JPS63191884A - Luminescent resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is transparent and colorless under usual light, emits bright red light upon being exposed to UV rays, has no effect on the human body through absorption of the UV rays, and has high durability and which comprises an Eu complex having a benzoyltrifluoroacetone ligand. CONSTITUTION:A resin compsn. comprising an Eu complex containing a benzoyltrifluoroacetone ligand of the formula (wherein R1 and R2 are each H, halogen, alkyl, alkoxy, amino, dialkylamino, alkylamino, aryl, or aralkyl; and A<+> is an org. or inorg. ammonium, pyridinium, or phosphonium or a metallic cation). Although this resin compsn. is transparent and colorless under usual light, it emits bright red light upon being exposed to UV rays, has no effect on the human body because it can absorb the UV rays, and can suppress the deterioration of the resin, which renders the compsn. suitable for use in toys, stage and interior decorations, show windows, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a resin molded product or resin film that is transparent and colorless under normal visible light and emits red light under ultraviolet light irradiation. It can be applied to fields that use bright colors, such as toys, stage decorations, interior decorations, and shop windows.

[Prior art and problems to be solved by the invention] Many luminescent compounds are known and are used as fluorescent whitening dyes, dyes for lasers, and pigments for luminescent resins such as solar concentrators. This is a well-known fact.

Most of these compounds have a small difference between the maximum absorption wavelength and the maximum emission wavelength, that is, the Stokes shift, and the difference is generally only about 1 On+s to 130 rv, and the overlap between the absorption spectrum and the emission spectrum is large, so they cannot be used at high concentrations. In this case, a reabsorption phenomenon occurs and the luminance of the emitted light decreases.

Therefore, for example, most compounds that emit red light have yellow to blue absorption, and cannot be applied to fields that utilize only red light emission because they have no absorption color.

Under these circumstances, as an exception, thenoyltrifluoroacetone europium complex was attempted to be used as an ink for documents or cards that require confidentiality by taking advantage of its colorless absorption and red luminescence, but it was not possible to preserve it. Stability was poor (improvement was desired for practical purposes.Also, benzoyltrifluoroacetone europium complex was also known to emit red light with colorless absorption and to emit laser light, but other At present, no developments have been made regarding applications.

On the other hand, luminescent compositions of all colors have been reported for inorganic compounds, but when attempts are made to incorporate them into resins, they not only impair transparency but also have low luminous intensity, so they have not been put to practical use.

[Means for solving problems]

In view of the above circumstances, the present inventors conducted intensive studies to obtain a highly durable resin composition that is completely insensitive to visible light and emits red light when exposed to ultraviolet light. The present inventors have discovered that a luminescent resin composition containing at least one type of europium complex having a ligand has unprecedented high durability and high red luminescence, and has completed the present invention.

That is, the present invention provides general formula (I) (wherein R3 and R2 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, a dialkylamino group, an alkylamino group, an aryl group or an aralkyl group, A light-emitting device characterized by containing at least one compound represented by (which may be the same or different from each other, and t represents an organic or inorganic ammonium cation, pyridinium cation, phosphonium cation, or metal cation) It is a synthetic resin composition.

The present invention will be explained in more detail below.

The luminescent compound of the present invention is represented by the general formula (I) 1, and specific examples of R1 and R2 in the general formula (I) include a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, etc. Halogen atoms, alkyl groups such as methyl, ethyl, isopropyl, alkoxy groups such as methoxy, ethoxy, butoxy, amino groups, dialkylamino groups such as dimethylamino, ethylamino, phenyl, p-tolyl, etc.
Examples include aralkyl groups such as phenethyl, 3-(2-methylphenyl)-propyl, and A
Specific examples include ammonium cations such as tetraethylammonium, tetrabutylammonium, piperidinium, and pyrrolidinium, N-hydropyridinium,
Examples include pyridinium cations such as N-methylpyridinium and 1,4-dimethylpyridinium, phosphonium cations such as tetraphenylphosphonium and tetrabutylphosphonium, and metal cations such as sodium and potassium.

At least one kind of compound represented by the general formula (I) is contained in various resins to obtain an atomized compound.

Resins that can be used in the present invention are optically transparent, such as polyvinyl alcohol, polyvinyl butyral, diethylene glycol bisallyl carbonate resin, polymethacrylate and copolymers thereof,
Examples include polyvinyl acetate, celluloses, polyester, polycarbonate, polystyrene and its copolymers, epoxy resins, optionally halogenated bisphenol A di(meth)acrylate resins and their copolymers, nylon resins, polyurethanes, etc. .

In the present invention, the concentration of the luminescent compound in the resin is
It is sufficient that the transparency of the resin is not lost, but -a
The amount is 0.001 to 10% by weight, preferably 0.01 to 5% by weight based on the resin.

[Action and effect]

The resin composition containing the europium complex having a benzoyltrifluoroacetone-based ligand of the present invention is transparent and colorless under normal light, but emits a bright red color under ultraviolet lamp light, and also absorbs ultraviolet light. Therefore, there is almost no harm to the human body, and deterioration of the resin can be suppressed.

In other words, the resin composition of the present invention is a high-intensity red light emitter with no absorption color, which was not seen before, and also has excellent high durability performance, providing a new composition that is effective in practical use. It is something to do.

〔Example〕

Hereinafter, the luminescent resin composition of the present invention will be explained in more detail with reference to Examples. Note that "parts" in the examples indicate "parts by weight."

Example 1 0.03 parts of piperidium tetra(benzoyltrifluoroacetone) europium complex and 3 parts of polyvinyl butyral resin were dissolved in 30 parts of tetrahydrofuran, and a cast film was obtained by distilling the tetrahydrofuran at normal pressure on a smooth glass surface. Ta.

This resin film is transparent and colorless under normal fluorescent lighting and outdoors, but when irradiated with an ultraviolet lamp, it emits a bright red color.
When the emission spectrum and excitation spectrum of this resin film were measured using
In part m, the excitation maximum wavelength was 348rIIB. Furthermore, when this film was left outdoors for one month, the luminescence intensity was almost the same as in the initial state, and no deterioration of the resin was observed.

Example 2 A resin plate was prepared by dissolving 3 parts of tetrabutylammonium tetra(P-methylbenzoyltrifluoroacetone) europium complex in 100 parts of methyl methacrylate and performing cast polymerization using azobisisobutyronitrile as a polymerization initiator. The 0 resin plate also exhibited a bright red luminescent color upon irradiation with ultraviolet rays.1 The maximum emission wavelength was 619 parts m, and the maximum excitation wavelength was 349 parts m. Similar to Example 1, good results were obtained in terms of durability and stability.

Example 3 A resin film was obtained in the same manner using the tetrabutylphosphonium tetra(p-dimethylaminobenzoyltrifluoroacetone) europium complex in place of the europium complex in Example 1. The film also became brighter when irradiated with ultraviolet rays. It exhibited a red luminescent color. The maximum emission wavelength of this film is 620nra, and the maximum excitation wavelength is 35nra.
It was 0ns+.

Similar to Example 1, good results were obtained in terms of storage stability.

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 and R_2 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, amino groups, It represents a dialkylamino group, alkylamino group, aryl group or aralkyl group, which may be the same or different from each other, and A^+ represents an organic or inorganic ammonium cation, pyridinium cation, phosphonium cation or metal cation. ) A luminescent resin composition comprising at least one of the compounds represented by: