JP3020968B2 - Glass with transparent protective film and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a glass with a transparent protective film and a method for producing the same, and more particularly, to a glass with a transparent protective film which does not show iris and is excellent in alkali resistance. It relates to the manufacturing method.

Technical Background of the Invention So-called crystal glass has excellent transparency and high reflectivity, so it is used for decorative items or high-quality tableware, but dirt or scratches on its surface are easily noticeable, and as a result, it has an aesthetic appearance. It was sometimes damaged.

In addition to the dirt generated on the glass surface as described above, there is a dirt caused by a minute amount of water adhering to the glass surface in addition to the dirt adhering. That is, the moisture adhering to the surface of the glass becomes alkaline, whereby the glass surface is eroded and roughened. Due to the scattering of light by the rough surface, the glass surface appears to be white and a phenomenon called “white burn” occurs.

Furthermore, in order to remove dirt such as dust and food debris, the above glass is usually washed with a neutral detergent, but an alkali detergent may be used to increase the washing speed. Will occur.

As one of means for protecting the glass surface from such dirt and scratches, a coating liquid for forming a transparent protective film having functions such as alkali resistance and scratch resistance is applied to the glass surface to protect the glass surface with a thin transparent protective film. A method of coating with a film is conceivable.

Various coating liquids having the above functions have been proposed. However, conventional coating liquids have a high refractive index and a high transparency such that the refractive index is 1.50 to 1.70 and the total light transmittance is 80% or more. When applied to a transparent glass surface to form a transparent protective film,
The following problems arise.

That is, if the difference between the refractive index of the glass and the refractive index of the transparent protective film formed on the glass surface is large, the lights reflected from each other interfere with each other, and an interference color appears on the surface. When such a glass surface exhibits a so-called red color, there is a problem that the original aesthetic appearance of the glass is impaired.

Object of the present invention, the refractive index as described above is 1.50 to 1.70,
The purpose is to solve the problems associated with glass having a total light transmittance of 80% or more, and a transparent protective film having functions such as alkali resistance without forming a so-called red color on the glass surface is formed. It is an object of the present invention to provide a glass with a transparent protective film and a method for producing the same.

SUMMARY OF THE INVENTION The glass with a transparent protective film according to the present invention has a refractive index of 1.50 to
1.70, the surface of the glass the total light transmittance of 80% or more, when a n _c the refractive index of (i) the glass, (n _c -0.0
5) has a refractive index in the range of _{~ (n c +0.05), (} ii) acetylacetonate represented by the partial hydrolyzate of the organic silicon compound represented by the following formula (I) and formula (II) It is characterized by having a transparent protective film formed by applying a coating liquid, in which a chelate compound and an organic solvent are dispersed or dissolved in an organic solvent, onto glass.

R _a -Si (OR ') _4-a (I) (where R is C _n H _{2n + 1-} (n = 1 to 4), a hydrogen atom or a halogen atom, and R' is C _n H _{2n + 1} − (n =
1-4), a hydrogen atom or _{C n H 2n + 1 OC 2} H 4 - (n = 1~
4). A is an integer of 0 to 3. ) (Where a + b = 2-4, a = 0-3, b = 1
4, R is C _n H _{2n + 1} (n = 3,4), and X is CH ₃ , CH ₃ O, C
₂ H ₅ or C ₂ H ₅ O, and M ₁ is a metal element. ).

Further, the first method for producing a glass with a transparent protective film according to the present invention, the coating liquid obtained by dispersing or dissolving an organosilicon compound and an acetylacetonate chelate compound in an organic solvent has a refractive index of 1.50 to 1.70. , The total light transmittance is 80%
Coating, drying or baking on the glass surface as described above to form a transparent protective film on the glass surface to produce a glass with a transparent protective film, a coating liquid application step, a coating drying step, a coating film During or after any one of the firing steps, the coating film formed on the glass surface is irradiated with an electromagnetic wave having a wavelength shorter than visible light.

Further, the method for producing a glass with a transparent protective film according to the second aspect of the present invention, the coating liquid obtained by dispersing or dissolving the organosilicon compound and the acetylacetonate chelate compound in an organic solvent has a refractive index of 1.50 to 1.70. , The total light transmittance is 80%
The above is applied to the glass surface, and dried or baked to form a transparent protective film on the glass surface to produce a glass with a transparent protective film. It is characterized by alkali treatment.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the glass with a transparent protective film according to the present invention and a method for producing the glass will be specifically described.

The glass on which the transparent protective film is formed in the present invention has a refractive index.
1.50 to 1.70, preferably 1.52 to 1.65, glass having a total light transmittance of 80% or more, preferably 85% or more,
Among them, glass called crystal glass is particularly preferably used.

