JP3357090B2 - Manufacturing method of ultraviolet absorbing glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates about the method of manufacturing a glass which was equipped with a UV absorbing by forming a film on the surface of the glass for buildings, the automotive and other.

[0002]

To shield the Prior Art UV entering the room or car or the like, not only preventing human sunburn, a deterioration of the room or car ornaments important in that it prevent. Conventionally, as the ultraviolet absorber, benzophenone, and organic compounds such as benzotriazole is known in the main, these organic compounds have a problem that not easy to occur degradation with the absorption of ultraviolet radiation.

Further, an ultraviolet absorbing film using zinc oxide, which is known as an inorganic compound and having high ultraviolet absorbing performance, has been proposed in Japanese Patent Application Laid-Open No. 1-217084.
Zinc oxide chemically poor durability and Tsu difficult der used as a glass surface treated.

[0004]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems of the prior art,
An object of the present invention is to provide a method for producing an ultraviolet-absorbing glass having, on its surface, an ultraviolet-absorbing film having three components of cerium oxide, titanium oxide and silicon oxide as main components and having no deterioration and high durability. It shall be the.

[0005]

SUMMARY OF THE INVENTION The present invention comprises a complex formed from the chelating ligand and the cerium salt, a silicon compound, viewed contains as main components a titanium compound, the Ti / Si
The molar ratio is 1.0 or more and 3.0 or less, and Ti / Ce
After the molar ratio is by coating a coating solution is 0.5 to 1.5 on a glass substrate, the ultraviolet absorbing glass that form a UV absorbing film on the surface by heating to 300 ° C. or higher manufacturing method you provide.

[0006] Se cerium chloride as potassium salts, cerium nitrate, and cerium sulfate and the like can be used, cerium chloride, in that not easy to dissolve in an organic solvent such as alcohol,
Cerium nitrate are relatively preferred.

[0007] Se potassium salt, it is important to use to form a chelating ligand and complex. Drying and cerium inorganic salt used as the crystal of the cerium oxide Ease precipitate no longer at the time of heating, there is a possibility that the transparency of the film is impaired. As a chelate ligand, acetylacetone C ₅ H ₈ O _2, which is a type of β- diketone With can prevent crystals precipitated whitening of cerium oxide upon drying after coating stability because of chelate rings. The amount of the ligand to be coordinated is preferably from 1 to 3 in terms of the molar ratio of C ₅ H ₈ O ₂ / Ce. If the amount of acetylacetone is less than this, it is easy to whiten, and if it is more than this, it cannot be reacted with cerium, so that it is wasted.

Formed from a chelating ligand and a cerium salt
The complex can be easily obtained by reacting a cerium salt with an organic compound serving as a chelating ligand. this
Occasionally, it may be reacted directly ligands and cerium salt without solvent, but it may also be reacted in an organic solvent such as alcohol as a solvent in the product. Further, <br/> when the reaction is difficult to proceeds may be to promote the reaction, such as by heating.

As the silicon compound, SiR _m (OR ′)
_4-m (where R and R 'are alkyl groups, m = 0 to 3), and at least one selected from the group consisting of silicon compounds and polymers thereof. These silicon compounds may be used as they are, or may be used after being hydrolyzed under an acid catalyst or the like.

As the titanium compound, TiL _m (OR)
_4-m (where L = chelating ligand, R = alkyl group,
m = 0 to 2 ) and at least one selected from titanium alkoxides, titanium chelate compounds, and polymers thereof.

[0011] By way of example, titanium tetraisopropoxide de _{Ti (OC 3 H 7) 4} , mono acetylacetonato titanium triisopropoxide Ti (C ₅ H ₇ O ₂ ) (O
C ₃ H ₇ ) ₃ , bis ( acetylacetonato ) titanium diisopropoxide Ti (C ₅ H ₇ O ₂ ) ₂ (OC ₃ H ₇ )
₂ , bis ( ethylacetoacetate ) titanium diisopropoxide Ti (C ₆ H ₉ O ₃ ) ₂ (OC ₃ H ₇₎ is _2, and so on.

[0012] Among these, the chelating ligand is used after at least one coordination, membranes produced is more difficult cloudy and storage stability of the solution is also preferable because more improved. The titanium compound may be used as it is,
It may be used after hydrolysis.

