JPS63268768A - Green coloring matter for filter - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R<1>-R<5> are each alkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, halogenoalkyl, cyanoalkyl, halogen or H). EXAMPLE:1,4-bis(2,4-dimethylanilino)-5,8-dihydroxyanthraquinone. USE:Green coloring matter for optical filters. Excellent in light and heat resistances and spectroscopic characteristics. PREPARATION:A reaction is carried out between a leucotetrahydroxyanthra quinone of formula II and aniline derivative of formula III in the presence of arsenic acid and boric acid.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a green dye for optical filters.

(Prior Art) Filters using gelatin as a substrate are known as optical filters necessary for television cameras, liquid crystal televisions, computer-mounted flat panels, displays, etc.
7), silica, and gelatin-based filters are not very durable.

Therefore, the use of durable resins or inorganic transparent substances as base materials is being considered (Japanese Patent Application Laid-Open No. 59-127
036).

(Problems to be Solved by the Invention) Oil-soluble dyes or disperse dyes are known as transparent colorants of resins or inorganic substances (Dye Handbook, published by Maruzen).

However, among these dyes, there has been no dye that has sufficient coloring properties, durability (particularly light resistance and heat resistance), and excellent spectral characteristics.

Furthermore, there was no dye suitable for the sublimation vapor deposition method (Japanese Patent Application Laid-Open No. 127036/1983), which is being considered as a new method for producing filters.

(Means for Solving the Problems) As a result of intensive studies, the present inventors discovered a pigment with good light resistance and heat resistance, and completed the present invention.

That is, the present invention relates to the general formula (1) (wherein R1 to RS are an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a halogenoalkyl group) , a cyanoalkyl group, a halogen atom, or a hydrogen atom).

The dye of the present invention is represented by the general formula (1), in which the alkyl group represented by R1-R1 is:
Examples include straight chain or branched alkyl groups having 1 to 20 carbon atoms, and examples of the cycloalkyl group include cyclopentyl group,
Examples of the alkoxy group include a cyclohexyl group and a cycloheptyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a hexyloxy group.
Examples of the alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a butoxyethyl group, a 3-methoxybutyl group, and examples of the alkoxyalkoxyalkyl group include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxyethyl group. Examples of the hydroxyalkyl group include ethoxyethyl group, etc.
Examples include hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group, and examples of hydroxyalkoxyalkyl group include hydroxyethoxyethyl group, hydroxypropoxy Examples of the halogenoalkyl group include chloroethyl group, chloropropyl group, bromoethyl group, etc.; examples of the cyanoalkyl group include cyanomethyl group, cyanoethyl group, cyanopropyl group, etc.; Examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The dye of the present invention can be obtained, for example, by reacting leucotetrahydroxyanthraquinone and an aniline derivative in the presence of arsenic acid and boric acid as shown in the following formula.

The dye of the present invention obtained by such a method includes:
Examples include dyes shown in Table 1.

Table 1 shows the dye of the present invention and its performance as a filter.

In Table-1, performance tests and evaluations are as follows.

1) Colorable PET: PET (polyethylene terephthalate)
Film, chromogen and ethylene glycol at 130℃
Coloring property PS when dyed for 1 hour with PS: Coloring property AI when mixing and molding PS (polystyrene) resin and dye! , : Coloring properties when transferring the dye to the base material (T-alumina) obtained by coating and firing alumina gel on glass 2) Each base material with heat-resistant coloring (PET, PS, r-alumina)
◎ if there is no change in the transmission spectrum after heating at 200°C in the air for 2 hours, 0130 if it is 10% or less
% or less, Δ, and 30% or more, ×.

3) Each base material with light-fast coloring (PET, PS, γ-alumina)
A case in which the amount of spectrum change after 20 hours of irradiation with the fade meter light was not evaluated as ◎, a case in which it was 10% or less, a case in which it was within 0.130% was evaluated as Δ, and a case in which it was 30% or more was evaluated as ×.

4) Sublimation: The case where O1 sublimated at 200°C or lower under atmospheric pressure was rated as ×, and the case where O1 did not sublimate was rated as ×.

5) Filter performance: 0 if the transmittance at 550 nm of a substrate colored with a density such that the transmittance at 630 nm is 5% or less is 60% or more.
．． Cases where it was less than 60% were marked as x.

Thermoplastic resins (polystyrene, polyethylene, polypropylene,
Acrylic resin, He〇S resin, polyacecool, polycarbonate, etc.), thermosetting resin (amino resin, phenolic resin, polyurethane, polyester, polyether sulfone, polyether ether ketone, etc.), alumina membrane (held on glass or resin), Examples include silica film (held on glass or resin), and coloring methods include kneading, transfer, dyeing, and sublimation.

(Functions and Effects) Conventional dyes had problems with durability, coloring properties, etc., but the dyes of the present invention have excellent coloring properties, heat resistance, light resistance, and sublimation properties.
Furthermore, it is a practically extremely useful dye with excellent spectral properties.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Example-1 11 parts of icotetrahydroxyanthraquinone, 2.4
- Charge 88 parts of xylidine and 9.4 parts of 60% arsenic acid solution, and while dehydrating by blowing air, bring the temperature to 170 °C,
The mixture was heated and stirred at 170°C for 3 hours. Then 120°C
Leukotetrahydroxyanthraquinone 4
．． 7 parts and 3.2 parts of boric acid at the same time and heated to 120'C.
The mixture was heated and stirred for 30 minutes. After the reaction was completed, it was cooled to 60°C, 120 parts of ethanol was added, and the precipitated solid was separated by filtration, washed with ethanol, washed with water, dried, and purified by column.
．． 20.5 parts of 4-bis(2,4-dimethylanilino)-5,8-dihydroxyanthraquinone was obtained.

λll1ax (in chloroform) 680r+a+ elemental analysis value (%) CHN Actual value? 5.25 5.50 5.74 Calculated value
? 5.30 5.48 5.85 10 parts of this dye was mixed with 100 parts of polypropylene glycol, made into fine particles, coated on paper, dried to make transfer paper, coated with alumina gel, and baked to make a 3II11 glass plate with a thickness of 3II. was transferred at 200°C to create a green filter. Figure 1 shows a chart of the spectral characteristics (transmittance) of this filter measured using a spectrophotometer.

Example 2 In the same manner as in Example 1, a reaction was carried out using 88 parts of 2.5-xylidine instead of 2,4-xylidine, and 1,4-bis(2,5- dimethylanilino)-5,8-hydroxyanthraquinone19.
I got 6 copies.

λmax (in chloroform) 680 parts m Elemental analysis value (%) CHN Actual value ? 5.15 5.53 5.82 Calculated value
? 5.30 5.48 5.85 10 g of polyester film, 2,000 g of ethylene glycol, and 2 g of the obtained dye were added and dyed at 130°C for 1 hour to create a green filter.

Figure 2 shows a chart of the spectral characteristics (transmittance) of this filter measured using a spectrophotometer needle.

Example 3 In the same manner as in Example 1, a reaction was carried out using 89 parts of p-anisidine instead of 2,4-xylidine, and 1,4-bis(4-methoxyanilino) was purified by column purification. 20.1 parts of -5,8-hydroxyanthraquinone was obtained.

λwax (in chloroform) 682 parts m Elemental analysis value (%) HN Actual value 69.83 4.42 5.80 Calculated value
69.85 4.40 5.82 1 g of the obtained dye and Pyronal MD are placed on a polymethyl methacrylate resin plate.
-1, 200 (product of Toyobo Co., Ltd.) A transfer paper prepared from 10 g of silica gel and 1 g of silica gel (dye arranged for a filter) was layered and passed through a calendar at 200°C to obtain a green filter.

Figure 3 shows a chart of the spectral characteristics (transmittance) of this filter measured using a spectrophotometer.

[Brief explanation of drawings]

Figures 1, 2 and 3 show that using the dye according to the present invention,
The spectral characteristics (transmittance) at each wavelength of the filters produced in Examples-1, -2, and Example-3 are shown. Patent applicant Mitsui Toatsu Chemical Co., Ltd. Figure-1 Figure-λ

Claims (1)

[Claims] 1) General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1 to R^5 are an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxy A green dye for filters represented by an alkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a halogenoalkyl group, a cyanoalkyl group, a halogen atom, or a hydrogen atom.