In the glass with a transparent protective film according to the present invention, a transparent protective film is provided on the surface of such a glass, but in the present invention, the refractive index of the transparent protective film and the refractive index of the glass are almost the same, By making the difference as small as possible,
It has become possible to suppress the appearance of iris due to interference of reflected light. That is the refractive index of the transparent protective film is n, if the refractive index of the glass was n _c, preferably nc-0.05 ≦ n ≦ nc + 0.05 is be in the range of nc-0.03 ≦ n ≦ nc + 0.03, glass It is possible to obtain a glass having no red color due to light interference on the surface and having excellent transparency.

Such a transparent protective film has a thickness of 0.01 to 3.0 μm.
Preferably, it is 0.1 to 1.0 μm. If the thickness of the transparent protective film is less than 0.01 μm, the scratch resistance tends to be insufficient, whereas if it exceeds 3.0 μm, it tends to be difficult to form the protective film uniformly.

Further, it is desirable that the total light transmittance of the glass with a transparent protective film according to the present invention is 85% or more, preferably 90% or more.

Such a transparent protective film is formed on a glass by a vapor phase method such as a vapor deposition method or a coating method using a coating solution. Of these, a coating method using a coating solution is particularly preferable.

In the present invention, as a coating solution for forming a transparent protective film on glass, a transparent protective film formed using this coating solution has the above refractive index, and is excellent in alkali resistance. Then, any coating liquid can be used, but a coating liquid in which an organosilicon compound and a metal compound are dissolved or dispersed in an organic solvent is particularly preferably used.

As the organosilicon compound, one or more compounds selected from the compounds represented by the following formula (I) are used in combination.

R _a -Si (OR ') _4-a (I) (where R is C _n H _{2n + 1-} (n = 1 to 4), a hydrogen atom or a halogen atom, and R' is C _n H _{2n + 1} − (n =
1-4), a hydrogen atom or _{C n H 2n + 1 OC 2} H 4 - (n = 1~
4). A is an integer of 0 to 3. ) As such an organosilicon compound, specifically,
Tetramethoxysilane, tetraethoxysilane, monomethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, tetrahydroxysilane, and the like are used.

A coating solution in which only such an organosilicon compound is dispersed or dissolved in an organic solvent has been conventionally known. However, when such a coating solution is coated on glass having a refractive index of 1.50 to 1.70 and a total light transmittance of 80% or more to form a transparent protection, the resulting transparent protective film is made of SiO ₂ , Its refractive index is about 1.46. Therefore, the refractive index
The refractive index is significantly different from that of glass having a total light transmittance of 1.50 to 1.70 and a total light transmittance of 80% or more, and an interference color of light appears on the glass surface to give a reddish color, which impairs aesthetic appearance.

Therefore, in the present invention, a coating liquid in which an organosilicon compound and a metal compound are dispersed or dissolved in an organic solvent is used. It is preferable that the refractive index of this metal compound when it becomes an oxide is substantially equal to or higher than the refractive index of the glass. The transparent protective film formed by applying such a coating solution to the glass is made of SiO ₂ and MOx
(M is a metal element), and the refractive index of the transparent protective film is adjusted to n _c −0.05 by adjusting the ratio of SiO ₂ and MOx.
And n _c +0.05.

As the metal species of the metal compound, it is preferable that the oxide obtained from the metal compound has the above values, and specifically, Al, In, IV A which is a group IIIB of the periodic table.
Group Ti, Zr, Hf, IVB group Sn or rare earth metals such as La and Ce are used. These metals may be used alone or as a mixture.

In the present invention, an acetylacetonate chelate compound is used as such a metal compound.

The acetylacetonato chelate compound is a chelate compound having acetylacetone as a ligand and has the following formula (I
Indicated by I).

(Wherein in a, b, R, X, M 1 is as follows.

R is C _n H _{2n +} 1 - a (n = 3,4), X is CH ₃ -, C ₂ H ₅
—, CH ₃ O— or C ₂ H ₅ O—, and M ₁ is a metal element. Examples of such acetylacetonatochelate compounds include, specifically, dibutoxy-bisacetylacetonatozirconium, tributoxy monoacetylacetonatozirconium, diisopropoxy-bisacetylacetonatotitanium, aluminum acetylacetonato, Dibutoxy-bisacetylacetonatohafnium,
Monoacetylacetonato-tributoxyhafnium and the like are preferably used.

In the present invention, as the metal compound, only the acetylacetonato chelate compound as described above, or a combination thereof with another metal compound such as an inorganic salt, an organic salt, an oxy salt or a metal alkoxide can be used.

Organic solvents include alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, ethylene glycol, hexylene glycol, esters such as methyl acetate, ethyl acetate, diethyl ether, ethylene glycol monomethyl. Ethers such as ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, and ketones such as acetone and methyl ethyl ketone are used alone or in combination.

Such a coating liquid for forming a transparent protective film is prepared by dissolving or dispersing an organosilicon compound and a metal compound in an organic solvent containing water. At this time, the organosilicon compound and the acetylacetonatochelate compound as the metal compound may be used as they are, or may be used after partial hydrolysis in advance.

In the present invention, a partially hydrolyzed organosilicon compound is used.

In order to partially hydrolyze the organosilicon compound, for example, a condition in which the organosilicon compound is mixed with methanol or ethanol and water and an acid are added to partially hydrolyze can be employed, but the following conditions are particularly preferable. As the acid, an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, or an organic acid such as acetic acid or acetic anhydride is used. The mixing ratio of the acid and the organosilicon compound is 0.01 ≦ acid / SiO ₂ ≦ 0.5 (the organosilicon compound is
(Weight ratio when converted to O ₂ ). If this value is less than 0.01, a large amount of unreacted organosilicon compound is present, while if this value exceeds 0.5, the partial hydrolysis rate becomes too fast, resulting in continuous productivity and storage stability of the coating solution. Tends to decrease. The mixing ratio of water and the organosilicon compound is preferably water / organosilicon compound ≧ 2 (molar ratio). If this value is less than 2,
Since the unreacted organosilicon compound remains in the coating, the adhesion between the coating and the substrate, the scratch resistance, and the durability are reduced. The partial hydrolysis temperature is preferably in the range from 30 to 80C.

The mixing ratio of the metal compound and the organosilicon compound in the transparent protective film forming coating solution prepared as described above is such that the refractive index n of the formed transparent protective film is n _c and the refractive index of the glass. when, it is preferable to adjust to be in the range of _{n c -0.05 ≦ n ≦ n c} +0.05, this proportion varies depending on the metal species in the metal compound, a transparent protective film formation conditions ( (For example, the firing temperature), and the range cannot be determined uniformly.

For example, a metal oxide formed from a metal compound is ZrO ₂
In the case of (n = 2.1) or TiO ₂ (n = 2.2), these have a large difference in refractive index from SiO ₂ , so that ZrO ₂ / SiO ₂ = about
0.1~1.5, TiO ₂ / SiO ₂ = about 0.05 to 1.0 (both by weight)
It is preferable to use an organosilicon compound and a metal compound in the range described above. In the case where, for example, Al ₂ O ₃ having a lower refractive index than ZrO ₂ and TiO ₂ is formed from a metal compound, this ratio is larger than the above range.

In the present invention, an acetylacetonatochelate compound is particularly preferably used as the metal compound, but the transparent protective film formed using the coating solution containing the acetylacetonatochelate compound has a chemical resistance such as alkali resistance. Is excellent.

In the coating solution containing such an acetylacetonatochelate compound, the mixing ratio between the acetylacetonatochelate compound and the organosilicon compound is M ₁ O _x / SiO ₂ or M ₁ O _x /
(SiO ₂ + M ₂ O _x ) (M ₁ O _x : oxide derived from acetylacetonato chelate compound, M ₂ O _x : oxide derived from other metal compounds) is preferably 0.05 or more.

In the present invention, as described above, the coating liquid for forming a transparent protective film contains water in order to hydrolyze the organosilicon compound and the metal compound.

The water concentration in this coating solution is preferably 0.1 to 50% by weight. If the water concentration is less than 0.1%, the hydrolysis becomes insufficient, while if it exceeds 50%, the glass tends to repel during coating.

In the present invention, the coating solution as described above on the glass surface,
By applying a coating method such as a dipping method, a spinner method, a spray method, a roll coater method, and a flexographic printing method to form a uniform film, and then drying and firing,
A transparent protective film can be formed on the glass. After coating and drying, if baked at a temperature of 120 ° C. or higher, and a glass transition point or lower, a transparent protective film having a refractive index in the above range, and also having excellent alkali resistance, scratch resistance, and transparency. Can be formed on glass. At this time, firing may be performed any number of times as long as the temperature is equal to or lower than the glass transition point.

Further, in the present invention, if the following method is adopted, a glass with a transparent protective film having more excellent properties can be obtained.

