JP2006328209A - Luminous agent-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminous agent-containing resin composition which can emit light having various colors in dark places, and to provide a luminous agent-containing resin composition which can also utilize light irradiated on portions except the luminous agent in the resin for luminousness, and has good luminous efficiency. <P>SOLUTION: This luminous agent-containing resin composition is characterized by containing a luminous agent and a fluorescent agent in a polylactic acid-polybutylene succinate blend polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a luminous agent-containing resin composition in which a luminous agent is contained in a resin.

Conventionally, phosphorescent agents that emit light over a long period of time after irradiation with ultraviolet rays or the like are known. In particular, a phosphorescent agent having long-time afterglow characteristics, chemically stable and excellent in light resistance has also been developed (Patent Document 1).
JP 7-11250 A

  Such phosphorescent agents are added to various resins such as acrylic, polyethylene, polypropylene, ABS, polystyrene, polycarbonate, etc., and as resin compositions that emit light in the dark, for example, watches, interiors, signs, disaster prevention equipment, home appliances, lighting It is used in a wide range of industrial fields such as equipment and fishing gear.

  However, the above conventional phosphorescent agent-containing resin composition has a very limited color such as pale yellowish green or pale blue in the dark place of the phosphorescent agent contained, and lacks diversity. Moreover, the light utilized for phosphorescence was only the light irradiated to the phosphorescent agent part in resin, and the light irradiated to the other part was not able to be utilized for phosphorescence. For this reason, the efficiency of phosphorescence was bad.

  This invention is made | formed in view of the said conventional situation, Comprising: It is set as the problem which should be solved to provide the luminous agent containing resin composition which can be made to color-produce in various colors in a dark place. Moreover, it is possible to use the light irradiated to parts other than the phosphorescent agent in the resin for phosphorescence, and it is an object to be solved to provide a phosphorescent agent-containing resin composition having a high luminous efficiency.

  The phosphorescent agent-containing resin composition of the first invention includes a phosphorescent agent and a fluorescent agent in the resin, and an emission spectrum of the phosphorescent agent in a dark place and a light absorption spectrum of the fluorescent agent overlap. It has a part.

  Here, the luminous agent refers to a substance that stores light energy in a light place and releases the stored energy in a dark place in the form of light emission. A fluorescent agent refers to a substance that emits light having a wavelength different from that of irradiated light.

  In the phosphorescent agent-containing resin composition of the first invention, the light emission spectrum in the dark place of the phosphorescent agent contained in the resin has an overlapping portion with the light absorption spectrum of the fluorescent agent contained in the resin. For this reason, the fluorescent agent is excited by light irradiated from the phosphorescent agent in a dark place, and light having a wavelength different from that of the light irradiated from the phosphorescent agent is irradiated from the fluorescent agent. For this reason, a luminous agent containing resin composition turns into a luminescent color different from the color of the light irradiated from a luminous agent in a dark place. Since the emission color is determined by the combination of the phosphorescent agent and the fluorescent agent, various colors of light can be emitted in a dark place. Furthermore, by using a plurality of types of phosphorescent agents and fluorescent agents, the fluorescence emitted from them can be mixed and more various emission colors can be obtained.

  The phosphorescent agent-containing resin composition of the second invention includes a phosphorescent agent and a fluorescent agent in the resin, and the fluorescence spectrum of the fluorescent agent and the excitation spectrum of the phosphorescent agent have an overlapping portion. Features.

  In the phosphorescent agent-containing resin composition of the second invention, the fluorescence spectrum of the fluorescent agent contained in the resin has an overlapping portion with the excitation spectrum of the phosphorescent agent contained in the resin. For this reason, the phosphorescent agent can store light by the light irradiated from the fluorescent agent in a bright place. For this reason, in addition to the light irradiated to the phosphorescent agent portion in the resin, the light irradiated to the fluorescent agent can be used for the phosphorescence, and the efficiency of the phosphorescence is improved.

