JP2574143B2 - Resin composition containing luminescent compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention provides a resin composition containing a compound which is colorless under ordinary visible light and emits a red color under ultraviolet irradiation. More specifically, the present invention provides a resin molded product or a resin film which can be applied to fields utilizing vivid coloring, such as toys, stage equipment, interior decoration, and show windows.

[0002]

2. Description of the Related Art Many luminescent organic compounds are known, and it is well known that they are used as fluorescent whitening dyes or laser dyes.

Most of these compounds have a small difference between the absorption maximum wavelength and the emission maximum wavelength, that is, the Stokes shift, and generally have a wavelength of only about 10 nm to 130 nm. If this occurs, a re-absorption phenomenon occurs and the emission intensity decreases.

Therefore, no practical organic compound has been found that emits red light with no absorption color, that is, absorbs at 400 nm or less and emits light at 590 nm or more. In an inorganic system, for example, europium oxide or the like is present, but is insoluble in a solvent or a resin and cannot be used in a field requiring transparency. Various organic tris (thenoyltrifluoroacetonate) europium and tris (benzoyltrifluoroacetonate) europium complexes are known, but have not been put to practical use in terms of durability.

[0005]

The above-mentioned conventional luminescent compounds listed above do not solve the problems of durability due to a decrease in luminescence intensity and the like, and the problems of solubility in solvents and resins, etc. The resin composition having high durability and high luminance used for such purposes has not yet been put to practical use.

[0006]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result, have found that tetra {4,4,4-trifluoro-1- having ammonium salt or the like as a counter ion.
The present inventors have found that a resin composition containing a (2-thienyl) -1,3-butandionate-europium complex has satisfactory performance, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula (I)

Embedded image [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an aryl group, or an aralkyl group. A ⁺ represents a cation represented by the following formula.

Embedded image (However, R ₃ , R ₄ , R ₅ , and R ₆ each represent a hydrogen atom, an alkyl group, or an aralkyl group, and may be bonded to each other to form a ring.) It is a resin composition characterized by containing.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The luminescent compound used in the present invention is represented by the above-mentioned general formula (I).
Specific examples of ₁ and R ₂ include a hydrogen atom, a chlorine atom, a fluorine atom, a halogen atom such as a bromine atom, an alkyl group such as methyl, ethyl and isopropyl, an alkoxy group such as methoxy, ethoxy and butoxy, an amino group and a dimethyl group. Amino group, dialkylamino group such as diethylamino group, methylamino group, alkylamino group such as ethylamino group,
Examples include aryl groups such as phenyl group and p-tolyl group, benzyl groups, phenethyl group, and aralkyl groups such as 3- (2-methylphenyl) propyl group.

Embedded image Specific examples of R ₃ , R ₄ , R ₅ , and R ₆ include a hydrogen atom,
Examples include an alkyl group such as a methyl group, an ethyl group, a butyl group, and an octyl group, and an aralkyl group such as a benzyl group and a phenethyl group.

When A ⁺ is an ammonium cation, specific examples include tetraethylammonium, tetra-n-
Butyl ammonium, methyl tri-n-octyl ammonium, trimethyl benzyl ammonium, dimethyl (β-phenyl) ethyl ammonium, tri-n-butyl (β-phenyl) ethyl ammonium, dimethyl diethyl ammonium, tetra-n-octyl ammonium, N-methyl Piperidium, N, N-dimethylpiperidinium, N-ethylpyrrolidium, N, N-diethylpyrrolidium and the like.

Specific examples of other cations represented by A ⁺ include pyridinium cations such as N-benzylpyridinium, N-methylpyridinium and 1,4-dimethylpyridinium, and phosphoniums such as tetraphenylphosphonium and tetrabutylphosphonium. Cations.

The compound of the formula (I) is prepared by converting europium perchlorate and a 4,4,4, -trifluoro-1- (2-thienyl) -1,3-butanedione compound into acetone in the presence of sodium hydroxide. a compound obtained by reaction at, a ⁺ X ^- (a ⁺ has the same meaning as in formula (I), X ^- represents an anion such as halogen.) easily getting by the action of Can be.

The resin composition of the present invention can be obtained by incorporating at least one compound represented by the general formula (I) into various resins.

The resins which can be used in the present invention are those which are optically transparent and include, for example, polyvinyl alcohol, polyvinyl butyral, diethylene glycol bisallyl carbonate resin, polymethacrylate and copolymers thereof, polyvinyl acetate, celluloses and the like. , Polyester, polycarbonate, polystyrene and copolymers thereof, epoxy resin, di (meth) acrylate resin of bisphenol A which may be halogenated and copolymers thereof, nylon resin, polyurethane and the like.

In the present invention, the concentration of the luminescent compound in the resin may be within a range that does not cause loss of the transparency of the resin. Is 0.01 to 5% by weight.

[0016]

EXAMPLES The luminescent compound according to the present invention will be described in more detail with reference to the following synthetic examples. In the examples, “parts” indicates “parts by weight”. Synthesis Example 1 28 parts of an aqueous solution containing 7.2% by weight of europium peroxide was mixed with 4,4,4-trifluoro-1- (2-thienyl).
35.6 parts of -1,3-butanedione, 6.4 sodium hydroxide
Parts, 500 parts of an acetone solution containing 10 parts of water.
After stirring for 1 hour, acetone was distilled off under reduced pressure, and ethanol 10
0 parts, 500 parts of water were added, and the mixture was stirred for 10 minutes, filtered, washed with water,
Dried. The obtained solid was dissolved in 370 parts of ethanol, 11.9 parts of tetra-n-butylammonium bromide was added, and after stirring for 1 hour, 1,000 parts of water was added and left for 1 hour. Filtration, washing with water and drying under reduced pressure gave 45 parts of the following compound (1) (yield 88%).

