JP2001011324A - Luminous resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flexible luminous resin composition excellent in the feel, freely processable with scissors, a knife, etc., having the degree of freedom of shape and a high luminous quantity, readily visible in the dark at night, etc., and having a long luminous duration. SOLUTION: This luminous thermoplastic resin composition comprises (A) a luminous pigment such as zinc sulfide and (B) a thermoplastic resin having <=3 haze in a sheet having 3 mm thickness and has 1.0×109 to 4.0×109 Pa storage modulus at 0 deg.C and 1×105 to 1×108 storage modulus at 100 deg.C determined by dynamic viscoelasticity measurements such as an acrylic or a methacrylic resin. Furthermore, the content of the component A is preferably 5-50 wt.% based on the whole composition and the content of the component B is preferably 95-50 wt.% based on the whole composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminous resin composition, and more particularly, to a luminous resin composition which is easily visible even without a light source at night and can be easily processed with scissors, a knife or the like.

[0002]

2. Description of the Related Art Luminescent resin materials containing a luminous pigment are conventionally known, and are used as various kinds of guide plates and signs. A hard material such as an ordinary acrylic resin or a soft resin material such as a rubber is used for these phosphorescent resin materials (see Japanese Patent Application Laid-Open No. 11-80476 and others).

[0003]

However, when a hard resin is used as the luminous resin material, there is a problem that the molded product is easily broken and the application is restricted. On the other hand, a luminous material composed of a soft resin has a problem that the resin itself is opaque, and the amount of light emission is smaller than that of a luminous material composed of a highly transparent hard resin such as an ordinary acrylic resin. . An object of the present invention is to be soft and excellent in tactile sensation, can be freely processed with scissors, knives, etc., has a degree of freedom in shape, has a large light emission amount, is easily visible in dark places such as at night, and has a long light emission. An object of the present invention is to provide a long-lasting phosphorescent resin composition.

[0004]

Means for Solving the Problems The present inventors have set forth the above-mentioned object.
As a result of intensive studies to achieve the target, the phosphorescent pigment (A) and
And the haze of a sheet having a thickness of 3 mm is 3 or less.
Made of thermoplastic resin (B), determined by dynamic viscoelasticity measurement
Measured at 0 ° C. is 1.0 × 10 ⁹~ 4.
0x10⁹Pa and 1 × 10 at 100 ° C.
⁵~ 1 × 10⁸Luminescent resin characterized by being Pa
It was found that the above-mentioned object was achieved by the composition,
The invention has been reached.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The luminous resin composition of the present invention comprises a luminous pigment (A) and a transparent thermoplastic resin (B). Here, the luminous pigment refers to a pigment containing, as a main component, a luminous substance having a property of storing external energy and radiating the stored energy to the outside as light. Examples of the luminous substance include, for example, sulfides such as zinc sulfide and calcium sulfide, strontium aluminate, calcium aluminate, and aluminates such as barium aluminate. It is preferable to use strontium aluminate in view of the fact that the afterglow time is long and that it can be visually recognized almost overnight, and that it has excellent weather resistance and can be used for a long time outdoors. In addition, the external energy in the luminous substance is light having a wavelength that excites the luminous substance, and various kinds of lighting and the like can be used in addition to sunlight.

The content of the luminous pigment (A) in the luminous resin composition is preferably from 5 to 50% by weight, more preferably from 20 to 40% by weight, based on the entire luminous resin composition. Further, the content of the thermoplastic resin (B) is preferably 95 to 50% by weight based on the entire luminous resin composition.
More preferably, it is 0 to 60% by weight. When the content of the luminous pigment (A) is within the above range, luminous properties can be exhibited without saturating, and a luminous resin composition having a sufficient luminescence amount can be obtained.

The thermoplastic resin (B) constituting the luminous resin composition of the present invention is a thermoplastic resin (B) alone having a thickness of 3 m.
m is a thermoplastic resin that gives a sheet having a haze of 3 or less when molded into a sheet of m. When a thermoplastic resin having a haze of greater than 3 is used, the resulting phosphorescent resin composition will be inferior in luminescence. The haze of the sheet having a thickness of 3 mm is preferably 2 or less, more preferably 1 or less.

[0008] As such a thermoplastic resin (B),
Although not particularly limited, it is preferable to use a (meth) acrylic resin from the viewpoint of transparency and weather resistance.
Specific examples of the (meth) acrylic monomer used for producing the (meth) acrylic resin include methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isoamyl acrylate, 2-ethylhexyl methacrylate, and lauryl acrylate. , Lauryl methacrylate, tridecyl methacrylate, stearyl acrylate and the like having an alkyl group having 1 to 18 carbon atoms, such as alkyl (meth) acrylate; butoxyethyl acrylate and methoxypropyl acrylate having an alkoxy group having 1 to 4 carbon atoms such as an alkoxyalkyl ( (Meth) acrylates; alkoxypolyalkylene glycols such as methoxydiethylene glycol acrylate and ethoxydiethylene glycol acrylate Acrylates; aromatic (meth) acrylates such as phenoxyethyl acrylate and phenoxy polyethylene glycol acrylate; and hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate. And one or more of these can be used.

[0009] Among the above monomers, the obtained (meth)
In order to make the dispersibility of the luminous pigment (A) in the acrylic resin and the storage modulus of the luminous resin composition appropriate, methyl acrylate, methyl methacrylate, ethoxydiethylene glycol acrylate, 2-hydroxy-3-
It is preferable to use phenoxypropyl acrylate and the like in an appropriate ratio in combination.

The luminous resin composition of the present invention has a storage elastic modulus determined by dynamic viscoelasticity measurement of 1.0 × at 0 ° C.
10 ^{9 to} 4.0 × 10 ⁹ Pa, and 10
At 0 ° C., it must be in the range of 1 × 10 ⁵ to 1 × 10 ⁸ Pa. The storage modulus is 1.0 × 1 at 0 ° C.
Less than 0 ⁹ Pa or 1 × 10
^{When the} pressure is less than ⁵ Pa, the surface of the phosphorescent resin composition becomes sticky and the handleability is reduced, or the mold releasability during molding is poor. Further, the storage elastic modulus is 4.
Exceeds 0 × 10 ⁹ Pa or 1 × at 100 ° C.
If it exceeds 10 ⁸ Pa, the phosphorescent resin composition may be easily broken, or may have poor bending workability or cutting workability with scissors, a knife or the like.

In order to make the storage elastic modulus of the phosphorescent resin composition at 0 ° C. and 100 ° C. fall within the above range, for example,
When the thermoplastic resin (B) constituting the phosphorescent resin composition is produced by copolymerizing a monomer containing methyl methacrylate and an alkoxypolyalkylene glycol (meth) acrylate such as ethoxydiethylene glycol acrylate, By increasing the copolymerization ratio of methyl methacrylate, the storage elastic modulus at 0 ° C. and 100 ° C. can be increased, and by increasing the copolymerization ratio of alkoxypolyalkylene glycol (meth) acrylate at 0 ° C. and 100 ° C. The storage modulus can be reduced. The weight ratio in the case of copolymerizing methyl methacrylate and alkoxypolyalkylene glycol (meth) acrylate is such that the storage elastic modulus of the obtained luminous resin composition falls within the above range and gives a thermoplastic resin having a small haze. Therefore, the ratio is preferably from 70:30 to 40:60, and more preferably from 60:40 to 50:50.

The method for producing the luminous resin composition of the present invention is not particularly limited. For example, a method of kneading a luminous pigment (A) and a thermoplastic resin (B) which has already been polymerized, a luminous method, A method of polymerizing a monomer in which the pigment (A) is dispersed in the presence of a polymerization initiator,
It can be produced by a method in which a phosphorescent pigment (A) dispersed in a syrup of a thermoplastic resin is poured into a mold and solidified. As the thermoplastic resin (B) in the above method, a (meth) acrylic resin, a styrene resin, a vinyl ester resin, a vinyl halide resin, a vinyl ether resin obtained by polymerizing the above-mentioned monomers are used. One or more types such as a series resin can be mentioned,
Examples of the monomer in the above method include one or more of the above-mentioned (meth) acrylate-based monomers, styrene-based monomers, and vinyl ester-based monomers.

The syrup in the above method is a composition in which a resin component is dissolved in a monomer or a partial polymer of a monomer, and is a syrup-like liquid having a high viscosity. Cured by the initiator. As the resin component, the thermoplastic resin (B) described in the above method can be used, and as the monomer component, the monomer described in the above method can be used. Above all, as the resin syrup, a methacrylic resin syrup mainly composed of methyl methacrylate is preferable. This methacrylic resin syrup is prepared by adding a radical polymerization initiator to methyl methacrylate and, if necessary, other (meth) acrylic monomers, heating in a prepolymerization tank, and partially polymerizing or separately polymerizing methacrylic resin. Is dissolved in a monomer. The viscosity of the syrup is preferably 300 to 2,000 centipoise from the viewpoint of easy mixing and casting.
The viscosity may be adjusted by additionally mixing the monomer after producing the syrup.

To the syrup, in addition to the above monomers, for example, a silane coupling agent, finely divided silica, etc. may be added for the purpose of preventing sedimentation of the phosphorescent pigment (A), improving dispersibility, adjusting viscosity, and the like. good. Examples of the method of polymerizing and curing the syrup in which the luminous pigment is dispersed include a method of heating in the presence of a radical polymerization initiator, a method using a so-called redox initiator composed of a radical polymerization initiator and an accelerator, and the like. However, the present invention is not limited to these.

In the above methods (1) to (4) for producing the luminous resin composition of the present invention, poor dispersion, aggregation,
The above method is preferably employed since a homogeneous luminous resin composition can be obtained without sedimentation or the like.

The luminous resin composition of the present invention is preferably used in the form of a sheet because it can be easily cut or bent with scissors, a knife or the like. As a method of forming into a sheet, extrusion molding, injection molding,
It can be performed by a cast molding method or the like. Among these methods, when the luminous resin composition is produced by the method using the above-mentioned resin syrup, the cast molding method is preferred because the steps can be simplified and a sheet having excellent surface properties can be obtained.

The luminous resin composition of the present invention requires a special power supply to take in and store the energy of daytime sunlight and artificial illumination light and radiate the stored energy as light in a dark place. Visual recognition is possible without performing. Also,
Since the molded article formed into a sheet shape has a degree of freedom in form, it can be wound around a handrail of a stair or a corner. Furthermore, since it is soft, it can be cut with scissors or a knife without using special cutting equipment, a running saw, or the like, and can be processed into various shapes having designability.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In addition, each characteristic in an Example and a comparative example was measured or evaluated as follows.

(1) Dynamic Viscoelasticity Measurement Dynamic Viscoelasticity Measurement Apparatus "Rheospectral DVE-V4"
(Rheology) was used to determine the storage modulus (E ′) under the following measurement conditions. Waveform: Sine wave Vibration method: Continuous Load: Automatic static load 200% 15g Jig: Tension Specimen dimensions: width 3mm x thickness 3mm x length 20mm Measurement temperature range: -50 ° C to 200 ° C Temperature change rate: 3 ° C / min

(2) Haze In each of the examples and comparative examples, a sheet having a thickness of 3 mm was produced in the same manner except that no luminous pigment was added, and the haze was measured according to ASTM D1003.

(3) Visibility The sheet made of the phosphorescent resin composition was placed in a dark room, and the duration of the visible state was measured.

(4) Workability Evaluation was made according to the following criteria. ：: Can be easily cut with scissors, and can be bent into an arbitrary shape by hand. ×: Cannot be cut with scissors. Or, they are cracked or cracked when cutting with scissors.

