JPS63235372A - Blue dye for filter - Google Patents

Abstract

NEW MATERIAL:Blue dyes for filters, represented by the formula, wherein R1, R2, R3, R4 and R5 are each an alkyl, a cycloalkyl, an alkoxy, an alkoxyalkyl, an alkoxyalkoxyalkyl, a hydroxyalkyl, a hydroxyalkoxyalkyl, an alkenyl, a halogen or H. USE:Coloring matters for filters, which are excellent in tinting, resistance to heat and light, sublimation, etc., as well as in spectral properties. PREPARATION:Quinizarin and its leuco compd. are reacted with an aniline derivative in the presence of boric acid to obtain a blue dye for filters, represented by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a blue dye for optical filters (prior art) Conventionally, most filters have been made of gelatin as a base material, so they have sufficient durability. It wasn't. Therefore, the use of highly durable resins or inorganic transparent substances as the base material is being considered (Japanese Patent Application Laid-Open No. 59-127036).

(Problems to be Solved by the Invention) Oil-soluble dyes or disperse dyes are known as transparent colorants made of resin 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 emission and heat resistance), and excellent spectral properties.

Furthermore, there were no dyes suitable for the sublimation vapor deposition method (Japanese Patent Application Laid-Open No. 59427036, etc.), which is being considered as a new method for producing filters.

(Means for Solving the Problems) As a result of extensive research into dyes suitable for the above-mentioned purpose, the present inventors found a dye with good light emitting and heat resistance, and completed the present invention.

That is, the present invention relates to the general formula (I) (wherein R3, R1, R3, R4, R3 are an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkyl group, a hydroxyalkoxy It is a blue dye for filters represented by an alkyl group, a halogenoalkyl group, a cyanoalkyl group, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, or a hydrogen atom.

The dye of the present invention is represented by the general formula (I), where R3 to l? The alkyl group represented by s means a linear or branched alkyl group having 1 to 20 carbon atoms, and the cycloalkyl group includes a cyclopentyl group,
It means a cyclohexyl group, a cycloheptyl group, etc.; an alkoxy group means a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, etc.; an alkoxyalkyl group means a methoxyethyl group, an ethoxyethyl group, propoxyethyl group, butquinethyl group,
3-methoxybutyl group, etc.; alkoxyalkoxyalkyl group includes methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, etc.; hydroxyalkyl group includes hydroxymethyl group, hydroxyethyl group, Means 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group, etc., and hydroxyalkoxyalkyl group means hydroxyethoxyethyl group, hydroxypropoxyethyl group, etc.
Halogenoalkyl groups include chloroethyl, chloropropyl, bromoethyl, trifluoromethyl, etc.; cyanoalkyl groups include cyanomethyl, cyanoethyl, cyanopropyl, etc.; aryl groups include: phenyl group, 0-tolyl group, m-tolyl 5, p-)ruyl group, p-chlorophenyl group,
It means p-methoxyphenyl group, P-trifluoromethylphenyl group, p-nitrophenyl group, etc. Aralkyl group means benzyl group, β-phenethyl group, etc., and alkenyl group means allyl group, 2 - Means a methylallyl group, 2-chloroallyl group, crotyl group, 3-phenylallyl group, etc., and the halogen atom means a chlorine atom, fluorine atom, bromine atom or iodine atom.

The dye of the present invention can be obtained by reacting quinizarin and its leuco form with an aniline derivative in the presence of boric acid. Table 1 shows the dye of the present invention and its performance as a filter.

(Left below) In Table 1, the performance tests and evaluations are as follows.

1) Colorable PET: Colorable when PET (polyethylene terephthalate) film and dye are dyed in ethylene glycol at 130'C for 1 hour PS: Colorable when PS (polystyrene) resin and dye are mixed and molded Al: Coloring property when transferring the dye to the base material (γ-alumina) obtained by coating and baking alumina gel on glass 2) Heat-resistant colored base materials (PET, PS, 7-alumina) ◎ when there is no change in the transmission spectrum after heating at 200℃ in the atmosphere for 2 hours, 0130 when it is 10% or less
% or less, Δ, and 30% or more, ×.

3) Each base material with light resistance coloring (PUT, PS, γ-alumina)
When the amount of change in the spectrum after 20 hours with the fade meter was rated ◎, when it was 171% or less, when it was within 0.130%, it was Δ, and when it was 30% or more, it was rated ×.

4) Sublimation: The case where O1 sublimated under atmospheric pressure at 200″C or less was marked as “×” and the case where O1 did not sublimate.

5) Filter performance: 0 if the transmittance at 460rv of a base material colored with a density such that the transmittance at 540n- is 5% or less is 60% or more
Cases of less than 260% were marked as x.

Thermoplastic resins (polystyrene, polyethylene, polypropylene,
Acrylic resin, HeBS resin, polyacecool, polycarbonate, etc.), thermosetting resin (amino resin, phenolic resin, polyurethane, polyester, polyether sulfone, polyether ether kedone, etc.), alumina membrane (held on glass or resin), silica Examples include films (held on glass or resin), and methods of coloring include kneading, transfer, dyeing, and sublimation deposition.

(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 Quinizarin 9.6 parts, leucoquinizarin 2.4 parts, boric acid 6.0 L 4-cyclohexylaniline 9.6 parts,
50 parts of 95% ethanol was mixed and heated under reflux at 79°C for 4 hours. It was left to cool to room temperature, the precipitated solid was separated by filtration, dried, and purified by column to yield I-(4-cyclohexylanilino)-4-hydroxyanthraquinone 6.3
I got the department.

λwax (in chloroform) 588nm elemental analysis value (
%) C) I N Actual value 78.60 5.85 3.50 Calculated value
78.57 5.83 3.52 5 parts of this dye,
It was mixed with 50 parts of polypropylene glycol, made into fine particles, coated on paper, dried to make a transfer paper, coated with alumina gel, and transferred to a baked 3ttm glass plate at 200°C to make a blue 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 6.8 parts of p-anisidine instead of 9.6 parts of 4-cyclohexylaniline, and 1-(4-methoxyaniline) was purified by column purification. 7.5 parts of lino)-4-hydroxyanthraquinone were obtained.

λwax (in chloroform) 587n* elemental analysis value (
%) HN Actual measurement 4fi 73.14 4.81 4.01 Calculated value 73.04 4.78 4.06 Add 10 g of polyester film, 2000 g of ethylene glycol, and 2 g of the obtained dye, and dye at 130°C for 1 hour. , created a blue filter.

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

Example-3 By the same method as in Example-1, 9.4 parts of 4-aminobiphenyl was added instead of 9.6 parts of 4-cyclohexylaniline.
1-(4-phenylanilino)-4-hydroxyanthraquinone 8.1
I got the department.

λmax (in chloroform) 588n11 elemental analysis (
It! (%) CI (N Actual value 79.61 4.42 3.52 Calculated value
79.78 4.38 3.58 Transfer paper (for filters) prepared from 1 g of the obtained dye, 10 g of Pyronal MD-1,200 (Toyobo Co., Ltd. product) and 1 g of silica gel was placed on a polymethyl methacrylate resin plate. A blue filter was obtained by overlapping the dyestuffs (dye arrangement) and calendering them at 200°C.

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 the spectral characteristics (transmittance) at each wavelength of the filters produced in Examples 1, 2, and 3 using the dye according to the present invention. . Patent applicant Mitsui Toatsu Chemical Co., Ltd. Figure-1 Time-2

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1, R_2, R_3, R_4, R_5 are an alkyl group, a cycloalkyl group, an alkoxy group, Alkoxyalkyl group, alkoxyalkoxyalkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group,
Halogenoalkyl group, cyanoalkyl group, aryl group,
It represents an aralkyl group, an alkenyl group, a halogen atom, or a hydrogen atom. ) is a blue dye for filters.