JP3514333B2 - Textile products having phosphorescent fluorescence - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a textile product having phosphorescent fluorescence, particularly a textile product having a phosphorescent fluorescent substance using a novel phosphorescent phosphor having an extremely long afterglow characteristic while having excellent light resistance. It is about.

[0002]

2. Description of the Related Art Conventionally, various methods such as emergency signs and artificial flowers have been prepared by applying a paint or colorant containing a phosphorescent phosphor to a material, or molding a plastic containing a phosphorescent phosphor. Emergency supplies and decorations are made.
In addition, some products made of fibers are mainly coated with a paint containing the above-described phosphorescent phosphor on a carpet or a non-woven wallpaper, and such products have a hard and smooth coated surface and a poor texture. However, there are drawbacks such as deterioration of the characteristics of the textile material as a material, and peeling off of the paint after long-term use.

Now, the phosphorescent phosphor used in a conventional product made of fibers will be described. Generally, the afterglow time of a phosphor is extremely short, and its emission is rapidly attenuated when external stimulus is stopped, but in rare cases, it is considerably long (several ten minutes to several Afterglow is visible to the naked eye over time)
These are called phosphorescent phosphors or phosphors to distinguish them from ordinary phosphors.

As the phosphorescent phosphor, CaS: Bi
(Purple blue emission), CaSrS: Bi (blue emission), Zn
Sulfide phosphors such as S: Cu (green light emission) and ZnCdS: Cu (yellow to orange light emission) are known, but any of these sulfide phosphors is chemically unstable or light resistant. There are many practical problems such as poor performance.

The zinc sulfide-based phosphorescent phosphor (ZnS: Cu), which is currently mainly used in the market, is exposed to sunlight directly outdoors because it is photolyzed by ultraviolet rays to become black and its brightness is lowered particularly in the presence of moisture. It is difficult to use it for such applications, and the applications such as night clocks, evacuation guidance signs, indoor nighttime displays, etc. were limited.

Therefore, when the conventional phosphorescent phosphor is used in a product made of the above-mentioned fiber material, even if it is applied to clothes, it will be photodecomposed by ultraviolet rays to be turned into black when the humidity is present, or the brightness is lowered. However, it was inferior in light resistance and was not practical.

Even when this zinc sulfide-based phosphor is used, the afterglow time at which the fluorescence can be visually recognized is about 3
It takes about 0 minutes to 2 hours, and in practice, it has been unavoidable to use a self-luminous luminescent coating which is added with a radioactive substance in a phosphor and stimulated by its energy to constantly emit light.

[0008]

Therefore, in view of the above-mentioned current situation, the present inventor has a much longer afterglow characteristic than the commercially available sulfide-based phosphor, and further, chemically. A textile product is manufactured by using a new phosphorescent phosphor that is stable and has excellent light resistance for a long period of time, and a textile product having phosphorescent fluorescence that eliminates the drawbacks of the conventional products of this type is provided. It is intended for.

[0009]

[Means for Solving the Problems] As a novel phosphorescent phosphor material which is completely different from the conventionally known sulfide-based phosphors, attention has been paid to aluminate of alkaline earth metal activated with europium or the like, and As a result of the experiment, the phosphorescent phosphor material has afterglow property for a much longer time than the commercially available sulfide-based phosphor, and further, it is chemically based on the oxide-based phosphor. It has been confirmed that it is stable and has excellent light resistance, all the conventional problems can be solved, and it is visible all night without containing radioactivity as a luminous paint or pigment for various applications, especially for textile products. It has been clarified that it is possible to provide a long-afterglow phosphorescent phosphor that can be applied to, and use this phosphorescent phosphor to make a textile product having phosphorescent fluorescence.

As the fiber product having phosphorescent fluorescence as described above, the fiber product according to claim 1 is a fiber product having phosphorescent fluorescence formed by blending a phosphorescent phosphor with a thermoplastic resin. Fluorescent phosphor, M _1-X Al ₂ O _4-X
In the compound represented by the formula, M is a compound composed of at least one metal element selected from the group consisting of calcium, strontium, and barium, and is used as a mother crystal, and X is -0.33 ≦ X ≦ 0. With a range of 60 ,
Europium as an activator for the metal element represented by M
0.001% or more and 10% or less in terms of mol%
Neodymium, samarium, dysprosium, as an activator,
Holmium, erbium, thulium, ytterbium,
At least one or more elements of the group consisting of lutetium,
0.001% or more in mol% with respect to the metal element represented by M
It is characterized by using a material added with 10% or less .

According to a second aspect of the present invention, the first component containing the phosphorescent phosphor and the second component substantially containing no phosphorescent phosphor are used, and the first component accounts for 60% or less of the fiber cross-sectional circumference. Fiber diameter 150 arranged in parallel or sheath-core type so as to occupy
A fiber product having phosphorescent fluorescence, which is composed of a composite fluorescent fiber having a size of μm or less alone or is used in combination with another fiber, wherein M _1-X Al ₂ is used as the phosphorescent phosphor.
O in the compound of the composition represented by _4-X, M is calcium, strontium, a compound composed of at least one or more metal element selected from the group consisting of barium to host crystal <br/>, a further X - in the range of 0.33 ≦ X ≦ 0.60
Together with europium as an activator, a metal element represented by M
Addition of 0.001% or more and 10% or less in mol% with respect to element
In addition, as a co-activator, neodymium, samarium, dysp
Rhosium, Holmium, Erbium, Thulium, Itte
At least one of the group consisting of rubium and lutetium
Element is 0.0 in mol% with respect to the metal element represented by M.
It is characterized in that it is added in an amount of 01% or more and 10% or less .

According to a third aspect of the present invention, in the fiber product having the phosphorescent fluorescent substance according to the second aspect, the composite fluorescent fiber is formed so as to weave a pattern on a knitted or woven fabric composed of other fibers. It is characterized by

Furthermore, a fourth aspect of the present invention is characterized in that the fiber product having the phosphorescent fluorescent substance according to the second aspect is formed by laminating a layer made of a composite fluorescent fiber on a layer made of another fiber. To do.

A fifth aspect of the present invention is characterized in that, in the fiber product having the phosphorescent fluorescent substance according to the second aspect, a layer made of the composite fluorescent fiber is laminated between layers made of other fibers.

In the synthesis of these phosphorescent phosphors, boric acid is used as a flux in an amount of 1 to 10% by weight.
Can be added within the range. Here, the addition amount is 1
If it is less than 10% by weight, the flux effect will be lost and 10
If it exceeds 5% by weight, it solidifies, and subsequent pulverization and classification work becomes difficult.

Further, the thermoplastic resin which can be used in the invention described in claim 1 is a linear polymer such as polyethylene, polyester or polyamide. Further, although the textile product having phosphorescent fluorescence according to claim 1 is slightly inferior in spinnability and stretchability, it can be used by being applied to applications such as ropes, braids, and nets.

On the other hand, in order to obtain a fiber product in the form of woven fabric, knitted fabric, non-woven fabric, paper, carpet, etc., it is necessary that the fiber as a raw material has appropriate fineness and strength.

Therefore, as in the invention described in claim 2,
A fiber in which a phosphorescent phosphor is mixed with a fiber-forming resin is a composite fiber composed of a first component containing a phosphorescent phosphor and a second component containing substantially no phosphorescent phosphor (hereinafter referred to as a composite phosphor fiber If so, the decrease in spinnability, stretchability, strength, etc. due to the incorporation of the phosphorescent phosphor is the second factor.
The coexistence of the components saves a fine fiber having a fiber diameter of about 10 μm.

[0019] Incidentally, used as the composite phosphor fiber material resin used in the present invention according to claim 2, polyamide, polyester, polyolefin fin, polyvinyl alcohol, fiber-forming resins such as polyvinyl chloride is alone or as a mixture it can.

Both components to be composited in the composite spinning may be the same kind or different kinds of resins. In particular, when a resin having a melting point lower than that of the resin used for the first component by 20 ° C. or more is used as the second component that does not substantially contain the phosphorescent phosphor, the obtained composite fluorescent fiber has both components. By heat-treating at a temperature between the melting points, it is possible to generate heat fusion between fibers while maintaining the fiber shape, which is useful for heat-bonding type fiber products.

The compounding amount of the phosphorescent phosphor blended in the first component of the composite fluorescent fiber used in the invention of claim 2 may be appropriately adjusted depending on the intended use of the final product. Due to restrictions such as spinnability and fiber physical properties, it is generally about 10 to 40 wt% with respect to the entire composite fluorescent fiber.

By mixing a pigment in the second component of the composite fluorescent fiber used in the invention described in claim 2 to such an extent that the brightness of fluorescence is not impaired, various types of mixed fluorescent fiber other than the color tone of the phosphorescent phosphor itself can be obtained. Can be obtained.

Further, the above-mentioned first component and second component are spun into a parallel type or a sheath-core type composite fiber using a conventionally known composite spinning device. In the case of the parallel type, the first component is a fiber cross section. The manufacturing conditions such as the composite ratio and the spinning temperature are set so as to occupy 60% or less of the circumference. In the case of the sheath-core type, the first component is used on the core component side. Furthermore, the fiber cross section is circular, triangular, Y
The sheath-core type composite may be a single-core type or a multi-core type.

Further, here, the first component is 60 around the fiber cross section.
The reason for limiting it to occupy less than or equal to 10% is to prevent the phosphorescent phosphor from falling off from the fiber surface and to prevent the texture of the fiber from decreasing, and thus the composite fluorescent fiber obtained by itself or Used in combination with other fibers to be processed into various forms of fiber products. As a processing method, a method of the woven fabric, knitted fabric, carpets, ropes, braid or the like as twisted, needle punching method as short fibers or long fibers c E Bed, stitch bond method, spun bond method, thermal bonding method, a binder method For example, a method of forming a non-woven fabric or a fiber molded product by the above method, a method of forming a synthetic paper by wet paper making, or the like can be used, and the shape of the final product is not particularly limited.

When the composite fluorescent fiber is used in combination with another fiber, the composite fluorescent fiber does not need to be uniformly dispersed in the entire fiber product, and is scattered at several points on the surface of the fiber product. In some cases, this is preferable because the fluorescence emission brightness is high. Examples of the method of interspersing include a method of embroidering using a composite fluorescent fiber twisted yarn, a method of pattern weaving or tufting, and a method of completely or partially laminating a cloth made of a composite fluorescent fiber on the surface of another fiber product.

The thus-obtained fluorescent fiber product of the invention according to claim 2 has a general texture, surface structure, flexibility, texture, strength, etc. without the phosphorescent substance falling off. It is equivalent to a textile product and has a much higher commercial value and a wider range of uses than a textile product coated with fluorescent paint or a textile product made of thick fluorescent fiber.

Specific examples of application of the fluorescent fiber product of the invention according to claim 2 include curtains, wallpaper, carpets, dresses, raincoats, night work clothes, hats, flags, signs, Lamp shades, artificial flowers, etc. are widely used for decoration or disaster prevention.

[0028]

EXAMPLES Next, a novel phosphorescent phosphor will be described first. The novel phosphorescent phosphor here is M
A compound having a composition represented by _1-X Al ₂ O _4-X , and M is
A mother crystal of a compound composed of at least one metal element selected from the group consisting of calcium, strontium and barium is used, and X is -0.33 ≦ X ≦.
It is in the range of 0.60.

However, for convenience of explanation, first, X =
The compound represented by MAl ₂ O ₄ , which is 0, will be described. Further, regarding the compound represented by MAl ₂ O _{4, the case} where the type of the metal element (M), the concentration of europium as the activator, or the type and the concentration of the co-activator are variously changed will be sequentially described.

First, strontium is used as the metal element (M) and europium is used as the activator,
The phosphorescent phosphor of the case of using no co-activator, to explain. S rAl ₂ O _4: Eu phosphor Synthesis and properties Sample 1- (1) reagent grade strontium carbonate 146.1 g (of 0.99 mol) and alumina 102 g of europium oxide, europium as an activator in (1 mol) (Eu ₂ O ₃₎ in 1.76g (0.00
5 mol) and, for example, boric acid as a flux.
After adding 5 g (0.08 mol) and mixing well using a ball mill, this sample was heated to 1300 in a nitrogen-hydrogen mixed gas (97: 3) gas stream (flow rate: 0.1 liter per minute) using an electric furnace.
Firing was performed at ℃ for 1 hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was classified by a sieve and passed through 100 mesh to obtain a phosphor sample 1- (1).

FIG. 1 shows the result of analyzing the crystal structure of the synthesized phosphor by XRD (X-ray diffraction). From the characteristics of the diffraction peak, it was revealed that the phosphor obtained had the spinel structure of SrAl ₂ O ₄ . FIG. 2 shows the excitation spectrum of this phosphor and the emission spectrum of the afterglow after the stimulation was stopped.

From the figure, it was clarified that the emission spectrum was green emission with a peak wavelength of about 520 nm.
Next, a ZnS: Cu phosphorescent phosphor (manufactured by Nemoto Special Chemical Co., Ltd .: product name GSS, emission peak wavelength: 530) that emits green light afterglow characteristics of this SrAl ₂ O ₄ : Eu phosphor is a commercial product.
(nm) afterglow characteristics and the measured results are shown in FIG. 3 and Table 2.

The afterglow characteristic is measured by measuring 0.05 g of phosphor powder.
Is weighed into an aluminum sample pan with an inner diameter of 8 mm (sample thickness:
0.1g / cm ² ), after 15 hours of storage in the dark to eliminate the afterglow, stimulated with a D ₆₅ standard light source at a brightness of 200 lux for 10 minutes, and then use the afterglow with a photomultiplier tube. It was measured by the brightness measuring device. As is clear from FIG. 3, the afterglow of the SrAl ₂ O ₄ : Eu phosphor according to the present invention is extremely large and its attenuation is gentle, and the afterglow intensity difference with the ZnS: Cu phosphorescent phosphor is large with the passage of time. I see. In the figure, the level of the emission intensity (corresponding to a brightness of about 0.3 mcd / m ² ) which can be sufficiently recognized by the naked eye is shown by a broken line. This SrAl ₂ O ₄ : E
It is estimated from the afterglow characteristics of the u phosphor that the emission can be recognized even after about 24 hours. When the SrAl ₂ O ₄ : Eu phosphor that had actually passed 15 hours after stimulation was observed with the naked eye, its afterglow could be sufficiently confirmed.

For sample 1- (1) in Table 2, the afterglow intensity after 10 minutes, 30 minutes and 100 minutes after the stimulation was stopped was measured.
S: Cu is shown as a relative value with respect to the intensity of the phosphorescent phosphor.
From this table, the afterglow brightness of the SrAl ₂ O ₄ : Eu phosphor according to the present invention was found to be 2.9 of that of the ZnS: Cu phosphorescent phosphor after 10 minutes.
It can be seen that it is doubled and 17 times after 100 minutes. Furthermore, the thermoluminescence property (glow curve) from room temperature to 250 ° C. when the SrAl ₂ O ₄ : Eu phosphor according to the present invention was photostimulated was investigated by using a TLD reader (KYOKKO TLD-2000 system). It was shown to. From the figure, it can be seen that the thermoluminescence of the present phosphor comprises three glow peaks of about 40 ° C., 90 ° C. and 130 ° C., and the peak of about 130 ° C. is the main glow peak. ZnS: Cu indicated by the broken line in the figure
In light of the fact that the main glow peak of the phosphorescent phosphor is about 40 ° C., the deep trap level of the SrAl ₂ O ₄ : Eu phosphor according to the present invention, which corresponds to a high temperature of 50 ° C. or higher, shows the afterglow time constant. It is considered that it is increased and contributes to the long-term light storage characteristics.

Samples 1- (2) to (7) Next, in the same manner as described above, the SrAl ₂ O ₄ : Eu phosphor sample having the composition ratio shown in Table 1 in which the concentration of europium was changed (Sample 1- (2) to (7)) were adjusted.

[0036]

[Table 1]

The results of examining the afterglow characteristics of Samples 1- (2) to (7) are shown in Table 2 together with the results of examining the afterglow characteristics of 1- (1). From Table 2, it is found that when the amount of Eu added is in the range of 0.0025 to 0.05 mol, the afterglow property is superior to that of the ZnS: Cu phosphorescent phosphor including the brightness after 10 minutes. Recognize. However, the addition amount of Eu is 0.
Even if the amount is 0,0001 mol or 0.1 mol, if 30 minutes or more elapses after the stimulation is stopped,
It can also be seen that the ZnS: Cu phosphor has a higher brightness than that of the phosphorescent phosphor.

Further, since Eu is expensive, it is meaningless to set Eu to 0.1 mol (10 mol%) or more in consideration of economical efficiency and deterioration of afterglow characteristics due to concentration quenching. Become. Conversely, judging from the afterglow characteristics, Eu is 0.00001 mol (0.001 mol%)
To 0.00005 mol (0.005 mol%), the brightness after 10 minutes was inferior to that of the ZnS: Cu phosphorescent phosphor, but when the stimulus was stopped for 30 minutes or more, the ZnS: Cu phosphorescent Since the luminance is higher than that of the fluorescent substance, the effect of adding Eu used as an activator is clear.

Further, since the SrAl ₂ O ₄ : Eu phosphor is an oxide type, it is chemically stable and excellent in light resistance as compared with the conventional sulfide type phosphorescent phosphor. (See Tables 21 and 22 ).

[0040]

[Table 2]

Next, a phosphorescent phosphor using strontium as the metal element (M), europium as the activator, and dysprosium as the coactivator will be described as Example 1 . Example 1 . Synthesis of SrAl ₂ O ₄ : Eu, Dy Phosphor and Its Properties Sample 2- (1) Strontium carbonate 144.6 g (0.98 mol) of reagent grade and europium oxide (Eu) as an activator were added to alumina 102 g (1 mol). ₂ O ₃ ) 1.76g (0.00
5 mol), and 1.87 g (0.005 mol) of dysprosium oxide (Dy ₂ O ₃ ) as a co-activator, and 5 g (0.08 mol) of boric acid as a flux.
Mol) and thoroughly mixed using a ball mill,
Nitrogen-hydrogen mixed gas (97: 3) using an electric furnace for this sample
Firing was performed in an air stream (flow rate: 0.1 liter per minute) at 1300 ° C. for 1 hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was classified by a sieve and passed through 100 mesh to obtain a phosphor sample 2- (1).

The afterglow characteristics of this phosphor were investigated by the same method as described above, and the results are shown in Sample 2- (1) of FIG. 5 and Table 4. As is clear from FIG. 5, SrAl ₂ according to the present invention
The afterglow brightness of the O ₄ : Eu, Dy phosphor, especially the brightness at the initial stage of the afterglow is extremely higher than that of the ZnS: Cu phosphorescent phosphor, and its decay time constant is large, which is epoch-making. It can be seen that it is a high brightness phosphorescent phosphor. The visible afterglow intensity level shown in the figure and this SrAl ₂ O ₄ : E
Even after about 16 hours from the afterglow characteristics of the u and Dy phosphors, the emitted light can be identified.

In Table 4, 10 minutes, 30 minutes and 100 minutes after stimulation are shown.
The afterglow intensity after minute is shown as a relative value with respect to the intensity of the ZnS: Cu phosphorescent phosphor.
The afterglow brightness of the l ₂ O ₄ : Eu, Dy phosphor is Z after 10 minutes.
nS: Cu 12.5 times that of phosphorescent phosphor, and after 100 minutes
It turns out that it is 37 times. Furthermore, SrAl according to the present invention
₂ O ₄ : Eu, Dy phosphor from room temperature to 2
FIG. 6 shows the results of an examination of the thermoluminescence characteristics (glow curve) up to 50 ° C. 6 and 4 that the main glow peak temperature of thermoluminescence changed from 130 ° C. to 90 ° C. by the action of Dy added as a co-activator.
The large emission from the trap level corresponding to the temperature of 90 ° C. is considered to be the cause of exhibiting higher brightness at the initial stage of afterglow as compared with the SrAl ₂ O ₄ : Eu phosphor.

Samples 2- (2) to (7) Next, in the same manner as described above, SrAl ₂ O ₄ : Eu, D having the composition ratio shown in Table 3 in which the concentration of dysprosium was changed.
y phosphor samples (Samples 2- (2) to (7)) were prepared.

[0045]

[Table 3]

The results of examining the afterglow characteristics of Samples 2- (2) to (7) are shown in Table 4 together with the results of examining the afterglow characteristics of 2- (1). From Table 4, D as a co-activator
Based on the fact that the addition amount of y is far superior to that of the ZnS: Cu phosphorescent phosphor including the luminance after 10 minutes, 0.0025 to 0.05 mol is found to be optimal. However, even when the amount of Dy added is 0.00001 mol, the luminescent material has a brightness higher than that of the ZnS: Cu phosphorescent phosphor 30 minutes or more after the stimulation is stopped. The effect of adding Eu and Dy used as the co-activator is clear. In addition, since Dy is expensive, Dy is 0.1 mol (1
It means that there is not much meaning in making it 0 mol% or more.

Since the SrAl ₂ O ₄ : Eu, Dy phosphor is an oxide type, it is chemically stable and excellent in light resistance as compared with the conventional sulfide type phosphorescent phosphor. (See Tables 21 and 22 ).

[0048]

[Table 4]

Next, using a strontium as the metal element (M), using a europium as an activator and further the phosphorescent phosphor in the case of using neodymium as a co-activator will be described as a second embodiment. Example 2 . SrAl ₂ O _4: Eu, Nd-phosphor Synthesis and properties Sample 3- (1) to (7) above and similar methods, Table 5 with varying concentrations of neodymium
The SrAl ₂ O ₄ : Eu, Nd-based phosphor samples (Samples 3- (1) to (7)) having the compounding ratio shown in (3) were prepared.

[0050]

[Table 5]

Table 6 shows the results of investigating the afterglow characteristics of these samples 3- (1) to (7).

[0052]

[Table 6]

From Table 6, it can be seen that when the addition amount of Nd as a co-activator is in the range of 0.0025 to 0.10 mol,
It can be seen that the ZnS: Cu phosphorescent phosphor is superior in afterglow characteristics including the brightness after 0 minutes. However, even when the amount of Nd added is 0.00001 mol, 6 after the stimulation is stopped.
After about 0 minutes, the ZnS: Cu phosphorescent phosphor has a higher brightness,
The effect of adding Eu and Nd used as the activator and co-activator is clear. Further, since Nd is expensive, it is meaningless to set Nd to 0.1 mol (10 mol%) or more in consideration of economy and deterioration of afterglow characteristics due to concentration quenching.

Since the SrAl ₂ O ₄ : Eu, Nd phosphor is an oxide type, it is chemically stable and excellent in light resistance as compared with the conventional sulfide type phosphorescent phosphor. (See Tables 21 and 22 ). Furthermore, when the SrAl ₂ O ₄ : Eu, Nd phosphor according to the present invention is photostimulated, the thermoluminescence property (glow curve) from room temperature to 250 ° C.
FIG. 7 shows the result of an examination of Sample 3- (4). From the figure, it can be seen that the main glow peak temperature of thermoluminescence of the phosphor to which Nd is added as a co-activator is about 50 ° C.

Next, use with strontium as the metal element (M), using a europium as an activator, as further co-activator, Sa Mariumu, Ho Rumiumu, erbium, thulium, ytterbium, and any element Rutechiu arm The phosphorescent phosphor in such a case will be described as Example 3 .

[0056] In this case, for the activator and the co-activator, the example of using the Yu c europium and neodymium or dysprosium, when added about each 0.005 moles to metal element (M) Considering that a very high afterglow brightness can be obtained, the Eu concentration of the activator is 0.5 mol%
(0.005 mol), the concentration of the co-activator is 0.5 mol% (0.
(005 mol) sample only. Example 3 . SrAl ₂ O _4: Other co-activator effect the method described above for the Eu phosphor, Sa as a co-activator Mariumu, e Rumiu <br/> arm, erbium, thulium, ytterbium, Rutechiu
Table 7 shows the results of an examination of the afterglow characteristics of the phosphor sample to which the phosphor was added.

As is clear from Table 7, in comparison with the afterglow characteristics of the commercially available ZnS: Cu phosphor used as a standard, all of the SrAl ₂ O ₄ : Eu phosphor samples were 30% after the stimulation was stopped. After a long time of 100 minutes to 100 minutes, the afterglow characteristic is improved, and it can be seen that it is at a practical level. Since the SrAl ₂ O ₄ : Eu-based phosphor is an oxide-based phosphor, it is chemically stable and excellent in light resistance as compared with the conventional sulfide-based phosphorescent phosphors (Table 21 and 22 ).

[0058]

[Table 7]

Next, although calcium is used as the metal element (M) and europium is used as the activator, a phosphorescent phosphor without a co-activator and calcium as the metal element and europium as the activator are used. ,
Ne o Jim as a co-activator, samarium, di Supuroshiu <br/> arm, holmium, erbium, thulium, ytterbium, a case of using at least one element of Rutechiu arm or Ranaru group, described as Example 4 . Example 4 . Synthesis of CaAl ₂ O ₄ : Eu-based phosphorescent phosphor and its characteristic reagent Europium oxide (Eu ₂ O ₃ ) as an activator was added to special grade calcium carbonate and alumina, as a coactivator. , the value o di
Arm, samarium, dysprosium, holmium, erbium, thulium, ytterbium, and any element Rutechiu beam relative to that added with the oxide, respectively, further as for example boric acid flux was added 5 g (0.08 mol), a ball mill After being thoroughly mixed with the above, the sample was baked in an electric furnace in a nitrogen-hydrogen mixed gas (97: 3) gas stream (flow rate: 0.1 liter per minute) at 1300 ° C. for 1 hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was classified by sieving and passed through 100 mesh to obtain phosphor samples 5- (1) to ( 34 ).

The XRD of sample 5- (2) obtained here
The results of the analysis are shown in FIG. From the figure, it became clear that this phosphor was composed of a monoclinic CaAl ₂ O ₄ crystal. Next, neodymium in a co-activator as a typical example, using samarium, dysprosium, the tool helium samples 5- (10),
9 (a) and 9 (b) show the results of investigating the thermoluminescence characteristics (glow curve) of 5- (16), 5- (22) and 5- (28).
It was shown to. Since each has a glow peak in a high temperature range of 50 ° C. or higher, it is suggested that these phosphors have long afterglow characteristics. Furthermore, when the emission spectrum of the afterglow of the sample was measured, as shown in FIG. 11, the emission peak wavelength of any of the phosphors was about 442n.
It was blue light emission of m.

