JP2803515B2 - Method for producing dyed polysilane 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 method for producing a dyed polysilane film which is particularly suitable for use as a color filter for optical equipment and lighting equipment.

[0002]

2. Description of the Related Art Conventionally, dyeing, printing, pigment dispersing, electrodeposition, and the like have been adopted as a method for producing a color filter used in an optical device or a lighting device. .

In the dyeing method, a polymer material to which a photosensitive dichromate is added is applied to a glass substrate surface, mask exposure is performed, and development is performed to form a film having a desired pattern. This is a method for producing a color filter by repeating the process of applying an antifouling layer on a film a plurality of times after dyeing with a color filter. When a color filter is manufactured by this dyeing method, a color filter with a high degree of perfection can be obtained, but there is a problem that the manufacturing process is complicated and the cost is disadvantageous.

There are stencil printing, offset printing, gravure printing, and the like as printing methods. Although the manufacturing process is simple, accuracy and stability are problems.

[0005] The pigment dispersion method, also called a color resist method, is a method of producing a color filter by repeating a step of patterning a colorant in which a pigment is dispersed by using a photolithography technique. The color filter manufactured by this method is excellent in heat resistance and light resistance, but has a problem that the manufacturing process is complicated and disadvantageous in cost.

As a method for solving the above-mentioned problems of the method for manufacturing a color filter, a method for manufacturing a color filter using a polysilane film has been proposed. That is, the polysilane film is exposed to ultraviolet light, and only the exposed portion is dyed by immersing in a cationic dye aqueous solution,
Furthermore, it has been found that multicolor pattern dyeing can be performed on a single film (Yokoyama et al., Chemical Society of Japan No. 6).
3 Spring Annual Meeting 4F808). According to this manufacturing method, it is possible to manufacture a color filter by a simplified manufacturing process, and therefore, it is possible to reduce the cost of the color filter.

However, although the method of manufacturing the above color filter is simplified as compared with the conventional manufacturing method, there are problems that the exposure time is long and that the polysilane film has poor mechanical strength.

[0008] The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a method for producing a dyed polysilane film that can be manufactured by a simple manufacturing process and can obtain a dyed polysilane film having excellent mechanical strength because an exposure time is short.

[0009]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that the following general formula (1) [(R ¹ R ² Si) _n (R ³ R ⁴ Si) _m ] _P ... (1) (where R ¹ , R ² , R ³ and R ⁴ are the same or different and are unsubstituted or substituted alkyl or aryl groups having 1 to 12 carbon atoms, n, m, p Is 0 ≦ n ≦ 10, 0 ≦ m ≦ 10, n
It is a positive number that satisfies + m ≧ 10 and p ≧ 1. The dyeable polysilane composition containing the polysilane represented by the formula (1) and the ester compound is applied to the substrate surface by dissolving in an organic solvent or the like, and dried to form a polysilane film. When a polysilane film is exposed to ultraviolet light, and a dyed polysilane film is produced by a method of dyeing the exposed portion with a cationic dye, the polysilane film is efficiently dyed even with a small amount of ultraviolet irradiation. It has been found that the dyed polysilane film obtained in a short time and has excellent mechanical strength and is suitable for use as a color filter has led to the present invention.

Therefore, the present invention provides a dyeable polysilane composition solution containing a polysilane represented by the above general formula (1) and an ester compound, which is applied to the surface of a substrate, and the resulting polysilane film Provided is a method for producing a dyed polysilane film, which comprises exposing the exposed portion to ultraviolet light and dyeing the exposed portion with a cationic dye.

Hereinafter, the present invention will be described in more detail. The present invention uses a dyeable polysilane composition containing a polysilane represented by the following general formula (1) and an ester compound.

[(R ¹ R ² Si) _n (R ³ R ⁴ Si) _m ] _P (1) (where R ¹ , R ² , R ³ and R ⁴ are the same or different, unsubstituted or Substituted alkyl group or aryl group having 1 to 12 carbon atoms, n, m and p are 0 ≦ n ≦ 10, 0 ≦ m ≦ 10, n
It is a positive number that satisfies + m ≧ 10 and p ≧ 1. )

Here, R ¹ , R ² , R ³ and R ⁴ are the same or different and are unsubstituted or substituted alkyl or aryl groups having 1 to 12 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of the aryl group include a phenyl group, a tolyl group, and an aryl group in which part or all of the hydrogen atoms of these groups are substituted with an alkyl group, an alkoxy group, or the like. n, m, and p are 0 ≦ n ≦ 10, 0 ≦
It is a positive number that satisfies m ≦ 10, n + m ≧ 10, and p ≧ 1.

On the other hand, examples of the ester compound include aromatic carboxylic acid esters such as phthalic acid esters, fatty acid esters, polyhydric alcohol esters, and phosphoric acid esters.

The amount of the ester compound is 1 to 10 parts by weight per 100 parts (parts by weight, hereinafter the same) of the above polysilane.
It is preferably 0 parts, particularly preferably 30 to 40 parts.

The dyeable polysilane composition of the present invention can be obtained by mixing the above components.

In order to produce a dyed polysilane film using the dyeable polysilane composition, first, the polysilane composition is dissolved in an organic solvent, applied to a transparent substrate such as glass, and dried. Form a polysilane film.

In this case, toluene, xylene and the like can be used as the organic solvent. The concentration of the polysilane composition when dissolved in an organic solvent is preferably 1 to 30% (% by weight, hereinafter the same). In addition, as a method for applying the solution of the polysilane composition on the substrate, a method such as spin coating can be employed.

When the dyed polysilane film of the present invention is used for a color filter, the thickness of the dried polysilane film is preferably 0.5 to 20 μm.

Next, the obtained polysilane film is exposed to ultraviolet rays. In this case, pattern exposure can be performed using a desired mask pattern as needed. The ultraviolet irradiation dose is 0.1 to 10 J / cm ² ,
More preferably, it is preferably 3 to 5 J / cm ² . Thereafter, a dyed polysilane film pattern can be obtained, for example, by immersion in an aqueous solution of a cationic dye in acetonitrile.

Here, examples of the cationic dye include rhodamine 6G, rhodamine B, safranin T, brilliant green, malachite green, crystal violet, basic blue 3, and indoin blue. These cationic dyes are preferably dissolved in an aqueous solution such as acetonitrile at a concentration of 0.01 to 10%. In this case, as the acetonitrile aqueous solution, a mixture of 100 parts of acetonitrile and 500 to 2000 parts of water can be used.

The immersion time of the polysilane film in the aqueous solution of the cationic dye such as acetonitrile is 1 to 1 hour.
Preferably, it is 0 minutes.

The dyed polysilane film obtained as described above is suitable for use as a color filter.

[0024]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 Methylphenylpolysilane [(CH ₃ C ₆ H ₅ S)
i) 100 parts of _n ] and 30 parts of n-butyl oleate (ester compound) were mixed and dissolved in toluene to obtain a toluene solution having a concentration of 20%. Next, this solution was spin-coated on a quartz substrate and dried under reduced pressure to form a polysilane film having a thickness of about 3 μm. Next, this film was irradiated with ultraviolet rays at 3 J / c using a high-pressure mercury lamp.
m ² was irradiated. After light irradiation, a 0.1% aqueous solution of rhodamine B in acetonitrile (acetonitrile / water = 10/10)
0) for 10 minutes to dye the polysilane film.

When the visible absorption spectrum of the obtained dyed film was measured, the transmittance derived from the characteristic absorption (556 nm) of the dye was 0.06%, and the polysilane film was sufficiently dyed.

Example 2 A dyed polysilane film was obtained in the same manner as in Example 1 except that diethylene glycol dibenzoate was used as the ester compound. When the visible absorption spectrum of the obtained dyed film was measured, the transmittance derived from the characteristic absorption (556 nm) of the dye was 0.06%, indicating that the dyed film was sufficiently dyed.

Comparative Example 1 A dyed polysilane film was obtained in the same manner as in Example 1 except that no ester compound was added (ultraviolet irradiation dose: 3 J / cm ² ). When the visible absorption spectrum of the obtained dyed film was measured, the transmittance derived from the characteristic absorption (556 nm) of the dye was 28%, and the degree of dyeing was insufficient.

Example 3 Diethylene glycol dibenzoate was used as an ester compound, and the added amount was 10, 20, 30, 40, 5 per 100 parts of polysilane.
A sample changed to 0 parts was prepared and irradiated with ultraviolet rays at 3 J / cm ² using a high-pressure mercury lamp to obtain a dyed polysilane film. When the visible absorption spectrum of the obtained dyed film was measured, the transmittances derived from the characteristic absorption (556 nm) of the dye were 0.60%, 0.24%, and 0.4%, respectively.
They were 06%, 0.12% and 0.30%, and were sufficiently stained.

Example 4 A polysilane film was formed in the same manner as in Example 1 except that di (ethylhexyl) adipate was used as the ester compound. Next, using a lattice pattern mask having a line width of 20 μm, pattern exposure was performed under the same irradiation conditions as in Example 1, and the obtained polysilane film pattern was dyed in the same manner as in Example 1. Could be obtained.

[0031]

When the dyed polysilane composition of the present invention is used for the production of a dyed polysilane film, the dyeing can be efficiently performed even with a small amount of light irradiation on the polysilane film. The resulting dyed film has excellent mechanical strength and is suitable for use as a color filter.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G02B 1/10 G03F 7/075 511 G03F 7/075 511 G02B 1/10 Z (72) Inventor Akira Hayashida Takatsu-ku, Kawasaki-shi, Kanagawa 3-2-1 Sakado, Shin-Etsu Chemical Co., Ltd. Corporate Research Center (72) Inventor Kotobuki Umehara 3-2-1, Sakado, Takatsu-ku, Kawasaki City, Kanagawa Prefecture Shin-Etsu Chemical Co., Ltd. Corporate Research Center (56) References JP-A-6-172656 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 83/16 C08J 5/18 C08K 5/10 C09D 183/16

Claims (1)

(57) [Claims] 1. The following general formula (1) [(R ¹ R ² Si) _n (R ³ R ⁴ Si) _m ] _p (1) (where R ¹ , R ² , R ³ and R ⁴ are mutually The same or different unsubstituted or substituted alkyl or aryl groups having 1 to 12 carbon atoms, n, m and p are 0 ≦ n ≦ 10, 0 ≦ m ≦ 1
0, n + m ≧ 10, and a positive number satisfying p ≧ 1. ), A solution of a dyeable polysilane composition containing the polysilane and the ester compound is applied to the substrate surface, and the resulting polysilane film is exposed to ultraviolet light, and the exposed portion is exposed to a cationic dye. A method for producing a dyed polysilane film, characterized by dyeing with a dye.