Example 1 Polymethyl methacrylate obtained by copolymerizing 13% by weight of methyl acrylate (average degree of polymerization = 5)
00) 12 parts by weight of 19 parts by weight of methyl methacrylate,
A phosphorescent pigment containing strontium aluminate as a main component in a resin syrup dissolved in 24 parts by weight of ethoxydiethylene glycol acrylate, 14 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate, and 1 part by weight of γ-methacryloxypropyltrimethoxysilane. 30 parts by weight of "N Luminescent Luminova" (manufactured by Nemoto Special Science Co., Ltd.) are dispersed, and 0.08 parts by weight of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis ( 0.02 parts by weight of (2,4-dimethylvaleronitrile) was added, stirred and defoamed. The resin syrup in which the luminous pigment prepared above was dispersed was poured into a glass cell (spacer thickness: 3 mm) to which the vinylon film for release was adhered, and the resultant was poured into a 40 ° C water bath for 4 hours, and then into a 120 ° C air bath for 2 hours. Hold, 3m thick made of luminous resin composition
m luminous sheet was obtained. The storage elastic modulus of this luminous sheet was 2.41 × 10 ⁹ Pa at 0 ° C. and 1.36 × 10 ⁵ Pa at 100 ° C. The haze of a transparent sheet having a thickness of 3 mm produced by the same method as described above without blending only the phosphorescent pigment was 1.0. After irradiating the obtained phosphorescent resin composition with sunlight for 3 hours, the visibility in a dark place was confirmed. As a result, the visibility was good, and the visibility was possible up to 8 hours later. It was easy to cut the obtained phosphorescent sheet with scissors, and it was also possible to bend it into an arbitrary shape.

Comparative Example 1 Polymethyl methacrylate (12 parts by weight) as in Example 1 was replaced with methyl methacrylate (19 parts by weight) and ethoxy-diethylene glycol acrylate 3
Example 1 except that 30 parts by weight of a luminous pigment "N Luminescent Luminova" (manufactured by Nemoto Special Science Co.) containing strontium aluminate as a main component was dispersed in a resin syrup dissolved in 7 parts by weight and 1 part by weight of acrylic acid. 3m thickness in the same manner as
m luminous sheet was obtained. The storage elastic modulus of this luminous sheet is 8.57 × 10 ⁸ Pa at 0 ° C. and 9.7 at 100 ° C.
The pressure was 1 × 10 ⁴ Pa, and the haze of 3 mm produced by the above-mentioned method without mixing only the phosphorescent material was 6.0. After irradiating the luminous resin composition with sunlight for 3 hours, the visibility in a dark place was confirmed. As a result, the visibility was poor, and the visible time was 4 hours. Although it was possible to cut the obtained phosphorescent sheet with scissors, it was broken and cracked, which was not practical.

<Comparative Example 2> A resin syrup in which 12 parts by weight of poly (methyl methacrylate) was dissolved in 57 parts by weight of methyl methacrylate as in Example 1 was added to a luminous pigment "N night light" containing strontium aluminate as a main component. Luminova "
A phosphorescent sheet having a thickness of 3 mm was obtained in the same manner as in Example 1 except that 30 parts by weight (manufactured by Nemoto Special Science) was dispersed. The storage modulus of this luminous sheet is 6.17 × at 0 ° C.
10 ⁹ Pa, 3.12 × 10 ⁹ Pa at 100 ° C.,
The haze of 3 mm produced by the above-described method without mixing only the phosphorescent material was 1.0. After irradiating this luminous resin composition with sunlight for 3 hours, the visibility in a dark place was confirmed. As a result, the visibility was good, and the visibility was possible up to 8 hours later. It was difficult to cut the obtained phosphorescent sheet with scissors, and it was impossible to bend it into an arbitrary shape.

[0026]

[Table 1]

[0027]

The luminous resin composition of the present invention is soft and excellent in tactile sensation, can be freely processed with scissors, knives, etc., has a high degree of freedom in shape, has a large amount of light emission, and is dark at night. It is easy to visually recognize the light, and the light emission duration is long.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H001 XA08 XA13 XA38 4J002 BG041 BG051 BG071 CH051 DE186 DG026 FD096

Claims (2)

[Claims] 1. A luminous pigment (A) and a thermoplastic resin (B) having a haze of 3 or less in a sheet having a thickness of 3 mm, wherein a storage elastic modulus obtained by dynamic viscoelasticity measurement is 0.
1.0 × 10 ^{9 to} 4.0 × 10 ⁹ Pa at 100 ° C. and 1 × 10 ⁵ to 1 × 10 ⁸ Pa at 100 ° C.
A luminous resin composition, characterized in that: 2. The phosphorescent resin composition according to claim 1, wherein the phosphorescent pigment contains strontium aluminate as a main component.