JPH0710605A - Formed article of light-scattering glass - Google Patents

Abstract

PURPOSE:To obtain a formed glass article free from see-through property while keeping the light transmittance and having frost-tone at a low cost without using hydrofluoric acid treatment by forming a coating film containing a siloxane-type compound on a treated surface of a formed glass article subjected to a treatment to inhibit the straight transmission of light. CONSTITUTION:This formed article of light-scattering glass is composed of a formed glass article subjected to a treatment to inhibit the straight transmission of light and a coating film formed on the treated surface and containing a compound expressed by the formula RxSiO(4-x)/2 (R is 1-9C organic group; Si is silicon; O is oxygen; O< x< 4). Grinding process can be used as the treatment to inhibit the straight transmission of light. The treatment may be applied to a part or total of the formed article. The formation of the coating film is preferably carried out by applying a solution or dispersion containing a precursor of the compound expressed by the formula RxSiO(4-x)/2 to the formed glass article and baking the coated product after drying. The precursor is preferably a compound having alkoxy group and/or acetoxy group and/or hydroxyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass molding which has a transparent property while maintaining the transmission of light.

[0002]

2. Description of the Related Art There has been a great demand for a lighting product having no see-through property, which is conventionally represented by shoji paper. Even in the case of glass molded products, light-proof products such as pickpocket plate glass and template plate glass, which cannot be seen through, have been manufactured and are widely used. However, the conventional frosted glass plate has the drawback that the white surface of the picked surface looks dirty, and in fact it is easily soiled and it is difficult to remove the adhered dirt. Therefore, I was disliked.

In order to make up for the drawbacks of these conventional products,
Frosted glass has been proposed. This is a sandblasted glass treated with hydrofluoric acid, and is preferred because it has a deep look and soft transmitted light. However, the handling of hydrofluoric acid is not popular because it is troublesome from the management of the treatment process to the disposal of waste liquid and the product is too expensive.

[0004]

As described above, most of the glass products for lighting that have not been used so far and have no see-through property are monotonous ones such as picked glass and template glass. In general, although there is a strong demand for expressive products, frosted glass with high decorativeness is too expensive, and there is no choice but to use inexpensive template glass.

In view of the above situation, the inventor of the present invention has conducted intensive studies, and as a result, has developed a novel light-scattering glass molded article having high decorativeness. That is, the present invention was developed by developing a method for producing frosted glass with a rich expression without using hydrofluoric acid treatment, which requires troublesome handling such as process control and environmental measures, and maintains the transmission of light. The present invention intends to provide a glass molded body that is transparent and loses its transparency at low cost.

[0006]

The present invention relates to a glass molded body that has been subjected to a treatment that prevents light from going straight ahead, and the treated surface of the molded body has R _X SiO _{(4-X) / 2} ( Here, R is an organic group having 1 to 9 carbon atoms, Si is silicon, O is oxygen,
X represents a number in the range of 0 <X <4), and a light-scattering glass molded body is provided with a coating film containing a compound represented by the formula.

The glass molding used in the present invention is a plate,
It can be applied to almost all molded articles made of glass, such as sticks, tubes, blocks, cups, figurines such as vases, ornaments such as pendants. Particularly, in the case of a plate-shaped glass molded body, it is preferable because the function that it can have is effectively exhibited.
In this case, the treatment of the present invention can be applied to one surface of the plate-shaped glass molded body. Also, the treatment of the present invention can be applied to two surfaces. Further, it is possible to process a part of one surface or a part of each of the two surfaces.

The light-scattering glass molding of the present invention formed in a plate shape can be used for various applications such as windows, partitions, doors and the like. Further, the light-scattering glass molded product of the present invention can be used alone, or can be used by being compounded with other glass molded products, resin molded products and the like.

In the present invention, the processing for preventing the light from going straight is as follows:
Made by picking. The picking can be carried out by water picking, sand picking, or another method, and is preferably used in the present invention. Further, it is also possible to subject the pattern-patterned product to a picking process and use it in the present invention.

