JP2000303067A - Luminescent material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a luminescent material which does not need low-temperature storage, or the like, and can be used at room temperature or in an aqueous system by combining a medium having hydrophilicity, hydrophobicity, and a mol.wt. in a specified range with a compound capable of emitting light by the reaction with a water-soluble peroxide. SOLUTION: The medium having hydrophilicity and hydrophobicity has a wt. average mol.wt. of 200-5,000,000, its examples being a coplolymer of a hydrophilic vinyl monomer and a hydrophobic vinyl monomer, a graft polymer formed by grafting a hydrophilic or hydrophobic monomer onto a hydrophobic or hydrophilic polymer, and a material formed by covalently bonding a hydrophilic or hydrophobic monomer to a hydrophobic or hydrophilic polymer by an organic reaction. The water-soluble peroxide is preferably hydrogen peroxide. The compound capable of emitting light is a compound having carbonyl or ester group (groups), preferable examples being oxalic acid and its derivatives. This luminescent material may further contain a fluorescent or phosphorescent substance which emits fluorescence or phosphorescence preferably by the decomposition of an oxalic ester, the use of a fluorescent substance being preferable. The luminescent material in the form of a coating film, a film, a plate or the like is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminescent material capable of emitting light as a water-soluble peroxide, and more particularly to a luminescent material which can be used in the form of a coating film, film, plate, rod or tube.

[0002]

2. Description of the Related Art Heretofore, a luminescent material which emits light by chemical luminescence (chemiluminescence) generally emits light in an organic solvent. In water systems, bioluminescence (bioluminescence) using luciferin and luciferase is known. In the case of bioluminescence, there is a problem that the enzyme must be stored at a low temperature in order to use the enzyme. It is well known that the luminous efficiency is reduced by 7 to 8 digits or more when an aqueous system is used for chemiluminescence.
Therefore, attempts have been made to increase the luminous efficiency by adding a water-soluble resin such as polyethylene glycol, but no significant improvement has been found. Therefore, test kits using chemiluminescence in an aqueous system cannot replace bioluminescence at this time due to these disadvantages.

[0003]

SUMMARY OF THE INVENTION The present invention provides a luminescent material that can be used at room temperature and in an aqueous system without the need for low-temperature storage.

[0004]

The present invention comprises a hydrophilic and hydrophobic medium having a molecular weight of 200 to 5,000,000 and a compound capable of reacting with a water-soluble peroxide to emit light. It relates to a light emitting material. Furthermore, the present invention relates to the above luminescent material, wherein the water-soluble peroxide is hydrogen peroxide. Further, regarding the light emitting material containing a fluorescent substance or a phosphorescent substance, the compound capable of emitting light is the above light emitting material which is an oxalate compound, and the light emitting material is a coating, a film, a plate, a rod, or a tube. About materials.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the present invention will be described below. Weight molecular weight having hydrophilicity and hydrophobicity of 200 to 5,0
As a medium of 000, a copolymer of a hydrophilic vinyl monomer and a hydrophobic vinyl monomer, a grafted polymer obtained by grafting a hydrophilic vinyl monomer or a hydrophobic vinyl monomer to a hydrophilic polymer or a hydrophobic polymer, respectively. Or a material in which a hydrophilic monomer or a hydrophobic monomer is covalently bonded to a hydrophilic polymer or a hydrophobic polymer by an organic reaction. There is also a medium in which a polymer from a hydrophilic vinyl monomer and a polymer from a hydrophobic vinyl monomer are mixed.

As the hydrophilic vinyl monomer, for example,
N-vinyl-2-pyrrolidone, vinyl ether, N-vinyl-ε-caprolactam, (meth) acrylamide,
N-methylol (meth) acrylamide, N-methoxy (meth) acrylamide, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, (meth) acrylic acid (salt), vinylsulfonic acid (salt), maleic acid ( Salt), maleic anhydride, itaconic acid (salt), polyethylene glycol, (meth) acrylic acid ester modified with polypropylene glycol, silicon-containing vinyl monomers, and the like. Any monomer can be used.

As the hydrophobic vinyl monomer, for example,
There are styrene, ethylene, propylene, butadiene, chloroprene, (meth) acrylic acid esters, vinylidene fluoride, vinyl acetate and the like, but there is no need to be limited to these, and vinyl monomers having hydrophobicity can be used.

[0008] Examples of the grafted polymer include polymers obtained by grafting (meth) acrylic esters or styrene derivatives, vinyl esters and vinyl ethers to polyvinyl alcohol. Any grafted polymer having hydrophobicity can be used.

A mixed system of a hydrophilic polymer and a hydrophobic polymer may be used as long as it is a mixed system of a polymer obtained by polymerizing a hydrophilic vinyl monomer and a polymer obtained by polymerizing a hydrophobic vinyl monomer. It is also possible to use a mixture of the mixed copolymers. In addition to polymers derived from vinyl monomers, polyamides, polyesters, polyethers, polyimines, polycarbonates, polysulfones and the like can be used, and natural polymers can also be used.
The weight average molecular weight of the medium having hydrophilicity and hydrophobicity used in the present invention is preferably from 200 to 5,000,000.
More preferably, it is 5,000 to 200,000.
When the weight average molecular weight is less than 200, the diffusion of water into the medium becomes large, and the light emission time becomes short. On the other hand, when the weight average molecular weight is larger than 5,000,000, the diffusion of the water-soluble peroxide into the medium becomes small, so that light emission does not occur.

As the water-soluble peroxide, any peroxide soluble or dispersible in water can be used. For example, hydrogen peroxide, benzoyl peroxide, perbenzoic acid, and hydroxyperoxide include t-butyl hydroperoxide, cumene hydroperoxide, other peroxysuccinic acids, benzoyl peroxide, and the like, but are not limited thereto, and are dissolved in water. Alternatively, it can be used if it is dispersed. Among them, hydrogen peroxide is preferred from the viewpoint of handling.

A catalyst may be used to increase the activity of the water-soluble peroxide. For example, a quaternary salt of a water-soluble amine, tetrabutylammonium salicylate and the like can be mentioned.

The compound capable of reacting with a water-soluble peroxide to emit light includes a compound having a carbonyl group or an ester group. Specifically, oxalic acid or a derivative thereof, luminol, lophine (2,4,5 -Triphenylimidazole), acridinium salts, acridinium esters, tetrakis (dimethylamino) ethylene, indole derivatives. These may be used in combination. Among them, oxalic acid or a derivative thereof is preferable from the viewpoint of handling.

Examples of the oxalic acid derivative include oxalic acid ester, oxalic acid dichloride, oxalic acid dibromide, oxalic acid amide and the like. Further, a structure of a copolymer such as a polyamide ester, a polyimide ester, or a polycarbonate ester is also possible.

Examples of the oxalate include dimethyl oxalate, dibutyl oxalate, monochloromethyl oxalate, dichloromethyl oxalate, trichloromethyl oxalate, diphenyl oxalate, monochloro (fluoro) phenyl oxalate, Dichloro (fluoro) phenyl oxalate, trichloro (fluoro) phenyl oxalate, tetrachloro (fluoro) phenyl oxalate, and 1 to 5 substituents such as bromo, iodo, nitro, methoxy and methyl Phenyl esters can also be used. It is also possible to use an ester of an aromatic compound having two phenolic hydroxyl groups, for example, a polyester or a copolymer polyester of oxalic acid and bisphenols. Also, oxalic acid esters can be used in combination.

As the fluorescent or phosphorescent substance, any substance which emits fluorescent or phosphorescent light by decomposition of an oxalate ester can be used. The mechanism of light emission is shown by the following equation.

[0016]

Materials that emit fluorescence include, for example, perylene, ruprene, rhodamine B, DNS-alanine, 3-methylcholanthrene, rose bengal, benzo {α} pyrene, NBD-proline, 9,10 dibromoanthracene, riboflavin, SBD- Mercaptoethanol,
Umbelliferone, α-tocopheron, anthracene,
Naphthacene, phenanthrene, bis (phenylethynyl) -naphthalene, bis (2,4,5-trichloro-6
Any substance that emits fluorescence or phosphorescence, such as (carbobutoxyphenyloxalate), can be used. The phosphorescent compound is an organic phosphorus-containing compound, such as triphenylene, but the use of a fluorescent substance is preferred from the viewpoint of handling and analysis.

The luminescent material of the present invention may contain pigments, plasticizers, inorganic salts, and reactive monomers. In addition, it is also possible to use a coating film in which a pattern is drawn by printing or the like in the state of a paint in order to obtain a coating film. The luminescent material of the present invention can be applied to a plate, a container, or the like as needed, and applied, or the like, to obtain a luminescent material formed into a coating, a film, a plate, a rod, or a tube. When this luminescent material is brought into contact with an aqueous solution containing a water-soluble peroxide and a fluorescent or phosphorescent substance, light emission occurs. When a fluorescent or phosphorescent substance is already contained in the luminescent material, light emission occurs when the substance is brought into contact with an aqueous solution containing only a water-soluble peroxide. If the water-soluble peroxide is present in a hydrophilic and hydrophobic polymer medium such as a microcapsule or a partition wall, it is possible for both to come into contact by external stimulus to cause light emission.

Applications include a simple test kit for environmental hormones using chemiluminescence, chemical light (penlight), application to chemiluminescence immunoassay, use for chemistry teaching materials, fishing float for night time, temperature, humidity and pressure. Indicators and luminescent inks that change color due to environmental changes such as In addition, since it can be used in an aqueous system and has good storage stability, it is a material that is also expected to be used as a substitute for bioluminescence analysis.

[0020]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

(Production Example 1) Synthesis of Copolymer Having Hydrophilicity and Hydrophobicity (Sample A) Methyl ethyl ketone (MEK) was placed in a one-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser. ) 254 ml Vinylpyrrolidone 78 g Methyl methacrylate (MMA) 30 g Azobisisobutyronitrile (AIBN) 1 g is charged, and the temperature without a flask is raised to 70 ° C. in a hot water bath. After continuing the reaction for 8 hours, 1 g of AIBN was added.
Add and continue stirring for another 2 hours. The weight average molecular weight was 32, as measured by GPC (polystyrene conversion).
000. The composition ratio of the copolymer of vinylpyrrolidone and MMA was approximately 3: 7.

Synthesis of copolymer having hydrophilicity and hydrophobicity (sample B) MEK 252 ml Vinylpyrrolidone 66 g MMA 55 g AIBN 1 g Polymerized under the same conditions as above and subjected to molecular weight measurement by GPC (polystyrene conversion) And the weight average molecular weight was 28,000. The composition ratio of the copolymer was approximately 5 to 5.

Preparation of Light Emitting Film (A) Polymer Solution of Sample A 5.0 g Bis (2,4,5-trichloro-6-carbobutoxy phenyloxalate (TCCPO) 0.200 g 9,10-bis {phenylethynyl} anthracene 0.0045 g ( BPEA) MEK 5.0 g The polymer solution containing the luminescent material was applied on a glass plate using a 2 mil applicator, and dried in an oven at 50 ° C. for 1 hour to obtain a luminescent film having a thickness of about 10 μm. .

Preparation of Light Emitting Film (B) Polymer Solution of Sample B 5.0 g TCCPO 0.200 g BPEA 0.0057 g MEK 5.0 g The polymer solution containing the above luminescent material was placed on a glass plate using a 2 mil applicator. And dried in an oven at 50 ° C. for 1 hour to obtain a light-emitting film having a thickness of about 10 μm.

Preparation of Luminescent Test Tube (A) A polymer solution containing a luminescent material for a luminescent film (A) is placed in a test tube, gently stirred and decanted to remove the polymer solution, and placed in an oven at 50 ° C. To obtain a coating film containing a luminescent material in the test tube.

Emission Evaluation Results 1.00 g of tetrabutylammonium salicylate was dissolved in 500 ml of a 1% hydrogen peroxide solution to prepare an evaluation reagent. 10 ml of this hydrogen peroxide solution was placed in a sample tube and a luminescence test was performed. Evaluation result --------------------------------- Sample emission time (minutes) -------- ------------------------------------------------------------------------------------------------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Evaluated visually at room temperature in a dark room.

[0027]

According to the present invention, a light-emitting material that can be stored at room temperature and is safe in a water-based environment, and that is safe in terms of environmental hygiene can be easily provided.

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Claims (5)

[Claims] 1. A weight molecular weight 2 having hydrophilicity and hydrophobicity
A light-emitting material comprising a medium of 0 to 5,000,000 and a compound capable of reacting with a water-soluble peroxide to emit light. 2. The luminescent material according to claim 1, wherein the water-soluble peroxide is hydrogen peroxide. 3. The luminescent material according to claim 1, further comprising a fluorescent or phosphorescent substance. 4. The compound capable of emitting light by reacting with a water-soluble peroxide is oxalic acid or a derivative thereof.
The luminescent material according to any one of the above. 5. A luminescent material obtained by molding the luminescent material according to claim 1 into a coating, a film, a plate, a rod, or a tube.