JP2772924B2 - Precursor composition for producing glassy film and method for producing glassy film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a precursor composition for producing a glassy film and a method for producing a glassy film, and more particularly, to a matrix of a coloring material such as glass, ceramics, tile, and plastic, a glass filter, and an infrared ray. Alternatively, the present invention relates to a precursor composition for producing a glassy film used for an ultraviolet cut filter, a coating material and the like, and a method for producing a glassy film using the same.

[0002]

2. Description of the Related Art A silicone resin is a crosslinked silicone resin having a siloxane bond as a main chain and a methyl group or a phenyl group in a side chain. This resin is particularly excellent in heat resistance and weather resistance. Widely used for protective coating. Further, there is a silicone-modified organic resin obtained by copolymerizing a silicone component and an organic resin for the purpose of improving the chemical resistance of the silicone resin, and this is also widely used as a paint.

[0003]

However, when the silicone resin is used alone, there is a problem in the chemical resistance to acids and alkalis. For this reason, the silicone-modified organic resin obtained by copolymerizing the organic resin with the aim of improving the chemical resistance has a low hardness and is not suitable for a protective coating on glass or a metal surface.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and provides a precursor composition for producing a glassy film, which has improved hardness, heat resistance, chemical resistance and boiling water resistance, and a method for producing the same. Provided is a method for producing a glassy film used.

[0005]

According to the present invention, a trifunctional silicon alkoxide containing at least a ureido group is added to 5-90% by weight of a silicone varnish having a hydroxyl group.
And an acrylic resin having a hydroxyl group of 10 to 50% by weight.
95% by weight of a precursor composition for producing a glassy film.

Furthermore, the present invention is 5 to 90 wt% silicone varnish having a hydroxyl group, and 1 to 50 wt% trifunctional silicon alkoxide containing at least ureido group
There is provided a method for producing a glassy film in which 10 to 95% by weight of an acrylic resin having a hydroxyl group is added, and this is hydrolyzed and condensed.

The silicone varnish having a hydroxyl group used in the present invention is a colorless or pale yellow transparent liquid having a hydroxyl equivalent of 300 to 700 g (weight of resin per mole of hydroxyl group) of 300 to 700 g. And dissolved in organic solvents such as dimethylimidazolidinone, metacresol, dimethylformamide, carbitol, terpinol, diacetone alcohol, triethylene glycol, paraxylene, toluene, ethanol, and acetone.

Specifically, KR21 manufactured by Shin-Etsu Chemical Co., Ltd.
1, KR212, KR216, TSR160, YR3168 manufactured by Toshiba Silicone Co., Ltd., or SH6018, DC6-223 manufactured by Toray Dow Corning Silicone Co., Ltd.
0 and the like.

The amount of the silicone varnish added is 5
The content is from 90 to 90% by weight, preferably from 10 to 50% by weight, and if it is less than 5% by weight, the weather resistance of the film decreases.

[0010] Urea group-containing 3 used in the present invention.
The functional silicon alkoxide is a specific one among the silane coupling agents, and includes, for example, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and the like. This addition amount is 1 to 50% by weight.
If the amount is less than 1% by weight, the adhesiveness of the film decreases, while if it exceeds 50% by weight, the film turns yellow and the heat resistance decreases.

[0011] Furthermore, the hydroxyl group-containing alcohol used in the present invention.
The krill resin has a hydroxyl value (the amount of hydroxyl groups in 1 g) of 10
２００200 mg. This resin is dissolved in an organic solvent such as dimethylimidazolidinone, metacresol, dimethylformamide, carbitol, terpinol, diacetone alcohol, triethylene glycol, paraxylene, toluene, ethanol and acetone. The addition amount is from 10 to 95% by weight, preferably from 20 to 60% by weight. When the amount is less than 10% by weight, the chemical resistance of the film is reduced. The weather resistance decreases.

The mixture of the above three components can be applied directly to the surface of a substrate such as glass by dipping, spraying, coating, printing, or the like, and the thickness can be adjusted to a thickness of about 500 μm. If the film thickness is larger than that, bubbles are likely to enter during the heat treatment stage. Of course, screen printing is also possible. In addition, the said heat treatment should just be the conditions on which the mixture of said 3 components performs a polycondensation reaction, and, specifically, 150 to 3
It is 10 to 60 minutes at an atmosphere temperature of 00 ° C.