[0013] Keru you to paint coating solution, the abundance ratio of Ti / Si in the liquid, Ru der 1.0 to 3.0 in a molar ratio. If the abundance ratio of Ti is lower than this, the ultraviolet absorbing ability is lowered and the transparency of the film is also deteriorated. On the other hand, if it is higher than this, the reflectance of visible light becomes extremely high, the visible light transmittance is reduced, and the film formability is also deteriorated.

[0014] In addition, Keru to paint coating solution, Ti / Ce in the liquid
Abundance ratio, Ru Oh 1.5 hereinafter 0.5 or more by molar ratio. Ti
The abundance ratio Ri is that the susceptibility rather <br/> name impair transparency of the film less than this, is also reduced ultraviolet absorptivity. The higher than this lowered even ultraviolet absorptivity and film forming property even drop. Preferred
Or more, 0.5 or more and 1.0 or less.

[0015]PaintCloth liquid is calculated as the total solid content of oxides.
It is preferably from 1.0% to 15.0%. Solid
This is the shapeLess thanThen, the thickness of the film obtained by one application
In order to obtain a film having the desired ultraviolet absorption ability
Must be applied several times.You.Also fixed
If the form weight is higher than this, the service life of the coating solution will be shortened.Ease
No. Normal alcohols and hydrocarbons are used as dilution solvents.
Such as hydrogen, ester, ether alcohol, glycol, etc.
Organic solvents can be used as appropriate. It also improves wettability with glass.
Various surfactants may be added to improve the performance.

[0016] The coating coating solution as a coating method at the time of applying onto a glass substrate, de Ippukoto method, spin coating, spray coating, roll coating method, a meniscus coating method, a screen printing method, flexographic printing method, or the like is available it can.

After the applied film is dried and heated, the metal compound is turned into an oxide by heating and becomes a dense transparent oxide film. The heating temperature at this time is between 300 ° C. and the softening point of glass. select can-option. For temperature does not decompose sufficiently proceed to the oxide from which less than the metal organic compound, ultraviolet absorptivity Ri poor, even lack the strength of the film.

Further, the ultraviolet absorbing glass obtained by the manufacturing method of the present invention, the antireflection performance by forming a transparent film having a low refractive index, such as silicon oxide and magnesium fluoride on the ultraviolet absorbing film to further Can also be provided.

[0019]

EXAMPLES further be described examples of the present invention are shown below, but the present invention is Lena have limited thereto. The evaluation of the glass with a film obtained in the following Examples and Comparative Examples was carried out in terms of appearance (visual observation), ultraviolet transmittance (T _uv : ISO9050 , single).
Position:% ), visible light transmittance (T _v : JIS- R310)
6 , unit:% ), abrasion resistance test (Taber test: JIS)
-R 3221), chemical resistance test (0.1N-NaOH, H
₂ SO _{4 for} 10 days). In addition, ultraviolet rays
The transmittance and visible light transmittance are the values including the glass substrate.
You.

[0020] [Example 1 and Comparative Example 1] acetylacetonate 10 cerium nitrate hexahydrate 150g
4 g was added and reacted at 90 ° C. for 1 hour with stirring to obtain a dark yellow viscous liquid (Solution A, acetylacetone / Ce).
= 3 (molar ratio) ). To 50 g of ethyl silicate polymer (ethyl silicate 40), 44 g of isopropanol, 0.2 N
6 g of an aqueous hydrochloric acid solution was added and reacted at room temperature for 12 hours (B
liquid).

18 g of acetylacetone was added to 50 g of titanium tetraisopropoxide and reacted at room temperature for 12 hours to obtain an isopropanol solution of monoacetylacetonatotitanium triisopropoxide (solution C). Liquid A, B
The solution and the solution C were mixed so that the metals had the compositions shown in Table 1 below, and diluted with isopropanol so that the total solid content became 8.3%.

[0022]

[Table 1]

Using a dip coater as shown in FIG. 1, this coating solution was pulled up and applied to the surface of soda lime glass having one side masked, dried at 150 ° C. for 5 minutes, and then placed in an electric furnace at 600 ° C. for 5 minutes. The firing was performed. The thickness of each of the formed ultraviolet absorbing films was 200 nm.
Table 2 shows properties of the obtained glass with a film.