R _X SiO _{(4-X) / 2} (where R is an organic group having 1 to 9 carbon atoms, Si is silicon, O is oxygen, and X is 0).
The formulas (1) below, each of which represents a number in the range of <X <4, are generally well known as siloxane-based inorganic polymer compounds, and are easily available. The Rs may be the same or different as long as they are organic groups having 1 to 9 carbon atoms.

Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group and an octyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, an alkenyl such as a vinyl group and an allyl group. Group, phenyl group, aryl group such as xylyl group, aralkyl group such as phenylethyl group, substituted mercaptopropyl group, aminopropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, and halogens thereof. Compounds such as chloromethyl group, trifluoroethyl group, hexafluoropropyl group, tetrahydroperfluorooctyl group, tetrachlorophenyl group and the like can be exemplified.

In the present invention, one kind of these may be used alone, or two or more different kinds may be used in combination. It is preferable that the number of carbon atoms does not exceed 6, more preferably an alkyl group, an alkenyl group, or a phenyl group whose carbon number does not exceed 4, from the viewpoint that excellent performance can be exhibited due to heat resistance, durability and the like. And it is desirable that these are halogenated products.

X in the equation (1) represents a number larger than 0 and smaller than 4 on average. More preferably,
It is desirable that X is 0.2 or more and 2 or less because a strong coating having a high surface hardness can be uniformly formed under a wide range of coating conditions. In addition, the content of the component based on R _X in the compound represented by the formula (1) is preferably 41% by weight or less. More preferably, it is 30% by weight or less for the same reason.

In order to form a coating film containing the compound represented by the formula (1) of the present invention on the surface which has been treated to prevent the light from advancing straight, a solution or dispersion liquid containing the precursor of the compound. It is effective to use. The term "precursor" as used herein refers to all the compounds at the previous stage where the compound finally represented by the formula (1) is obtained by drying, firing, chemical reaction and the like. Examples of such precursors include chlorinated products of Si, hydrogenated products, hydroxides, alkoxides, acetates, and reaction products and polymers thereof. Among them, monomers and polymers having a hydroxyl group, an alkoxy group and an acetoxy group are preferable as the precursor of the present invention because they are easy to handle and have high storage stability.

Further, since a uniform film without cracks can be stably formed, the solution or dispersion liquid of the precursor of the present invention contains at least a polymer partially condensed with a hydroxide. Is preferred. In this case,
It is desirable that the condensation polymer is not gelled.

In the present invention, a solution or dispersion containing 0.1% by weight to 100% by weight of such precursor composition is preferably used. Many of the precursor compositions of the present invention, even if they are substantially 100% by weight, are in the form of solutions or dispersions having excellent coatability, and are preferably used as solvent-free paints.

Further, in the present invention, in order to dissolve or disperse such a precursor composition, an appropriate solvent or dispersion medium can be used. In this case, a suitable one is selected in order to uniformly mix a plurality of components constituting the precursor composition and to uniformly proceed the hydrolysis reaction and the polymerization reaction of the hydrolyzate and the partial condensate.

Specifically, hexane, cyclohexane,
Aliphatic hydrocarbons such as heptane and octane, benzene,
Aromatic hydrocarbons such as toluene, xylene, styrene, and tetralin, methanol, ethanol, propanol,
Butanol, pentanol, alcohols such as hexanol, ethylene glycol, propylene glycol, hexylene glycol, polyhydric alcohols such as glycerin, ethylene glycol monomethyl ether acetate, glycol derivatives such as ethylene glycol monoethyl ether, acetone, methyl ethyl ketone, Ketones such as acetophenone, esters such as ethyl acetate and methyl benzoate, ethers such as tetrahydrofuran and dioxane, amides such as dimethylformamide and dimethylacetamide, amines such as dimethylamine and triethanolamine, chloroform, methylene chloride , Halogen compounds such as trichlorotrifluoroethane, acids, alkalis, diacetone alcohol, dimethyl sulfoxide, tetramethylene sulfone Nitrobenzene, compounds such as water and the like can be exemplified, and these one or more of the mixture can be used as a solvent or dispersion.