  The fluorescent agent contained in the phosphorescent agent-containing resin composition of the first and second inventions is preferably an organic fluorescent material that is compatible with the resin. If it is like this, when a fluorescent agent is kneaded and contained in transparent resin, transparency can be maintained. For this reason, the light irradiated from the outside can reach the inside without being attenuated, and the attenuation of the fluorescence emitted from the fluorescent agent and the light emitted from the phosphorescent agent can be further reduced.

  Moreover, resin which comprises the luminous agent containing resin composition of 1st invention and 2nd invention can be made into a biodegradable plastic. If this is the case, it becomes a biodegradable resin that emits light in a dark place. By using a photosensor that can detect the light, or by visually confirming the light, the biodegradable resin It can be collected separately from waste. Since the biodegradable resin thus separated can be disposed as landfill as it is, the amount of waste that needs to be incinerated can be reduced. In particular, when the biodegradable resin is derived from a carbon neutral natural source, since the amount of carbon dioxide in the atmosphere is not increased, global warming can be suppressed. Here, the biodegradable resin is a general term for resins that can be biodegraded by microorganisms in the soil, for example, those derived from natural polymers such as starch, cellulose acetate, (chitosan / cellulose / starch) polymerization system, etc. And synthetic polymers such as polylactic acid, polycaprolactone, polybutylene succinate, poly (butylene succinate / adipate), poly (butylene succinate / carbonate), polyethylene succinate, poly (butylene succinate / terephthalate) polyvinyl alcohol, etc. And microorganism-producing polymers such as poly (hydroxybutyrate / hydroxyvalidate), mixtures thereof (compounds), and the like. Specifically, Nature Works (registered trademark) manufactured by Cargill-DOW, which is a chemically synthesized green plastic (registered trademark), TONE (registered trademark) manufactured by UCC, and Lacty (registered trademark) manufactured by Shimadzu Corporation. Terramac (registered trademark) manufactured by Unitika Ltd., Bionore (registered trademark) manufactured by Showa Polymer Co., Ltd., Upec (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., and Lacia manufactured by Mitsui Chemicals, Inc. ), Lunar (registered trademark) manufactured by Nippon Shokubai Co., Ltd., Biomax (registered trademark) manufactured by Du Pont, Ecoflex (registered trademark) manufactured by BASF, Poval (registered trademark) manufactured by Kuraray, and manufactured by Eastman Chemicals Easter Bio (registered trademark), Gohsenol (registered trademark) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Delon (registered trademark) VA manufactured by Aicero Chemical Co., Ltd., Empol (registered trademark) manufactured by IRe CHEMICAL, Daicel Chemical Industries ( Cell Green (ascending) Registered trademark) or the like. Furthermore, it can be expected that all biodegradable resins that will be studied in the future can be used.

There is no limitation in particular as a luminous material used for the luminous agent containing resin composition of 1st invention and 2nd invention, Various well-known things can be used. For example, a compound represented by MAl ₂ O ₄ (M is at least one metal element selected from the group consisting of calcium, strontium, and barium) is used as a mother crystal, europium as an activator, and a coactivator. A phosphorescent agent to which at least one element of the group consisting of cerium, praseodymium, neodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium is added can be used. Since this luminous agent has high light emission intensity, lasts for a long time, and is chemically stable, it can be used suitably. In addition, sulfide-based phosphorescent agents such as CaS: Bi, CaSrS: Bi, ZnS: Cu, and ZnCdS: Cu can also be used.

  Moreover, the well-known various thing can be used for the fluorescent agent used for the luminous agent containing resin composition of 1st invention and 2nd invention. For example, 9,10-dianilinoanthracene, 2-hydroxy-1-naphthaldazine, 2-anilino-4- (2,5-dichlorobenzoylamino) -1,9-pyrimidoanthrone, 1,4-bis (β- Organic fluorescent materials such as cyano-β-carboethoxy-vinyl) benzene, riboflavin, and polymeric fluorescent materials, “CI Disperse Yellow 82”, “CI Disperse Yellow 124”, “CI” Solvent Yellow 94 ”,“ CI Disperse Red 60 ”,“ CI Solvent Red 43 ”,“ CI Solvent Red 44 ”,“ CI Solvent Red 45 ”,“ C.I. Solvent Red 49 "" BASF Lumogen Red, Yellow, Violet Fluorescent agents such as organic and solvent soluble fluorescent material a solid solution of a synthetic resin and pulverized the like. Further, inorganic fluorescent pigments such as calcium tungstate, potassium chloride, and thallium can also be used. Among these, a fluorescent agent obtained by powdering a solid solution of an organic fluorescent substance or a fluorescent substance that can be dissolved in an organic solvent and a synthetic resin can be compatible with the resin and kneaded into a transparent resin. When it is contained, transparency can be maintained. For this reason, the light from the outside can reach the inside without being attenuated, and the fluorescence emitted from the fluorescent agent and the attenuation of the light emitted from the phosphorescent agent can be further reduced, which is preferable.

Hereinafter, examples embodying the present invention will be described in detail in comparison with comparative examples.
Example 1
Example 1 is a blend polymer of polylactic acid (MFR 14 g / 10 min) and polybutylene succinate (Bionore 1020 manufactured by Showa High Polymer Co., Ltd.), a phosphorescent agent (GLL-300M manufactured by Nemoto Special Chemical Co., Ltd.), and And a phosphorescent agent-containing resin composition containing a fluorescent agent (Lumogen F Orange 240 manufactured by BASF). These substances were weighed out at the ratios shown below, and the set temperature was 180 ° C. using a kneading extruder, and the extruded resin was cut and granulated into pellets.
Polylactic acid ... 76% by weight
Polybutylene succinate ... 18.99% by weight
Luminescent agent (GLL-300M) ... 5% by weight
Fluorescent agent (Lumogen F Orange 240) ... 0.01% by weight

(Comparative Example 1)
In Comparative Example 1, polylactic acid, polybutylene succinate, and a phosphorescent agent were kneaded at the following ratios under the same conditions as in Example 1 and did not contain a fluorescent agent.
Polylactic acid ... 76% by weight
Polybutylene succinate ... 19% by weight
Luminescent agent (GLL-300M) ... 5% by weight

(Comparative Example 2)
In Comparative Example 1, polylactic acid and a fluorescent agent are kneaded at the following ratios under the same conditions as in Example 1 and do not contain a phosphorescent agent.
Polylactic acid ... 99.6% by weight
Phosphorescent agent (GLL-300M): 0.4% by weight

<Evaluation>
The pellets of Example 1 and Comparative Examples 1 and 2 thus obtained were irradiated with 364 nm ultraviolet light from the excitation side for 1 minute using a spectrofluorimeter, and then the excitation side shutter was closed, and the pellets from the fluorescence side The fluorescence spectrum was measured. The fluorescence spectra thus obtained are shown in FIGS. As a result, in Comparative Example 1 in which the blend polymer of polylactic acid and polybutylene succinate contains only the phosphorescent agent, a spectrum of light from the phosphorescent agent having a peak at 510 nm was observed (see FIG. 2). The emission color by observation was yellowish green.

  On the other hand, in the sample of Example 1 in which the blend polymer of polylactic acid and polybutylene succinate contains the phosphorescent agent and the fluorescent agent, the phosphorescent agent is used even though the excitation side shutter is closed. Peaks based on fluorescence from the fluorescent agent were observed in the vicinity of 540 nm and 570 nm on the longer wavelength side of the wavelength of the light, and the emission color by visual observation was yellow, which was different from the original fluorescent color of the phosphorescent agent.

  In Comparative Example 2 in which only the fluorescent agent was contained in the blend polymer of polylactic acid and polybutylene succinate, no fluorescence spectrum was observed when the shutter on the excitation side was closed. For this reason, the fluorescence spectrum of Comparative Example 2 was measured with the shutter on the excitation side opened (see FIG. 3). As a result, peaks were observed at the same wavelengths as those in the vicinity of 540 nm and 570 nm shown in FIG.

  The above results can be explained as follows. That is, in Comparative Example 1, the fluorescence spectrum from the phosphorescent agent is observed with the excitation-side shutter closed (see FIG. 1). On the other hand, in Example 1, fluorescence is emitted from the phosphorescent agent in a state where the shutter on the excitation side is closed, and the fluorescent agent further emits light by the fluorescence. For this reason, the light emitted from the phosphorescent agent itself and the light emitted from the fluorescent agent are mixed, and the emission color changes. In addition, when the light absorption spectrum of the fluorescent agent (Lumogen F Orange 240) was measured, it was found that a large absorption was observed in the vicinity of 510 nm that is the fluorescence wavelength from the phosphorescent agent (see FIG. 4). From this fact, it is theoretically confirmed that fluorescence is emitted from the phosphorescent agent, and that the fluorescent agent further emits light by the fluorescence.

  The pellets of Example 1 and Comparative Example 1 were tested for afterglow luminance characteristics. That is, a D65 regular light source (F65D-A manufactured by Suga Test Instruments Co., Ltd.) was used as a light source, and after irradiating ultraviolet rays at 400 lx for 20 minutes, a color luminance meter (made by BM-5A TOPCON) and a radiograph analyzer (NIM-1000 fundamental special Measurement was carried out using Chemical). As a result, as shown in FIG. 5, the afterglow time was longer in Example 1 than in Comparative Example 1. This is because the fluorescent agent used in Example 1 is an organic fluorescent material that is compatible with a blend polymer of polylactic acid and polybutylene succinate, so that the light irradiated from the outside is further attenuated to the inside. This is presumably because it is possible to reduce the attenuation of the fluorescence emitted from the fluorescent agent and the light emitted from the phosphorescent agent.

(Example 2)
Example 2 is a phosphorescent agent-containing resin composition in which polymethyl methacrylate (PMMA) contains a phosphorescent agent (GLL-300M manufactured by Nemoto Special Chemical Co., Ltd.) and a fluorescent agent (Lumogen F Orange 240 manufactured by BASF). It is a thing. These substances were weighed out at the ratios shown below, and the set temperature was 180 ° C. using a kneading extruder, and the extruded resin was cut and granulated into pellets.
PMMA ... 94.95% by weight
Luminescent agent (GLL-300M) ... 5% by weight
Fluorescent agent (Lumogen F Orange 240) ... 0.05% by weight

<Evaluation>
About the pellet of Example 2 obtained in this way, when the luminescent color in the dark place was observed with the naked eye, it became pale yellow and was clearly different from the pale yellow green, which is the luminescent color unique to the phosphorescent agent.

(Example 3)
Example 3 is a phosphorescent agent-containing resin in which polymethyl methacrylate (PMMA) contains a phosphorescent agent (GLL-300M manufactured by Nemoto Special Chemical Co., Ltd.) and a phenazacillin polymer represented by the following chemical formula (1). It is a composition. These substances were weighed out at the ratios shown below, and the set temperature was 180 ° C. using a kneading extruder, and the extruded resin was cut and granulated into pellets.
PMMA ... 99.99% by weight
Luminescent agent (GLL-300M) ... 5% by weight
Fluorescent agent (phenazacillin polymer (1)): 0.01% by weight

(Comparative Example 3)
Comparative Example 3 is a resin composition containing polymethyl methacrylate (PMMA) containing the phenazacillin polymer represented by the above chemical formula (1), and these substances were weighed in the proportions shown below. Was granulated into pellets by the same method.
PMMA ... 99.99% by weight
Fluorescent agent (phenazacillin polymer (1)): 0.01% by weight

<Evaluation>
With respect to the pellets of Example 3 and Comparative Example 3 obtained in this way, a fluorescence spectrum was measured using a spectrofluorometer while irradiating ultraviolet rays of 364 nm. As a result, in Comparative Example 3 in which only the fluorescent agent is contained in PMMA, as shown in FIG. 7, a shoulder peak is observed in the vicinity of 400 nm, whereas the fluorescent agent and the phosphorescent agent are contained in PMMA. In Example 3, as shown in FIG. 8, the shoulder peak near 400 nm disappeared. Further, the wavelength range of the excitation spectrum of the phosphorescent agent (GLL-300M) has a portion overlapping 450 nm as shown in FIG. From the above, it can be seen that the pellet of Example 3 is excited and stored by the phosphorescent material (see FIG. 6) around 450 nm emitted from the fluorescent agent (phenazacillin polymer). Moreover, it turns out that the light irradiated to parts other than the phosphorescent agent in resin can also be utilized for phosphorescence, and it turns out that the efficiency of phosphorescence becomes favorable.

  In place of the fluorescent agent in Example 3, a phenazacillin polymer represented by the following chemical formula (2) can also be used.

In the fluorescence spectrum of this compound (2), fluorescence was observed at around 400 nm as shown in FIG. Since this wavelength range has a larger overlap with the excitation spectrum (see FIG. 9) of the phosphorescent agent (GLL-300M) than the phenazacillin compound of the chemical formula (1), energy transfer can be performed more efficiently. The luminous efficiency can be raised.

一般式（３）及び一般式（４）において、Ｒ１ 及びＲ２ は、それぞれ独立に、置換されていてもよいアルキル基、アリール基、アルコキシ基またはアリーロキシ基であり、また、Ｒ３ は水素原子、置換されていてもよいアルキル基、アリール基、アルコキシ基またはアリーロキシ基である。 Moreover, as a phenazacillin polymer other than the above, a phenazacillin polymer represented by the general formula (3) or the general formula (4) may be used as a fluorescent agent.

In General Formula (3) and General Formula (4), R 1 and R 2 are each independently an optionally substituted alkyl group, aryl group, alkoxy group, or aryloxy group, and R 3 is a hydrogen atom, substituted An alkyl group, an aryl group, an alkoxy group or an aryloxy group which may be substituted.

Examples of the alkyl group in R1 to R3 include methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, n-, iso- or neo-pentyl, n-hexyl, cyclohexyl, n- Examples include linear, branched and cyclic alkyl groups having 1 to 20, preferably 1 to 10, carbon atoms such as heptyl and n-octyl. Examples of the alkoxy group include methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neo-pentoxy, n-hexoxy, cyclohexoxy, n-heptoxy, Examples thereof include linear, branched and cyclic alkoxy groups having 1 to 20, preferably 1 to 10, such as n-octoxy. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms such as a phenyl group, o-, m-, p-tolyl group, 1- and 2-naphthyl group, and anthryl group. . Examples of the aryloxy group include aryloxy groups having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms such as a phenoxy group, o-, m-, p-triloxy group, 1- and 2-naphthoxy group, and anthoxy group.

Next, in the general formula (4), the optionally substituted divalent aromatic group represented by Ar includes o-, p-phenylene, thiophene-2,5-diyl, thiophene-2, 3-diyl, pyridine-2,5-diyl, pyridine-2,3-diyl, pyridine-4,5-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-1,2- Diyl, naphthalene-1,7-diyl, anthracene-9,10-diyl, anthracene-9,10-diyl, anthracene-1,4-diyl, anthracene-2,6-diyl, anthracene-1,7-diyl Biphenylene-4,4′-diyl, and compounds in which the aromatic ring of these aromatic compounds is substituted are also included.

In addition, as Ar in the general formula (4), compounds substituted on the aromatic ring include alkoxybenzene-1,4-diyl, alkylbenzene-1,4-diyl, arylbenzene-1,4-diyl, and aryl. Roxybenzene-1,4-diyl, 2,5-, 2,3-, 2,6-dialkoxybenzene-1,4-diyl, 2,3,5-trialkoxybenzene-1,4-diyl, 2 , 3,5,6-tetraalkoxybenzene-1,4-diyl, 2,5-, 2,3-, 2,6-dialkylbenzene-1,4-diyl, 2,3,5-trialkylbenzene-1 , 4-diyl, 2,3,5,6-tetraalkylbenzene-1,4-diyl, 2,5-, 2,3-, 2,6-diarylbenzene-1,4-diyl, 2,3,5 -Triarylbenzene-1,4-diyl, 2,3,5,6-tetraarylben 1,4-diyl, 2,5-, 2,3-, 2,6-diallyloxybenzene-1,4-diyl, 2,3,5-triallyloxybenzene-1,4-diyl, 2,3,5,6-tetraaryloxybenzene-1,4-diyl, alkoxythiophene-2,5-diyl, alkylthiophene-2,5-diyl, arylthiophene-2,5-diyl, aryloxythiophene- 2,5-diyl, dialkoxythiophene-2,5-diyl, dialkylthiophene-2,5-diyl, diarylthiophene-2,5-diyl, diaryloxythiophene-2,5-diyl.

Furthermore, in the general formula (3) and the general formula (4), the substituent of “optionally substituted” in R1 to R3 may be any substituent that does not participate in the polymerization reaction described later. Examples include an alkoxy group, an alkyl group, an aryl group, and an aryloxy group. Moreover, n in General formula (1) is a number average degree of polymerization, Comprising: It is an integer of the range of 3-30,000.

  The luminous agent-containing resin composition of the present invention is used as a resin composition that emits light in a dark place, for example, in a wide range of industrial fields such as watches, interiors, signs, disaster prevention equipment, home appliances, lighting equipment, fishing gear, and the like.

It is a fluorescence spectrum in the state which closed the excitation side shutter which concerns on Example 1. FIG. It is a fluorescence spectrum in the state where the excitation side shutter concerning comparative example 1 was closed. It is a fluorescence spectrum in the state where the excitation side shutter which concerns on the comparative example 2 was opened. It is a light absorption spectrum of a fluorescent agent (Lumogen F Orange 240). 5 is a graph showing afterglow luminance characteristics of Example 1 and Comparative Example 1. It is a fluorescence spectrum of resin which made the polystyrene contain the phenazacillin polymer (1). It is a fluorescence spectrum in the state where the excitation side shutter which concerns on the comparative example 3 was opened. It is a fluorescence spectrum in the state which opened the excitation side shutter which concerns on Example 3. FIG. It is the excitation spectrum and fluorescence spectrum of a luminous agent (GLL-300M). . It is a fluorescence spectrum of resin which made the polystyrene contain the phenazacillin polymer (2).

Claims (4)

  A phosphorescent agent-containing resin characterized in that a phosphorescent agent and a fluorescent agent are contained in the resin, and the fluorescence spectrum in the dark of the phosphorescent agent and the light absorption spectrum of the fluorescent agent have an overlapping portion. Composition.   A phosphorescent agent-containing resin composition, wherein a phosphorescent agent and a fluorescent agent are contained in a resin, and a fluorescence spectrum of the fluorescent agent and an excitation spectrum of the phosphorescent agent have an overlapping portion.   The phosphorescent agent-containing resin composition according to claim 1, wherein the fluorescent agent is an organic fluorescent material that is compatible with the resin.   4. The phosphorescent agent-containing resin composition according to any one of claims 1 to 3, wherein the resin is a biodegradable plastic.

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