[0024]

[Table 2]

Here, the abrasion resistance test was performed by Taber test 30.
After 0 rotation, chemical test shows the film state of after immersion for 10 days, ○ indicates no peeling of the film even after the test.
Furthermore, to indicate that the ○ appearance is KuToru bright cracks and cloudiness that the membrane (hereinafter the same).

[0026] Example 2 and Comparative Example 2] acetylacetonate cerium nitrate hexahydrate 150 g 69
g, and reacted at 90 ° C. for 1 hour with stirring to obtain a yellow viscous liquid (solution D, acetylacetone / Ce = 2).
(Molar ratio) ).

36 g of acetylacetone was added to 50 g of titanium tetraisopropoxide and reacted at room temperature for 12 hours to obtain an isopropanol solution of bis ( acetylacetonato ) titanium diisopropoxide (Solution E). Liquid D, E
The solution and the solution B shown in Example 1 were mixed so that the metals had the compositions shown in Table 3 below, and diluted with ethanol so that the total solid content became 10.0%.

[0028]

[Table 3]

This coating solution was pulled up and applied to both sides of soda lime glass using a dip coater as shown in FIG. 1, dried at 150 ° C. for 5 minutes, and baked at 300 ° C. for 30 minutes. The sample was cooled to room temperature, on the ultraviolet absorbing film, the B solution a solution obtained by diluting silicon oxide in terms of solid content of 4 wt% in isopropanol, pulling while applied to both sides at the same dip coating apparatus, at 0.99 ° C. After drying for 5 minutes, firing was performed again at 300 ° C. for 30 minutes. The thickness of the formed lower layer (ultraviolet ray absorbing film) was 200 nm, and the thickness of the upper layer (silicon oxide film) was 100 nm. Table 4 shows the properties of the obtained glass with a film.

[0030]

[Table 4]

[0031] [Example 3 and Comparative Example 3] acetylacetone 3 cerium nitrate hexahydrate 150g
4.5 g and 100 g of hexylene glycol were added and reacted at 90 ° C. for 1 hour with stirring to obtain a pale yellow viscous liquid (solution F, acetylacetone / Ce = 1 (molar ratio) ).

Ethyl silicate polymer (ethyl silicate 4
0) 50 g of hexylene glycol 44 g, 0.2 N
6 g of an aqueous hydrochloric acid solution was added and reacted at room temperature for 12 hours (G
liquid). F liquid metal each G solution and a titanium tetra-n- butoxide were mixed so that the compositions shown in Table 5 below,
Diluted with hexylene glycol to a total solids of 12%.

[0033]

[Table 5]

This coating solution was printed and applied on soda lime glass using a flexographic printing machine, dried at 150 ° C. for 5 minutes, and then baked in an electric furnace at 500 ° C. for 10 minutes. The thickness of each of the formed ultraviolet absorbing films was 160 nm. Table 6 shows the properties of the obtained glass with a film.

[0035]

[Table 6]

Comparative Example 4 Instead of the solution A shown in Example 1, an ethanol solution of cerium nitrate (10% by weight in terms of CeO ₂ ) was used . The same composition as each composition of Example 1b and Example 1d of Table 1
Except for using the synthesized coating solution so as was performed in the same manner as in Example 1. Table 7 shows properties of the obtained glass with a film.

[0037]

[Table 7]

[0038]

According to the present invention, it is possible to provide an ultraviolet absorbing glass which can block ultraviolet rays by 90% or more, does not deteriorate, and has a good appearance. In addition, since it has excellent durability, it can be used for architectural and automotive window glass.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a dip coating apparatus used in Example 1.

[Explanation of symbols]

 1: glass substrate 2: liquid reservoir 3: coating liquid 4: hood 5: pulley

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 15/00-23/00

Claims (2)

(57) [Claims] 1. A method comprising the steps of: forming a chelate ligand and a cerium salt;
And complex, and a silicon compound, viewed contains as main components a titanium compound, the molar ratio of Ti / Si is 1.0 to 3.0
And the molar ratio of Ti / Ce is 0.5 or more and 1.5 or less.
After applying the lower coating solution on the glass substrate,
Method for producing ultraviolet absorbing glass you form <br/> an ultraviolet absorbing film on the surface by heating to above. Wherein forming the low refractive index film composed mainly of silicon oxide further on the ultraviolet absorbing film of the ultraviolet absorbing glass produced by the production method according to claim 1, anti-reflection property is imparted Method of producing ultraviolet absorbing glass.