Further, other components can be optionally mixed in the solution or dispersion of the precursor of the present invention. Examples of such components include silane, titanium, zirconium, aluminum, sodium, vanadium, chromium, manganese, iron, copper, yttrium, indium,
Metal oxides such as tin, antimony, barium, lanthanum, tungsten and lead, organic metal oxides, and particles thereof, colloids, whiskers such as potassium titanate and silicon nitride, dyes, organic pigments such as phthalocyanine and quinacridone, and cobalt. , Inorganic pigments such as chromium and iron, various surfactants, coupling agents, ultraviolet absorbers, stabilizers such as antioxidants, and the like.

The solution or dispersion of the precursor of the present invention is
It is applied to the surface that has been treated to prevent the light from going straight,
A film containing the compound represented by the formula (1) is formed. The application of the solution or dispersion is performed by roll coating, flow coating, spraying, dipping, or any other method to provide a wet coating layer. By drying this layer and subjecting it to heat treatment or the like, a coating film containing the compound represented by formula (1) is obtained. The thickness of the coating is
It is determined depending on the permissible transparency and the roughness of the surface due to the treatment that prevents the light from going straight, but generally it is 10Å on average.
It is preferably about 200 μm. Since a film without cracks can be evenly coated on the uneven surface, it is more preferably 100 Å to 50 µ on average.

[0021]

As described above, the light-scattering glass molded article of the present invention is characterized in that a coating containing the compound represented by the formula (1) is provided on the surface which is treated to prevent the light from going straight. There is. Hitherto, in order to manufacture frosted glass having a deep expression and soft transmitted light, a troublesome process such as sandblasting and hydrofluoric acid treatment has been required.

The present invention enables the production of frosted glass without using this hydrofluoric acid treatment.
That is, the light-scattering glass molded article of the present invention has a frosted appearance by forming a coating film containing the compound represented by the formula (1) on the surface of the glass which has been subjected to the scribing treatment. The frosted glass, which has been apt to be disliked in the past, can be finished into a frosted glass with rich expression as in the present invention for the following reason.

That is, the whitishness and susceptibility of frosted glass are due to microscopic cracks on the surface formed during processing. It can be seen that filling the cracks with the coating film of the present invention avoids whitishness and susceptibility to stains to soften the transmitted light. Moreover, since the thin coating leaves the surface unevenness, the transparency is not greatly enhanced.

[0024]

EXAMPLES Examples of the present invention will now be specifically described, but it goes without saying that the present invention is not limited to these examples.

Example 1 3 g of water containing 2 mmol of HCl was mixed with 10 g of a 20% tetrahydrtofuran solution of isopropyl alcohol in a solution, and 17 g of methyltriethoxysilane and methoxy-type polydimethylsiloxane having an average molecular weight of 380 at both ends were mixed. 1 g was added, and the mixture was stirred at 80 ° C. for 2 hours. This was left to stand at room temperature for 2 days to obtain a viscous transparent solution. To this, 67 g of a 15% isopropyl alcohol solution of dimethylformamide and 10 g of tetraethoxysilane were added, mixed and stirred to obtain a coating liquid A. Next, a commercially available picked plate glass was washed and dried, and then heated to 65 ° C., and then the picked surface was spray-coated with the coating liquid A. This was dried at 100 ° C. for 10 minutes and then baked at 250 ° C. for 1 hour to obtain a light scattering glass 1. Various physical properties of this glass are shown in Table 1.

Example 2 A solution prepared by mixing 2.8 g of water containing 2 mmol of HCl with 10 g of a 20% tetrahydrofuran solution of isopropyl alcohol was added to 17 g of methyltriethoxysilane and 1 g of both-end silanol-type polydimethylsiloxane having an average molecular weight of 1700. Was added and the mixture was stirred at 80 ° C. for 2 hours. This was left to stand at room temperature for 2 days to obtain a viscous transparent solution. To this, 98 g of a 10% isopropyl alcohol solution of dimethylformamide and 10 g of tetrabutoxytitanium were added, mixed and stirred to obtain a coating liquid B. A light scattering glass 2 was obtained in the same manner as in Example 1 except that this coating liquid B was used. Various physical properties of this glass are shown in Table 1.

Comparative Example 1 20 g of a 20% tetrahydrofuran solution of isopropyl alcohol, 1.75 of water containing 3 mmol of HCl.
g, 68 g of a 15% isopropyl alcohol solution of dimethylformamide, and 20.73 to each mixed solution.
Coating solution C was obtained by adding g of tetraethoxysilane. A light-scattering glass 3 was obtained in the same manner as in Example 1 except that this coating liquid C was used. Various physical properties of this glass are shown in Table 1.

Example 3 A coating solution A prepared in the same manner as in Example 1 was added to a commercially available surfactant Florard FC-430 [Sumitomo 3M].
0.1 g and 1 g of a xylene dispersion of Tiosorb UF01 [Ultrafine particle titanium oxide manufactured by Tiooxide Japan, solid content concentration 61.7% by weight] were mixed and stirred to obtain a coating liquid D. A light-scattering glass 4 was obtained in the same manner as in Example 1 except that this coating liquid D was used. Various physical properties of this glass are shown in Table 1.

Example 4 A commercially available float glass was coated with 2 of Sucrandom R # 100.
It was sprayed for 15 minutes per 1 m ^{2 by} applying atmospheric pressure to give a pickpocket. A light-scattering glass 5 was obtained by coating the coating liquid A in the same manner as in Example 1 except that this glass was used instead of the commercially available ground glass. Various physical properties of this glass are shown in Table 1.

Example 5 6 g of a commercially available coating agent Ceraton PT [Suzuki Sangyo],
A coating liquid E was obtained by mixing and stirring 10 g of dimethylformamide and 84 g of isopropyl alcohol. A light-scattering glass 6 was obtained in the same manner as in Example 1 except that this coating liquid was used. Various physical properties of this glass are shown in Table 1.

[0031]

[Table 1]

[0032]

EFFECTS OF THE INVENTION The light-scattering glass molding of the present invention has a deep expression and softness on a glass molding without using hydrofluoric acid treatment which requires extremely troublesome handling in process control, environmental measures, waste liquid disposal and the like. Transparent transmitted light can be provided, and frosted glass can be manufactured at low cost.

Since the coating film used in the present invention is an organic / inorganic composite mainly composed of siloxane bonds, the surface provided with the coating film also has an effect of holding the cold and heavy appearance of glass without impairing it. It also has the effect of exhibiting high weather resistance, heat resistance, chemical resistance, stain resistance, hardness and the like.

Claims (9)

[Claims] 1. A glass molded body, which has been subjected to a treatment for preventing the light from going straight, wherein R _x Si is formed on the treated surface of the molded body.
O _{(4-X) / 2} (wherein R is an organic group having 1 to 9 carbon atoms, Si is silicon, O is oxygen, and X is a number in the range of 0 <X <4). A light-scattering glass molded article provided with a coating film containing the compound represented. 2. The light-scattering glass molded body according to claim 1, wherein the glass molded body is a plate-shaped glass molded body. 3. A process for preventing the straight movement of light is performed on a part or the whole of a molded body.
Or the light-scattering glass molded article according to 2. 4. The light-scattering glass molded article according to claim 1, wherein the treatment for preventing the light from going straight is performed by picking. 5. The content of the component based on R _X in the coating film containing the compound represented by R _X SiO _{(4-X) / 2} is 40% by weight or less. The light-scattering glass molded body according to any one of claims 1 to 4. 6. A solution wherein _{R X SiO (4-X)} / 2 with a film comprising a compound represented is, including a precursor _{R X SiO (4-X)} / 2 in the compound represented by Alternatively, the film is formed after applying the dispersion liquid.
5. The light-scattering glass molded article according to any one of 5 above. 7. The light-scattering glass molding according to claim 6, wherein the precursor has an alkoxy group and / or an acetoxy group and / or a hydroxyl group. 8. The method according to claim 6, wherein the precursor contains a condensation polymer derived from a hydroxide of Si in R _X SiO _{(4-X) / 2} . The light diffusion glass molding described. 9. The light-scattering glass molding according to claim 7, wherein the condensation polymer is not gelled.