This screen printing procedure involves a screen placed horizontally (eg, polyester plain fabric, 255
The printed circuit board (glass) is placed under the mesh with a distance of several millimeters. After placing the composition on the screen, the composition is spread over the entire screen using a squeegee. At this time, the screen and the printed circuit board have an interval. Subsequently, printing is performed by pressing and moving the screen with a squeegee to such an extent that the screen contacts the print substrate. Thereafter, this is repeated.

In the present invention, in addition to the above three components, various additives, for example, silica powder, various dyes, fluorescent dyes, and metal or ceramic powders can be used.

[0015]

Next, the present invention will be described in more detail with reference to specific examples. Examples 1-2 As shown in Table 1, as a silicone varnish having a hydroxyl group, a silicone varnish for modification (KR21 manufactured by Shin-Etsu Chemical Co., Ltd.)
2), an acrylic resin (A817 manufactured by Dainippon Ink and Chemicals, Inc.) as a resin having a hydroxyl group, and γ-ureidopropyltriethoxysilane as a trifunctional silicon alkoxide containing a ureide group.

These raw materials are mixed according to the composition shown in Table 1, and the resulting mixture is dipped on a glass plate.
The polymerization was completed by heat treatment in an oven set at 50 ° C. for 30 minutes, and a 20 μm-thick glassy film was formed on a glass plate.

The above film has a heat resistance test, a hardness test, an acid resistance test,
An alkali resistance test and a boiling water resistance test were performed. Table 1 also shows the obtained results. The evaluation method is as follows.

1. Heat resistance test The film prepared on the glass plate was heat-treated in an oven at 250 ° C. for 30 minutes, and the state of the film was visually observed.
○ indicates that there was no change in the appearance of the film.

2. Hardness test A pencil lead was rubbed against a glassy film to evaluate the presence or absence of scratches due to the hardness of the pencil lead. In addition, the hardest pencil lead without scratches was defined as pencil hardness.

3. Acid resistance test The state of the glassy film after immersion in a 1N aqueous sulfuric acid solution for 24 hours was visually evaluated.は indicates the case where there was no change in the appearance of the film, and × indicates the case where the glassy film was separated from the glass plate.

4. Alkali resistance test The state of the glassy film after immersion in a 1N aqueous sodium hydroxide solution for 24 hours was visually evaluated.は indicates the case where there was no change in the appearance of the film, and × indicates the case where the glassy film was separated from the glass plate.

5. Boiling water test The state of the glassy film after immersion in boiling water at 100 ° C for 3 hours was visually evaluated.は indicates the case where there was no change in the appearance of the film, and × indicates the case where the glassy film was separated from the glass plate.

[0023]

[Table 1]

The results show that the glassy film obtained in this example has excellent heat resistance, acid resistance, alkali resistance, boiling water resistance, and high hardness.

Comparative Examples 1 to 8 Each raw material was mixed in accordance with the composition shown in Table 1, various silane coupling agents were added, and these were mixed and stirred. The obtained composition was dipped on a glass plate and heat-treated in an oven set at 250 ° C. for 30 minutes to complete the polymerization, and a 20 μm thick glassy film was formed on the glass plate. The film was subjected to a heat resistance test, a hardness test, an acid resistance test, an alkali resistance test, and a boiling water resistance test. Table 1 also shows the obtained results.

According to the results, none of the glassy films obtained in the comparative examples satisfy all of the properties of heat resistance, acid resistance, alkali resistance, boiling water resistance and high hardness. Was lacking.

[0027]

As described above, by using a trifunctional silicon alkoxide containing a specific ureide group as a silane coupling agent as in the present invention, heat resistance, acid resistance, alkali resistance and boiling water resistance are improved. There is an effect that a glassy film that satisfies all the properties of high performance and high hardness can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 83 / 06,83 / 08 C08K 5/54 C08L 101/06

Claims (2)

(57) [Claims] 1. A silicone varnish having a hydroxyl group.
0% by weight, at least 1 to 50% by weight of a trifunctional silicon alkoxide containing a ureide group, and a hydroxyl group.
A precursor composition for producing a glassy film, comprising 10 to 95% by weight of an acrylic resin . 2. A silicone varnish having a hydroxyl group 5 to 9.
0% by weight, at least 1 to 50% by weight of trifunctional silicon alkoxide containing at least ureido group and hydroxyl group
A method for producing a glassy film, comprising adding 10 to 95% by weight of an acrylic resin , followed by hydrolysis and condensation.