JPH1017571A - Red color fluorescent material and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material represented by a specific formula, soluble in organic solvents, having excellent heat resistance and light resistance, colorless under ordinary light, emitting red color light on the irradiation of UV light and useful for concealed ink materials, etc. SOLUTION: The material of the formula [X is methyl, furan ring; Y is (n-C4 H9 )4 N<+> , (H2 O)n ; (n) is 0-2]. The material comprises is obtained e.g. by reacting 4,4,4-trifluoro-1-(2-furanyl)-1,3-butanedione compound or a 4,4,4- trifluoro-1-(2-methyl)-1,3-butanedione compound with europium perchlorate in the presence of sodium hydroxide in acetone, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a novel compound which is colorless under ordinary visible light but has red fluorescence under irradiation of ultraviolet rays, and relates to a red fluorescent material used for inks, paints and plastic compositions.

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent material used for printed matter or various plastic molded articles, paints, inks, etc., which is colorless under visible light and emits red light under irradiation of ultraviolet rays, and the fluorescent material. And a resin composition for a paint binder, and an ink composition comprising an ink binder.

[0002]

2. Description of the Related Art There are many luminescent organic compounds, which have been used as fluorescent whitening agents or dyes for lasers. Especially,
For various special uses, inks and paints that are difficult to recognize in the visible region but are made visible by special light or readable by a sensor have been developed. Conventionally, for such applications, substances that emit purple light, such as fluorescent whitening agents, have been used. Since the fluorescent brightener is an aqueous dye, there is a disadvantage that the water resistance of the recorded matter is inferior. Further, since the fluorescent whitening agent is widely used for paper, fiber and the like, there is a disadvantage that it is difficult to distinguish the light emission from the light emission. In addition, a fluorescent pigment in which a fluorescent dye is made into particles with a resin is a mixture of a fluorescent dye with a resin or the like, and can be used like a dye by dissolving in an organic solvent, but also has absorption in the visible region. In addition, the display object can be visually confirmed without applying fluorescent light, and could not be used as a material for so-called hidden ink.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorescent material which emits red light when irradiated with ultraviolet light, and which has excellent heat resistance, solvent resistance and light resistance, an ink composition comprising the fluorescent material and an ink binder, An object of the present invention is to provide a plastic molded article including a master batch composed of a paint composition containing a resin for a paint binder and a resin.

[0004]

Means for Solving the Problems The present invention is a red fluorescent material represented by the following general formula [1]. General formula [1]

Embedded image [Wherein, X is or a methyl group, a furan ring group, Y _{(n-C 4 H 9)} 4 N +, or a (H ₂ O) _{n, n} is an integer of 0 to 2. ]

Further, the present invention is an ink composition comprising an ink binder containing the above-mentioned red fluorescent material.

Further, the present invention is a coating composition containing a resin for a coating binder containing the above-mentioned red fluorescent material.

Further, the present invention is a plastic molded product made of a resin containing the above-mentioned red fluorescent material.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

The compound represented by the general formula [1] in the present invention can be used at a wavelength of 600 to 650 nm, particularly 620 n
It has fluorescence emission near m. In addition, when ultraviolet light is not irradiated, since it is not colored, it is not easy to discriminate and is useful as a material for hidden ink.

An example of a method for synthesizing the compound represented by the general formula [1] of the present invention is shown below.

The present fluorescent material is a 4,4,4-trifluoro-1- (2-furanyl) -1,3-butanedione compound or 4,4,4-trifluoro-1- (2-methyl)- A tetra-n-butylammonium salt or tetra (4,4,4) produced by reacting a 1,3-butanedione compound with europium perchlorate together with sodium hydroxide in acetone to prepare a tetra-n-butylammonium salt or water as a counter ion. 4-trifluoro-1- (2-furanyl)-
1,3-butanedionato) europium complex or tetra (4,4,4-trifluoro-1-) having a tetra-n-butylammonium salt or water as a counter ion
(2-methyl) -1,3-butanedionate) europium complex. Instead of sodium hydroxide, potassium hydroxide, ammonia water, or the like can be used. In addition, benzene, toluene, xylene, or the like can be used instead of acetone. The above synthesis method is not limited. The synthesis method is shown in the following synthesis examples (a) to (d).

Each of these compounds is colorless when irradiated with visible light, emits red light when irradiated with ultraviolet light, has high fluorescence intensity, and is excellent in light resistance and the like.
These compounds may be used alone or in combination of two or more. These compounds have little solubility in water but have sufficient solubility in solvents, so that the water resistance of the recorded matter is also good, and the ink composition for printing hidden letters and the like, for coating compositions Very suitable as a fluorescent material.

The fluorescent material of the present invention is soluble in an organic solvent and can be incorporated into inks, paints and the like. Examples of the solvent used include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and propanol; ester solvents such as ethyl acetate; dimethyl sulfoxide; N-methyl-2-pyrrolidone; Cellosolve solvents such as -butyl lactone, dioxane, methyl cellosolve, ethyl cellosolve and butyl cellosolve, and halogen solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane and chloroform.

The ink composition of the present invention selects the type of solvent, the presence or absence of a binder, the type, the amount used, etc.
By adjusting the surface tension, conductivity, drying property, and the like, it can be applied to various printers and recording media. As the ink, it can be blended with offset printing ink, gravure printing ink, printing ink such as silk screen, inkjet ink, writing ink and the like. Examples of paint resins and ink resins include acrylic resins such as polymethyl acrylate, polyethylene acrylate, polymethyl methacrylate, and polyvinyl acrylate, polyurethane resins, acrylic urethane resins, polyester resins, polyacrylate resins, vinyl chloride resins, and ethylene-acetic acid. Vinyl copolymer, polyvinyl formal resin, amino resin, alkyd resin, epoxy resin, phenol resin, polyester resin, polyesterimide resin, polyaminoimide resin, silicone resin, polyvinylidene chloride resin, polyethylene vinyl alcohol resin, polyolefin resin, Vinylidene chloride resin, butadiene resin, styrene resin, phenol resin,
Resins such as polyamide resin, cellophane, ethyl cellulose, nitrocellulose and the like can be mentioned. The mixing ratio of the fluorescent material is 0.001 to 50% by weight, preferably 0.1% by weight, based on the resin of the ink composition or the coating composition.
To 5% by weight.

By using the fluorescent material of the present invention together with the ultraviolet absorber in the above composition, the light stability can be improved. Ultraviolet absorbers include benzophenones such as o-hydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2′-hydroxyphenyl) benzotriazole, 2- ( 2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5 '
-Methylphenyl) -5-chlorobenzotriazole,
Benzotriazoles such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, ethyl-2
Cyanoacrylates such as cyano-3,3-diphenylacrylate and 5-ethylhexyl-2-cyano-3,3-diphenylacrylate, salicylic acids such as phenylsalicylate and 4-t-butylphenylsalicylate, Oxalic acid anilides such as 2-ethyl-5'-t-butyl-2'-ethoxy-N, N'-diphenyloxalamide, and ultrafine inorganic oxides such as zinc oxide, titanium oxide and zirconium oxide Can be used.

The fluorescent material of the present invention can be blended with a molded plastic. At this time, the fluorescent material of the present invention can be blended in a high concentration with a composition comprising a base resin and a dispersant such as metal soap and wax, and extruded to form a masterbatch. The plastic molding of the present invention comprises a masterbatch. Examples of the resin for molded plastic include polyolefin resin such as polyethylene resin and polypropylene resin, polyester resin, polyamide resin, PVC resin, ABS resin, styrene resin, acrylic resin, polycarbonate resin, urethane resin, amino resin and the like. These thermoplastic resins are made into plastic molded articles by inflation molding, calender molding or other methods. The fluorescent material of the present invention can be blended in a thermosetting plastic such as an epoxy resin, a phenol resin, a polyester resin, a polyesterimide resin, and a polyamideimide resin.

The fluorescent material of the present invention includes rosin acid soap, stearic acid soap, oleic acid soap, Na-di-β-naphthylmethane disulfate, Na-lauryl sulfate, Na-diethylhexyl sulfoxylate,
Dispersed in a surfactant such as dioctyl sulfosuccinate and used for inks or coatings.

Although the recorded matter of the present invention is difficult to visually discriminate, it is also possible to use a coloring agent to make the recorded matter easily identifiable. For this reason, a general pigment or dye can be used together with the fluorescent material in the recording liquid. As the dye, an oil dye, a metal-containing dye, a disperse dye, or the like is used. These dyes are preferably purified dyes from which inorganic salts have been removed.

The recorded matter produced according to the present invention has remarkably good water resistance and is used for ink, paint, etc., and it is difficult to recognize hidden letters, symbols, cardboard markings, numbering, bar codes, etc. on documents. And a recorded matter having a security function. Further, it has better water resistance than a recording solution prepared by using a dye such as a fluorescent whitening agent, and can form a special image having excellent storage stability of a recorded matter.

[0020]

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

Synthesis Example 1 Synthesis of compound (a) In a mixture of 3.6 parts of europium oxide and 10 parts of water, perchloric acid (6
(0% aqueous solution) was added and stirred at room temperature for 30 minutes. This aqueous solution was treated with 4,4,4-trifluoro-1- (2
-Furanyl) -1,3-butanedione, 16.5 parts of sodium hydroxide, 3.2 parts of sodium hydroxide, 5 parts of water, and 250 parts of acetone were added dropwise at room temperature and stirred for 1 hour. After the reaction,
Acetone was removed with an evaporator, and the resulting yellow paste-like solid was dissolved in 50 parts of ethanol.
It dropped into 00 parts. The precipitated white solid is dried by oven,
15.5 parts of a compound (a) represented by the following formula was obtained.

[0022]

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Synthesis Example 2 Synthesis of Compound (b) 10 parts of the compound (a) was dissolved in 200 parts of ethanol, and 6 parts of tetra-n-butylammonium bromide was added.
After stirring at room temperature for 1 hour, 500 parts of water was added, and the precipitated solid was separated by filtration and dried under reduced pressure at 50 ° C. to obtain 11.5 parts of a compound (b) represented by the following formula.

[0024]

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Synthesis Example 3 Synthesis of Compound (c) 3.6 parts of europium oxide and 10 parts of water were mixed with perchloric acid (6
(0% aqueous solution) was added and stirred at room temperature for 30 minutes. This aqueous solution was treated with 4,4,4-trifluoro-1- (2
-Methyl) -1,3-butanedione, 16.5 parts of sodium hydroxide, 3.2 parts of sodium hydroxide, 5 parts of water, and 250 parts of acetone were added dropwise at room temperature and stirred for 1 hour. After completion of the reaction, acetone was removed with an evaporator, and the resulting yellow paste-like solid was dissolved in 50 parts of ethanol.
It was dropped into 0 parts. The precipitated white solid was dried by a furnace to obtain 15.5 parts of a compound (c) represented by the following formula.

[0026]

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Synthesis Example 4 Synthesis of Compound (d) 10 parts of the compound (c) was dissolved in 200 parts of ethanol, and 6 parts of tetra-n-butylammonium bromide was added.
After stirring at room temperature for 1 hour, 500 parts of water was added, and the precipitated solid was separated by filtration and dried under reduced pressure at 50 ° C. to obtain 11.5 parts of a compound (d) represented by the following formula.

[0028]

Embedded image

Example 1 9 parts of compound (a), 49 parts of varnish for aqueous gravure (styrene acrylic acid type), 3 mm Φ glass beads 15
0 parts was placed in a 225 ml mayonnaise bottle, dispersed with a paint conditioner for 90 minutes, 35 parts of an additional varnish was added, and the mixture was further dispersed with a paint conditioner for 10 minutes, and the glass beads were separated by filtration. I got This ink was spread on manila board paper with a # 3 bar coater. This coated paper under normal light (fluorescent light)
Although indistinguishable from the paper before coating, it emitted a bright red luminescent color when irradiated with an ultraviolet lamp. The emission spectrum and excitation spectrum of this coated paper were measured using a Fluorometer FP-770 manufactured by JASCO Corporation. The emission fluorescence wavelength was 620 nm and the excitation maximum wavelength was 310 nm. Further, as a result of visually observing the change in the color fading of the fluorescence after exposing the coated paper for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

Example 2 A composition comprising 3 parts of the compound (b), an acrylic varnish (300 parts of a xylene solution of methyl methacrylate and 100 parts of methyl ethyl ketone) was prepared and applied to flat glass. Is normal light (fluorescent light)
Below, it was indistinguishable from the glass plate before coating, but when irradiated with an ultraviolet lamp, it emitted a bright red luminescent color. The emission spectrum and excitation spectrum of this coated paper were measured using a Fluorometer FP-770 manufactured by JASCO Corporation. The emission fluorescence wavelength was 620 nm and the excitation maximum wavelength was 310 nm. Further, as a result of visually observing the change in the color fading of the fluorescence after exposing the coated paper for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

Example 3 1 part of compound (b), 100 parts of polyvinyl butyral,
An ink composition comprising 250 parts of xylene and 150 parts of methyl ethyl ketone was prepared, and was colored on a colorless paper. This coated paper cannot be distinguished from the paper before coating under normal light (fluorescent lamp), but when illuminated by an ultraviolet lamp, it exhibited a bright red emission color. JASCO Fluorometer FP-7
When the emission spectrum and the excitation spectrum of the coated paper were measured by using No. 70, the emission fluorescence wavelength was 620 nm.
m, the excitation maximum wavelength was 310 nm. Further, as a result of visually observing the change in the color fading of the fluorescence after exposing the coated paper for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

Example 4 Five parts of the compound (d) and 20 parts of a rosin phenolic resin-based offset varnish were milled at 1000 rotations, 1501 bs, and 4 rotations with a Hoover-type muller to prepare an ink. Colored on art paper using a machine (RI tester). This coated paper under normal light (fluorescent light)
Although indistinguishable from the paper before application, it emitted a bright red luminescent color when irradiated with an ultraviolet lamp. The emission spectrum and excitation spectrum of this coated paper were measured using a Fluorometer FP-770 manufactured by JASCO Corporation. The emission fluorescence wavelength was 620 nm and the excitation maximum wavelength was 310 nm. Further, as a result of visually observing the change in the color fading of the fluorescence after exposing the coated paper for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

Example 5 30 parts of compound (d) were mixed with 300 parts of polyethylene (trade name "Sumikacene G-808" manufactured by Sumitomo Chemical Co., Ltd.) and 400 parts of polyethylene wax (trade name "Sunwax 131P" manufactured by Sanyo Chemical Industry Co., Ltd.) Was kneaded in a kneader and then pelletized in an extruder to obtain a masterbatch, and 4 parts of the masterbatch were mixed with 100 parts of high-density polyethylene (trade name: "HIZEX2208", trade name of Mitsui Petrochemical Industries, Ltd.), and resin molding was performed by extrusion molding. The resin molded product was colorless under normal light (fluorescent light), but exhibited a bright red emission color when irradiated with an ultraviolet lamp.Fluorescence photometer FP-770 manufactured by JASCO Corporation. The emission spectrum and the excitation spectrum of this resin molded product were measured using, and the emission fluorescence wavelength was 620 nm and the excitation maximum wavelength was Is 3
It was 10 nm. Further, as a result of visually observing a change in the fading of the fluorescence after exposure to the resin molded product for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

Example 6 A resin plate was prepared by dissolving 4 parts of the compound (c) in 110 parts of methyl methacrylate and performing cast polymerization using azobisisobutyronitrile as a polymerization initiator. The resin film was colorless under normal light (fluorescent light) or outdoors, but emitted a bright red color when irradiated with an ultraviolet lamp. Further, as a result of visually observing a change in the fading of the fluorescence after exposure to the resin molded product for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

[0035]

The fluorescent material of the present invention is soluble in an organic solvent,
In addition, it has excellent heat resistance and light resistance, is colorless under ordinary light, but emits red light when irradiated with ultraviolet light, so that it is an extremely valuable compound. Printed materials, films, etc. using this luminescent material cannot recognize the color under normal light, so it is possible to perform recording that is difficult to distinguish from the base, and it emits red light by irradiating ultraviolet light, so it has a special luminescent property The present invention can be used for hidden characters that can be used in a system in which a light-receiving element reads a recorded matter, printing related to security, and the like.

Claims (4)

[Claims] 1. A red fluorescent material represented by the following general formula [1]. General formula [1] [Wherein, X is or a methyl group, a furan ring group, Y _{(n-C 4 H 9)} 4 N +, or a (H ₂ O) _{n, n} is an integer of 0 to 2. ] 2. An ink composition comprising an ink binder containing the red fluorescent material according to claim 1. 3. A coating composition comprising a resin for a coating binder containing the red fluorescent material according to claim 1. 4. A plastic molded article comprising a resin containing the red fluorescent material according to claim 1.