JP2545650B2 - Red pigment for filters - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device such as a liquid crystal television or an image pickup tube, a color copying machine and a printer.
The present invention relates to a red pigment for a color separation filter used in, for example,

[0002]

2. Description of the Related Art Conventionally, as dyes for red filters,
Azo (90's "Development and market trend of special functional dyes"
CMC, paragraph 47), perinone system (JP-A-62-136)
No. 606), anthraquinone type (JP-A-62-7496).
No. 0) is known. However, since the azo red dye is water-soluble, it is suitable for coloring a filter using gelatin or casein as a base material, and although it was used for a gelatin filter, the heat resistance of the filter itself was used. However, due to its poor moisture resistance, it cannot be used as a general display element due to its use limit and its poor light resistance, heat resistance and moisture resistance of the dye itself. Also, the perinone-based and anthraquinone-based red dyes have good durability,
It had the defects of low transmittance and lack of color clarity.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to improve the drawbacks of conventional filters and filter dyes as described above, and to provide red dyes for filters which are excellent in transmittance, light resistance and heat resistance. Is to get.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that the anthraquinone derivative of the present invention, particularly the anthraquinone derivative having a specific substituent at the 2-position, is 560 to The inventors have found that a clear red filter can be obtained by suppressing the light transmittance in the range of 600 nm, and completed the present invention.

That is, the present invention provides the following general formula (I)

[0006]

Embedded image And a red dye for anthraquinone filters. As R in the general formula (I) of the present invention, as described above, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an aryl group, an unsubstituted or substituted benzyl group, an allyl group Or a group (Chemical Formula 3) represented by the following formula (II),

[0007]

Embedded image Here, as the alkyl group having 1 to 20 carbon atoms, a straight chain,
Any branched or cyclic alkyl group may be used. Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include hydroxymethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyoctyl group, 2,3-dihydroxypropyl group and the like. Examples of the aryl group include phenyl group, p-tolyl group, m-tolyl group, 2,4-xylyl group, p-chlorophenyl group, 2,
4-dichlorophenyl group, p-bromophenyl group, pentachlorophenyl group, pentafluorophenyl group, p-
Examples thereof include a hydroxyphenyl group and a 2,4-dihydroxyphenyl group. Examples of the benzyl group having a substituent include a p-methylbenzyl group, a 2,4-dimethylbenzyl group, a p-chlorobenzyl group, a p-bromobenzyl group and the like.

The substituent R is represented by the above formula (II), wherein R ₁ is an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group having 1 to 20 carbon atoms is Any linear, branched or cyclic alkyl group may be used. Further, X in the formula (II) is —CH ₂ CH
_2- , -CH ₂ CH (CH ₃ )-or an isomer thereof, -CH ₂ CH (C
The isomer of H ₃ )-means —CH (CH ₃ ) CH ₂ —.

As a method for synthesizing the dye represented by the general formula (I), the following general formula (III)

[0010]

Embedded image (In the formula, Hal means Cl or Br, and Z has the same meaning as Z in the general formula (I)), and an anthraquinone derivative represented by the following general formula (1.0 to 5.0 mol times): I
V) HS-R (IV) (In the formula, R represents the same meaning as R in formula (I).) A thiol represented by a deoxidizing agent such as potassium carbonate, sodium carbonate or magnesium oxide can be used. In existence,
A method of heating and stirring in a solvent such as hydrocarbon, halogenated hydrocarbon, sulfolane, dimethylsulfoxide, and quinoline at a temperature of 50 to 150 ° C. for about 1 to 20 hours can be mentioned.

As a method for producing a filter, the dye of the present invention is mixed with a thermoplastic resin such as polystyrene, polymethylmethacrylate, polycarbonate, polyester, polyvinyl chloride or the like, and injection molding or stretching is used. Alternatively, the dye of the present invention alone or dissolved in a solvent with a binder, cast on a substrate,
There are a method of forming a film by spin coating or the like, a method of forming a film on a substrate by vapor deposition, a method of mixing a resin monomer or a polyamide resin intermediate with a varnish and a dye, and then polymerizing and processing. The dye of the present invention can be used as a mixture with other dyes.

[0012]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 1 part of 1-amino-2-hydroxyethylthio-4-hydroxyanthraquinone was added to 100 parts of polystyrene,
A filter was produced by injection molding. This filter had good durability and transmission characteristics. The characteristics of the filter are shown in Table 1 (Table 1), and the transmission spectrum of the filter is shown in FIG. 1 (FIG. 1). [Synthesis of 1-amino-2-hydroxyethylthio-4-hydroxyanthraquinone] 10 parts of 1-amino-2-bromo-4-hydroxyanthraquinone, mercaptoethanol 2.
8 parts of 50 parts of sulfolane with 7 parts and 4.2 parts of potassium carbonate
The reaction was carried out at 0 ° C for 3 hours. The reaction solution is methanol 500
Then, 4.0 parts of the target compound was obtained.

[0013]

[Table 1] Comparative Example 1 A filter was produced in the same manner as in Example 1 using a known dye. The characteristics of the filter are shown in Table 1 (Table 1), and the transmission spectrum of the filter is shown in FIG. 2 (FIG. 2).

Example 2 In a container equipped with a stirrer and a nitrogen inlet tube, 4,4'-
36.8 parts of bis (2-aminophenoxy) biphenyl and 202 parts of N, N-dimethylformamide were inserted, and 4,4 ′-(p-phenylenedioxy) diphthalic acid dianhydride 39. 8 parts divided and added 2
Stir for 0 hours. To the polyamic acid solution thus obtained, 3.0 parts of 1-amino-2-phenylthio-4-hydroxyanthraquinone was added, mixed, cast on glass, and heat-treated at 180 ° C. for 5 hours. The red filter thus obtained had good transmission characteristics and was excellent in heat resistance and humidity resistance. The characteristics of the filter are shown in Table 1 (Table 1), and the transmission spectrum of the filter is shown in FIG. 2 (FIG. 2). [1-amino-
Synthesis of 2-phenylthio-4-hydroxyanthraquinone] 10 parts of 1-amino-2-bromo-4-hydroxyanthraquinone, 7.0 parts of thiophenol, 4.6 parts of potassium carbonate in 100 parts of sulfolane at 90 ° C. Reacted for hours. The reaction solution was discharged into 700 parts of methanol to obtain 3.5 parts of the target compound. Comparative Example 2 A filter was prepared by coloring gelatin with a known dye. The characteristics of the gelatin filter are shown in Table 1 (Table 1), and the transmission spectrum of the gelatin filter is shown in FIG. 3 (FIG. 3).

Example 3 122 parts of 1,4-bis (α, α-dimethylisocyanatomethyl) benzene, 117 parts of 1,3,5-tris (3-mercaptopropyl) isocyanurate, and 1-
Amino-2-allylthio-4-hydroxyanthraquinone (10 parts) and dibutyltin dilaurate (0.3 parts) were mixed to obtain a uniform solution. This liquid was poured into a mold composed of a glass mold surface-treated with a fluorine-based external release agent and a vinyl chloride gasket. Then, 4 hours at 70 ℃, 2 hours at 80 ℃, 2 hours at 90 ℃, 2 hours at 100 ℃, 120 ℃
After heating for 2 hours, it was cooled and released from the mold. The obtained filter showed good transmission characteristics and was excellent in light resistance and moisture resistance.

Example 4 100 parts of polymethylmethacrylate, 1-amino-2
3-Hydroxybutylthio-4-hydroxyanthraquinone (3 parts) was dissolved in 500 parts of chloroform, cast on a glass substrate and dried. The filter thus produced had good durability and filter characteristics.

Examples 5 to 22 Red dyes having R and Z in the general formula (I) as shown in Table 2 (Table 2) were mixed with the resins shown in Table 2, and Examples 5 to 19 were prepared. And molded in the same manner as in Example 1 to obtain Examples 20 to 22.
A filter was prepared in the same manner as in Example 4. These filters had good durability and filter characteristics.

[0018]

[Table 2]

[0019]

The anthraquinone derivative of the present invention, especially 2
The anthraquinone derivative having a specific substituent at the position gives a red dye for a filter having excellent transmission characteristics and also excellent durability such as light resistance and heat resistance.
It is possible to provide a clear red filter having extremely low light transmittance in the range of 0 nm.

[Brief description of drawings]

FIG. 1 is a transmission spectrum of a filter using the dye of Example 1.

2 is a transmission spectrum of a filter using the dye of Example 2 and a dye of Comparative Example 1, the solid line is the filter of Example 2, and the broken line is the transmission spectrum of the filter of Comparative Example 1. FIG.

FIG. 3 is a transmission spectrum of a gelatin filter of Comparative Example 2.

Claims (1)

(57) [Claims] 1. A red dye for an anthraquinone filter represented by the following general formula (I) (Chemical formula 1). Embedded image