That is, in the present invention, in the above manufacturing process, after and / or during any one or more of the steps of applying the coating liquid to the glass substrate, drying the coating film, and firing the coating film. It is preferable to irradiate a coating film formed on the glass surface with an electromagnetic wave having a shorter wavelength than visible light. By irradiating the coating with electromagnetic waves, the baking temperature of the coating can be lowered.For example, if the coating is irradiated with electromagnetic waves, even if the baking temperature of the coating is set at 300 ° C., the baking temperature may be reduced to 400 without irradiation with electromagnetic waves. A coating having the same properties as those baked at ℃ is obtained.

As an electromagnetic wave having a shorter wavelength than visible light, specifically,
Examples include ultraviolet rays, electron beams, X-rays, and γ-rays. Of these, ultraviolet rays are preferably used. As an ultraviolet source,
Emission maximum at around 250nm and 360nm, irradiation intensity 10mW
It is desirable to use a high-pressure mercury lamp of at least / cm ² , preferably 100 mW / cm ² . 10
0 mJ / cm ² or more, preferably highly durable coating is obtained at low temperatures by irradiating a 1000 mJ / cm ² or more irradiation energy on the coating film.

In the present invention, it is preferable that after the above-described drying step, the coating film formed on the glass is subjected to an alkali treatment and then fired.

As a method of alkali treatment, there is a method of dipping in an aqueous alkali solution for a certain time, washing with water, and drying and firing, or a method of exposing to an ammonia gas atmosphere for a certain time and then drying and firing.

By applying the above-described electromagnetic wave treatment or alkali treatment to the coating film, a transparent protective film having higher density and excellent durability can be obtained.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Preparation of Coating Solutions Coating solutions 1 to 12 shown in Table 1 were prepared using the following organosilicon compounds and metal compounds, respectively.

(Organic silicon compound) E-40: Ethyl silicate (SiO ₂ 40% by weight, ethyl silicate 40, manufactured by Tama Chemical Industry) E-28: Same as above (28% by weight of SiO ₂ , Ethyl silicate 28, manufactured by Tama Chemical Industry) M-51: Methyl silicate (51% by weight of SiO ₂ , methyl silicate 51 manufactured by Tama Chemical Industry) (metal compound) ZAB-1: Tributoxyacetylacetonato zirconium (14.9% by weight of ZrO ₂ , ZR-181 manufactured by Nippon Soda) ZAB-2: Dibutoxy bis acetylacetonato zirconium (ZrO ₂ 19.9 wt%, Matsumoto交商manufactured ZC-550) TB: butyl titanate _{dimer, (C 4 H 9 O)} 3 · Ti
O ・ Ti (C ₄ H ₉ O) ₃ , (TiO ₂ 29.1% by weight, TA-
22) TAP: Diisopropoxybisacetylacetonato titanium (TiO ₂ 16.5% by weight, TC-100 manufactured by Matsumoto Kosho) ZB: Tetrabutoxy zirconium (ZrO ₂ 27.3% by weight, Nippon Soda TBZr) AA: Aluminum monoacetyl Acetonato / bisethylacetoacetate (Al ₂ O ₃ 10% by weight, manufactured by Kawaken Fine Chemicals) ZN: 10% by weight of zirconium nitrate ethanol solution as ZrO ₂ A predetermined amount of the above organosilicon compound and a solvent were mixed. . The obtained mixed solution was gradually added to 120 g of pure water while stirring, and 1.1 g of concentrated nitric acid was further added. Then 50
° C and maintained at this temperature for 60 minutes to prepare solution A.

Next, a predetermined amount of the above metal compound and a solvent were mixed to prepare a solution B.

The solution A and the solution B thus obtained are mixed at a predetermined ratio,
A coating solution as shown in Table 1 was obtained.

Example 1 The coating liquids 1 to 12 prepared as described above were treated with a refractive index of
1.56 glass with a total light transmittance of 92% (40 mm x
60mm x 2mm) under the conditions shown in Table 2.
A glass with a transparent protective film having a thickness of 0.2 μm was obtained.

The ultraviolet treatment was performed by irradiating the dried glass with a protective film with ultraviolet light for 3 minutes using a 2 kw high-pressure mercury lamp. The alkali treatment was performed by immersing the dried glass with a protective film in a 1% aqueous NaOH solution at 25 ° C. for 5 seconds.

Next, the glass having a transparent protective film obtained as described above was evaluated as shown below.

 Table 2 shows the results.

(1) Total light transmittance: Measured with a haze computer (manufactured by Suga Test Instruments Co., Ltd.).

(2) Red: Determined visually.

(3) Refractive index: ellipsometer (ULSM ESM-
(Type 2).

(4) Alkali resistance: After immersion in a 1% NaOH aqueous solution at 80 ° C. for 3 hours, the presence or absence of white burn on the surface was visually judged.

(5) Adhesion: A part of commercially available cellophane tape (12mm width) is stuck on the protective film, the rest is kept at right angles to the protective film, peeled off instantaneously, and the presence or absence of peeling of the protective film at that time is visually observed. Judged.

(6) Membrane strength: A steel wool (#
0000) was reciprocated on the film surface 30 times, and the presence or absence of a scratch on the film surface was visually determined.

Comparative Example A coating solution was prepared in the same manner as described above using only the organosilicon compound or only the metal compound as shown in Table 1.

Using this coating solution, a glass with a transparent protective film was obtained in the same manner as in Example 1, and the same evaluation was performed.

 Table 2 shows the results.

Continuation of the front page (56) References JP-A-59-155801 (JP, A) JP-A-62-191448 (JP, A) JP-A-61-502121 (JP, A)

Claims (3)

(57) [Claims] 1. A refractive index of 1.50 to 1.70, the surface of the glass the total light transmittance of 80% or more, when a n _c the refractive index of (i) the glass, (n _c -0.0
5) having - a refractive index in the range of _{(n c +0.05), (ii} ) a partial hydrolyzate of an organic silicon compound represented by the following formula (I), acetyl acetonate represented by the following formula (II) A glass with a transparent protective film, characterized by having a transparent protective film formed by applying a coating solution in which a natto chelate compound is dispersed or dissolved in an organic solvent onto glass. R _a -Si (OR ') _4-a (I) (where R is C _n H _{2n + 1-} (n = 1 to 4), a hydrogen atom or a halogen atom, and R' is C _n H _{2n + 1} − (n =
1-4), a hydrogen atom or _{C n H 2n + 1 OC 2} H 4 - (n = 1~
4). A is an integer of 0 to 3. ) (Where a + b = 2-4, a = 0-3, b = 1
4, R is C _n H _{2n + 1} (n = 3,4), and X is CH ₃ , CH ₃ O, C
₂ H ₅ or C ₂ H ₅ O, and M ₁ is a metal element. ) 2. A coating solution comprising a partial hydrolyzate of an organosilicon compound represented by the following formula (I) and an acetylacetonate chelate compound represented by the following formula (II) dispersed or dissolved in an organic solvent: , Applied to a glass surface having a refractive index of 1.50 to 1.70 and a total light transmittance of 80% or more, dried or fired,
When producing a glass with a transparent protective film by forming a transparent protective film on the surface of the glass, it is visible during or after any one of a coating liquid application step, a coating film drying step, and a coating film baking step. A method for producing a glass with a transparent protective film, comprising irradiating a coating film formed on a glass surface with an electromagnetic wave having a shorter wavelength than a light beam. R _a -Si (OR ') _4-a (I) (where R is C _n H _{2n + 1-} (n = 1 to 4), a hydrogen atom or a halogen atom, and R' is C _n H _{2n + 1} − (n =
1-4), a hydrogen atom or _{C n H 2n + 1 OC 2} H 4 - (n = 1~
4). A is an integer of 0 to 3. ) (Where a + b = 2-4, a = 0-3, b = 1
4, R is C _n H _{2n + 1} (n = 3,4), and X is CH ₃ , CH ₃ O, C
₂ H ₅ or C ₂ H ₅ O, and M ₁ is a metal element. ) 3. A coating solution in which a partial hydrolysis of an organosilicon compound represented by the following formula (I) and an acetylacetonato chelate compound represented by the following formula (II) are dispersed or dissolved in an organic solvent: Coating on a glass surface with a refractive index of 1.50 to 1.70 and total light transmittance of 80% or more, drying or subsequent baking to form a transparent protective film on the glass surface to produce a glass with a transparent protective film A method for producing a glass with a transparent protective film, comprising applying a coating solution to the surface of the glass, drying the coating solution, and subjecting the coating film formed on the glass to an alkali treatment. R _a -Si (OR ') _4-a (I) (where R is C _n H _{2n + 1-} (n = 1 to 4), a hydrogen atom or a halogen atom, and R' is C _n H _{2n + 1} − (n =
1-4), a hydrogen atom or _{C n H 2n + 1 OC 2} H 4 - (n = 1~
4). A is an integer of 0 to 3. ) (Where a + b = 2-4, a = 0-3, b = 1
4, R is C _n H _{2n + 1} (n = 3,4), and X is CH ₃ , CH ₃ O, C
₂ H ₅ or C ₂ H ₅ O, and M ₁ is a metal element. )