[0017]

Embedded image

The compound (1), that is, n-tetrabutylammonium tetra {4,4,4-trifluoro-1
The melting point of-(2-thienyl) -1,3-butanedionate @ europium complex is 172 to 175 ° C. and the decomposition temperature is 2
56 ° C. and the maximum emission wavelength in acetone is 619 n
m, the excitation maximum wavelength was 360 nm.

Synthesis Examples 2 to 10 Table 1 shows compounds of ammonium salts obtained by the same operation as in Synthesis Example 1.

[0020]

[Table 1]

Synthesis Examples 11 to 15 In the same manner as in Synthesis Example 1, compounds of a pyridinium cation salt were obtained as A ⁺ as a counter ion, and are shown in Table 2.

[0022]

[Table 2]

Synthetic Examples 16 to 18 In the same manner as in Synthetic Example 1, a compound of a phosphonium cation salt was obtained as A ⁺ as a counter ion, and is shown in Table 3.

[0024]

[Table 3]

Hereinafter, the resin composition of the present invention containing the luminescent compound described in the present application will be described in more detail by way of examples. In the examples, “parts” indicates “parts by weight”. Example 1 3 parts of tetrabutylammonium tetra {4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedionate} europium complex (compound (1)) was dissolved in 100 parts of methyl methacrylate. Then, cast polymerization was performed using azobisisobutyronitrile as a polymerization initiator to prepare a resin plate.

The resin film is transparent and colorless outdoors under normal fluorescent light, but emits a bright red color when irradiated from an ultraviolet lamp. When the emission spectrum and excitation spectrum of this resin film were measured, the emission maximum wavelength was 620 nm and the excitation maximum wavelength was 360 nm. When this film was left outdoors for one month, the luminescence intensity was almost the same as that in the initial state, and no deterioration of the resin was observed.

Example 2 n-tetrabutylammonium tetra {4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedionate} europium complex (compound (1)) 0.2
Parts and 100 parts of polystyrene were mixed and melted at 200 ° C., and a resin plate was prepared using an injection molding machine. This resin plate exhibited a vivid red color under ultraviolet irradiation, and showed only 2% decrease in luminous intensity after a 300-hour light resistance test with a sunshine weatherometer, indicating excellent stability performance.

Example 3 Dimethyldidodecylammonium tetra {4,4,4-
Trifluoro-1- (5-chloro-2-thienyl)-
After dissolving 0.01 part of 1,3-butanedionate europium complex (compound (6)) and 1 part of polyvinyl butyral resin in 10 parts of tetrahydrofuran, applying the solution on a smooth glass surface, tetrahydrofuran as a solvent under normal pressure is added. The film was gradually evaporated to obtain a cast film.

This resin film can be used under ordinary fluorescent lighting.
Although it was indistinguishable from the paper before application, it emitted a bright red luminescent color when irradiated from an ultraviolet lamp. When this resin film was left under a fluorescent lamp for one month, the emission intensity was the same as that in the initial state, and no deterioration of the resin was observed.

Example 4 Tetrabutylphosphonium tetra {4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedionate} europium complex (compound (17)) 0.03
And 3 parts of a polyvinyl butyral resin were dissolved in 30 parts of tetrahydrofuran, and a cast film was obtained while distilling tetrahydrofuran under normal pressure on a smooth glass surface.

The resin film was transparent and colorless outdoors under a normal fluorescent lamp, but emitted a bright red color when irradiated from an ultraviolet lamp. When the emission spectrum and the excitation spectrum of this resin film were measured, the emission maximum wavelength was 620 nm and the excitation maximum wavelength was 360 nm. When this film was left outdoors for one month, the luminescence intensity was almost the same as that in the initial state, and no deterioration of the resin was observed.

Example 5 Instead of the europium complex of Example 3, N-benzylpyridinium tetra {4,4,4-trifluoro-1-
When a resin plate was prepared using (2-thienyl) -1,3-butanedionate ナ ー europium complex (compound (11)), the same excellent results as in Example 3 were obtained.

Example 6 Instead of the europium complex of Example 3, N, N-diethylpiperidium tetra {4,4,4-trifluoro-1
When a resin plate was prepared using-(4-benzyl-2-thienyl) -1,3-butanedionate @ europium complex (compound (8)), good results were obtained in exactly the same manner as in Example 3.

[0034]

According to the present invention, the tetra ｛4,4,4-
The trifluoro-1- (2-thienyl) -1,3-butanedionato @ europium complex is a compound that is colorless under ordinary visible light and emits red light under irradiation with ultraviolet light. The resin composition containing at least one of the following,
Although no color can be recognized at all under normal light, it emits a bright red color when irradiated with an ultraviolet lamp, has excellent performance with high durability and high luminance, and has extremely high practical value.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09D 11/02 PSY C09D 11/02 PSY

Claims (1)

(57) [Claims] 1. A compound of the general formula (I) [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an aryl group, or an aralkyl group. A ⁺ represents a cation represented by the following formula. Embedded image (However, R ₃ , R ₄ , R ₅ , and R ₆ each represent a hydrogen atom, an alkyl group, or an aralkyl group, and may be bonded to each other to form a ring.) A resin composition characterized by containing: