JPH01233401A - Green dye for filter - Google Patents

Abstract

PURPOSE:To improve light resistance and heat resistance by using specific phthalocyanine or the isomer thereof. CONSTITUTION:The phthalocyanine expressed by the formula I or the isomer thereof is used as the green dye for filters. In the formula I, R denotes an alkyl group of 1-20C, substd. or unsubstd. alkoxy group of 1-20C, hydroxyalkyl group of 1-20C, alkoxyalkyl group of 1-20C. Met denotes 2 hydrogen atoms, metals or metal oxides. The metals expressed by Met are exemplified by Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe and include also the metal chlorides and hydroxides such as AlCl, InCl, FeCl, TiCl2, SnCl2, SiCl2 and GeCl2. The Cu, Ni, Co, and Fe are more particularly preferable for the high durability and low cost thereof. The metal oxides are exemplified by TiO, VO, MnO, etc. The resistances to light, heat and moisture of the green dye are thereby improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a green absorbent used in display elements such as liquid crystal televisions or color separation filters used for storage.

[Conventional technology and problems]

Conventionally, dyes for green filters include anthraquinone (Japanese Patent Application Laid-Open No. 61-246258), naphthoquinone (
Japanese Patent Application No. 60-110290), triphenylmethane type (surface: "Special Functional Colorants J CMC, p. 111), etc. are known.

However, the anthraquinone-based and naphthoquinone-based green pigments did not have sufficient transmission of light of 500 to 600 r+a+, and also did not have sufficient sunlight fastness.

In addition, triphenylmethane is suitable for coloring filters using gelatin or casein because its molecules are ionized, and although it was used for gelatin filters, the moisture resistance of the filter itself There is a limit to its use due to its poor heat resistance, and it could not be used in general display elements due to the dye itself's poor light resistance, heat resistance, and moisture resistance.

[Problem to be solved by the invention]

As mentioned above, the present invention aims to improve the poor light resistance and heat resistance, which are the drawbacks of conventional filters and filter dyes.

[Structure of the invention]

The present invention is based on the following general formula (+) [In formula (I), R is an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or
20 hydroxyalkyl group, an alkoxyalkyl group having 1 to 20 carbon atoms, and Met represents 2 hydrogen atoms, a metal or a metal oxide. ] This invention relates to a green filter dye that is a phthalocyanine or an isomer thereof.

In formula (I), the alkyl group having 1 to 20 carbon atoms represented by R may be any linear, branched, or cyclic alkyl group. Examples of substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms include branched or straight chain methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentoxy groups,
Hexyloxy group, heptyloxy group, octyloxy group, cetyloxy group, dodecyloxy group, cyclohexyloxy group, methoxymethoxy group, methoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxyethoxy group, ethoxyethoxyethoxy group, ethoxy Ethoxyethoxyethoxy group, methoxyethoxyethoxyethoxy group, butoxyethoxy group, cetyloxyethoxy group, methoxypropoxy group, methoxypropoxypropoxy group, ethoxyproboxybroboxybroboxy group, hydroxyethoxy group, hydroxyethoxyethoxy group, hydroxyethoxyethoxy Examples include ethoxy group, hydroxyproboxyproboxyproboxy group, hydroxybutoxy group, hydroxyhexyloxy group, p-butylphenoxy group, and the like.

Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, and hydroxyoctyl group.

Examples of alkoxyalkyl groups having 1 to 20 carbon atoms include:
Examples include ethoxymethyl group, butoxymethyl group, hexyloxymethyl group, methoxyethoxyethoxymethyl group, cetyloxymethyl group, butoxyethoxyethoxymethyl group, and the like.

Metals represented by Met include Zn, Mg, S
i.

5nSRh, PL, Pd, Mo, Mn, Pb
, Cu, Ni, Go, Pe, etc., as well as ^IcI, InCl, FeCl, TiChS
Also included are metal chlorides and hydroxides such as nCIg, 5iCIz, and GeCIx. In particular, Cu, Ni, Co, and Fe are preferred because of their higher durability and low cost. Examples of metal oxides include TiO, VOlMnO, and the like.

As a method for producing a filter, the dye of the present invention and
It can be produced by mixing thermoplastic resins such as polystyrene, polymethyl methacrylate, polycarbonate, polyester, etc. and then injection molding, stretching, etc., or by dissolving the dye of the present invention alone or together with a binder in a solvent and casting it on a substrate. Form a film using a spin code, etc., or
Alternatively, there is a method in which a film is formed on a substrate by vapor deposition, or a method in which a dye is mixed together with a resin monomer, a resin intermediate, or a resin, and then polymerized and processed.

As a method for synthesizing the dye represented by the general formula (I), the following general formula (If) [In the formula (II), R means the same group as R in the formula (I). ] A phthalonitrile derivative represented by the following formula (III) M
et-X z (m) [Formula (I
In [I), Met is the same as Met in formula (I), and
is a monovalent or divalent atom such as a halogen atom, an acetate anion, or oxygen.
means a valent ligand. ] There is a method of heating a metal compound represented by the following in a solvent such as alcohol, alkylamine urea, halogenated hydrocarbon, or quinoline.

〔Example〕

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

Example 1 A filter was manufactured by adding 1 part of tetra-(n-butyl)phthalocyanine oxyvanadium to 100 parts of polystyrene and injection molding. This filter is
The durability and transmission characteristics were good.

Tetra-(n-butyl)phthalocyanine oxyvanadium was synthesized as follows.

184 parts of 4-n-butylphthalonitrile and 25 parts of vanadyl trichloride were reacted in 1000 parts of chlornaphthalene at 200°C for 3 hours, and the reaction solution was discharged into 10000 parts of methanol to obtain 100 parts of the target compound.

Example 2 4.4°-
Bis(3-aminophenoxy)biphenyl 36.8g
and 202 g of N,N-dimethylformamide were charged, 39.8 g of 4.4'-(p-phenylenedioxy)cyphthalic dianhydride was added in portions under a nitrogen atmosphere at room temperature, and the mixture was heated at room temperature for 20 hours. Stirred. 3.0 g of 1M tetra-(hydroxyethoxyethoxyethoxy)phthalocyanine was added to the thus obtained polyamic acid solution, mixed, and then cast on glass.

Heat treatment was performed at 180°C for 5 hours. The green filter thus obtained had good absorption characteristics and excellent heat resistance and moisture resistance.

Tetra-(hydroxyethoxyethoxyethoxy)phthalocyanine was synthesized as follows.

276 parts of 4-hydroxyethoxyethoxyethoxyphthalonitrile, 45 parts of copper acetate, 7 parts of diazabicycloundace
10 parts of N,N-dimethylaminoethanol were reacted under reflux and purified using a column to obtain 100 parts of the target compound.
I got the department.

Example 3 122 parts of 1.4-bis(α,α-dimethylisocyanatomethyl)benzene, 117 parts of 1,3.5-1-lis(3-mercaptopropyl)isocyanurate, and Htetra(ethoxyethoxy)phthalocyanine vanadyl oxide 10 parts of dibutyltin dilaurate and 0.3 parts of dibutyltin dilaurate were mixed to form a homogeneous liquid. This liquid was poured into a mold consisting of a glass mold whose surface had been treated with a fluorine-based external mold release agent and a PVC gasket.

Then at 70°C for 4 hours, at 80°C for 2 hours, at 90°C
After heating for 2 hours at 100°C and 2 hours at 120°C, the mold was cooled and released from the mold. The obtained filter had good absorption characteristics and was excellent in light resistance and moisture resistance.

Example 4 100 parts of polymethyl methacrylate and 3 parts of tetra-(butoxymethylene)phthalocyanine vanadium were dissolved in 500 parts of chloroform, cast on a glass substrate, and dried. The filter made from this birch had good durability and filter properties.

Examples 5 to 22 Phthalocyanine and isomeric dyes having the following general formula Met and R as shown in Table 1 are mixed with resins shown in Table 1, and Examples 5 to 19 are the same as Example 1. In Examples 20 to 22, filters were produced in the same manner as in Example 4. These filters had good durability and filter properties.

(Left below) Table 1 (Note-1) PS Polystyrene PMMA
Polymethyl methacrylate PC Polycarbonate PET Polyethylene terephthalate Table 2 (Note-1) Produced in the same manner as Example 1 using the dye of JP-A-61-246258 (Note-2) Surface: "Special Functional Dye J" Published by CMC Mitsui Toatsu Chemical Co., Ltd. Patent applicant for a filter that uses gelatin as Pill pigment

Claims (1)

[Claims] 1) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included. [In formula (I), R is an alkyl group having 1 to 20 carbon atoms, a substituted group having 1 to 20 carbon atoms, or Unsubstituted alkoxy group, carbon number 1
~20 hydroxyalkyl group, represents a C1-20 alkoxyalkyl group, Met is two hydrogen atoms,
Represents a metal or metal oxide. ] A green filter dye that is a phthalocyanine or an isomer thereof.