink”) and poured into water, it was confirmed that all the oil-based ink was peeled off and the antifouling property was good. It was. Moreover, when the hardness of the amorphous film was measured as pencil hardness, it had a hardness of 9H or more. Furthermore, when the adhesiveness of the amorphous coating film was subjected to a cross-cut test, no peeling was observed in 100 × 100 of a 1 mm cross-cut, indicating strong adhesiveness. Further, when the transmittance of the amorphous film was measured, the decrease in the transmittance was 1% or less as compared with the glass on which the film was not formed.

(Example 2)
A film was formed in the same manner as in Example 1 except that the heating temperature after coating the film forming liquid on the glass plate was changed to 250 ° C.

  The film thus obtained is an amorphous film as in Example 1, and the contact angle, antifogging property, antifouling property against oil-based ink, pencil hardness, adhesion, and light transmittance are also described in Example. The same effect as 1 was obtained.

(Example 3)
A film was formed in the same manner as in Example 1 except that the heating temperature after coating the film forming liquid on the glass plate was changed to 150 ° C.

  The film thus obtained is an amorphous film as in Example 1, and the contact angle, antifogging property, antifouling property against oil-based ink, pencil hardness, adhesion, and light transmittance are also described in Example. The same effect as 1 was obtained.

Example 4
By mixing and uniformly stirring 1000 parts by mass of the liquid A obtained in Example 1, 2.5 parts by mass of phosphoric acid, 1 part by mass of magnesium hydroxide, and 250 parts by mass of sodium silicate No. 3, a film forming solution was obtained. It was.

  The film forming solution was coated on a glass plate by dipping, dried at room temperature, and then heated at 50 ° C. for 30 minutes to form a film. When the film thus formed was measured by X-ray diffraction, it was in an amorphous state.

  When the contact angle of the surface of the amorphous coating thus obtained with respect to water was measured, it was 5 ° or less and had high hydrophilicity. Further, when this amorphous film was cooled to a temperature 5 ° C. lower than the dew point temperature and allowed to stand in the air, the occurrence of fogging was not visually recognized, and good antifogging properties were exhibited. In addition, when the surface of this film was written with a rice field with an oil-based ink pen (Terani Chemical Co., Ltd. “Magic Ink”) and poured into water, it was confirmed that all the oil-based ink was peeled off and the antifouling property was good. It was. Moreover, when the hardness of the amorphous film was measured as pencil hardness, it had a hardness of 9H or more. Furthermore, when the adhesiveness of the amorphous coating film was subjected to a cross-cut test, no peeling was observed in 100 × 100 of a 1 mm cross-cut, indicating strong adhesiveness. Further, when the transmittance of the amorphous film was measured, the decrease in the transmittance was 1% or less as compared with the glass on which the film was not formed.

(Example 5)
A film was formed in the same manner as in Example 4 except that the heating temperature after coating the film forming liquid on the glass plate and drying was changed to 100 ° C.

  The film thus obtained is an amorphous film as in Example 4, and the contact angle, antifogging property, antifouling property against oil-based ink, pencil hardness, adhesion, and light transmittance are also described in Example. The same effect as 4 was obtained.

  Moreover, the amorphous coating film of Example 4 and Example 5 described above is applied to the ship bottom material, the outer wall material, the bathroom material, the bathtub material, the ornamental water tank material, the circulating water utilization facility, the outdoor building material, the solar cell cover, and the solar water heater collection. Covers for thermal devices, railings, tunnel walls, sound barriers, sound barriers, guard fences, road structures, blinds, glass, wheels, automobile bodies, railroad car bodies, aircraft bodies and wings, vehicle housings, construction Window glass for objects, window glass for vehicles, windshield for vehicles, vehicle mirrors, road mirrors, wash mirrors, instrument panel covers, eyeglass lenses, helmet shields, goggles, warming showcases, heat exchanger fins, glass / tubs It was formed on the surface of the wash counter, kitchen counter, roofing material, roof toy, antenna, power line, and contact lens. The adhesion and hardness of the amorphous coating show the same characteristics as in Examples 4 and 5 above, and are highly hydrophilic and exhibit excellent antifouling properties. Were both high and all showed sustainability of more than one year.

  Furthermore, when the amorphous coatings of Examples 4 and 5 were formed on the surfaces of bathroom mirrors, mirrors for washing, glass inner surfaces for automobiles, goggles, heat insulating showcases, and window glass for buildings, all were untreated. Compared with No. 1, it showed remarkably high antifogging properties.

Claims (2)

A mixture of titanium tetrachloride with water and a mixture obtained by mixing phosphoric acid and magnesium hydroxide in this mixed solution is a supernatant liquid in which precipitates are precipitated, phosphoric acid, titanic acid, and Mg. An amorphous film characterized by being obtained by forming a film forming liquid containing a cation and forming the film forming liquid . A mixture of titanium tetrachloride with water and a mixture obtained by mixing phosphoric acid and magnesium hydroxide in this mixed solution is a supernatant liquid in which precipitates are precipitated, phosphoric acid, titanic acid, and Mg. An antifogging amorphous film obtained by forming a film forming liquid containing a cation and depositing the film forming liquid .