Therefore, the afterglow characteristics of the blue-emitting phosphorescent phosphors CaSrS: Bi (brand name BA-S: emission wavelength 454 nm manufactured by Nemoto Special Chemical Co., Ltd.), which are commercially available, are used as a standard. The results of the comparative investigation are shown in Tables 8 to 13. From Table 8 CaAl ₂ O ₄ : Eu
With regard to the phosphor, when Eu is 0.005 mol (0.5 mol%), there is a phosphor having a low brightness at the initial stage of afterglow, but a brightness almost equal to that of the commercial standard product after 100 minutes, Further, as shown in Tables 9 to 13, the addition of a co-activator greatly sensitized the phosphor, and it was possible to obtain a sufficiently practical phosphor using any co-activator. In particular, Nd, Sm, and Tm have an extremely large addition effect, and it is clear that an ultrahigh-luminance blue-light-emitting phosphorescent phosphor that is one digit or more brighter than a commercial product can be obtained, and it can be said that this is an epoch-making phosphor. FIG. 12 shows the results of investigating the afterglow characteristics of the high-brightness phosphor obtained by co-activating Nd, Sm, and Tm over a long period of time.

More specifically, although calcium is used as the metal element (M) and europium is used as the activator, it is used as a phosphorescent phosphor in the case where the coactivator is not used.
Table 8 shows the afterglow characteristics of the phosphorescent phosphors shown in-(1) to (6).

[0063]

[Table 8]

[0064] Also using calcium as the metal element (M), using a europium as an activator, as phosphorescent phosphor in the case of using the <br/> neodymium as a co-activator, 5- (7)
Table 9 shows the afterglow characteristics of the phosphorescent phosphors shown in (12) to (12).

[0065]

[Table 9]

Furthermore, when calcium is used as the metal element (M), europium is used as the activator, and samarium is used as the co-activator, 5- (1
Table 10 shows afterglow characteristics of the phosphorescent phosphors shown in 3) to (18).

[0067]

[Table 10]

When calcium is used as the metal element (M), europium is used as the activator, and dysprosium is used as the co-activator, the phosphorescent phosphor is 5
Table 11 shows afterglow characteristics of the phosphorescent phosphors shown in (19) to (24).
It was shown to.

[0069]

[Table 11]

When calcium is used as the metal element (M), europium is used as the activator, and thulium is used as the co-activator, 5- (25)
Table 12 shows the afterglow characteristics of the phosphorescent phosphors shown in (30) to (30).

[0071]

[Table 12]

[0072] Note that using calcium as the metal element (M), using a europium as an activator, and the co-activator
Ho Rumiumu, erbium, ytterbium, Rutechiu arm
As a phosphorescent phosphor when using any of the elements of
Table 13 collectively shows the afterglow characteristics of the phosphorescent phosphors shown in 5- (31) to ( 34 ).

[0073] Note that in phosphorescent phosphors shown in this 5- (31) - (34), Yu c europium and other co-activator as an activator are both obtained by adding increments 0.5 mol%.

[0074]

[Table 13]

[0075] Then using calcium as the metal element (M), using a europium as an activator, but using <br/> neodymium as a co-activator, Example 5 the case of adding at the same time other co-activator As described below. Example 5 . CaAl ₂ O _4: Eu, adding europium as Nd-based phosphorescent phosphors synthesized with activator to its characteristics reagent grade calcium carbonate and alumina as europium oxide (Eu ₂ O _3), neodymium thereto as a co-activator With the addition of
And, as still another co-activator, neodymium other sub Mali <br/> um, dysprosium, holmium, erbium, thulium, ytterbium, and any element Rutechiu beam to that added in the oxide, respectively After adding 5 g (0.08 mol) of boric acid as a flux and thoroughly mixing it with a ball mill, this sample was put in an electric furnace in a nitrogen-hydrogen mixed gas (97: 3) stream (flow rate: 0.1 It was baked at 1300 ° C. for 1 hour. Then, the mixture was cooled to room temperature for about 1 hour, and the obtained compound powder was sieved and classified to pass through 100 mesh.
-(1) to ( 24 ).

Here, first, various phosphor samples were prepared with Eu: 0.5 mol%, Nd: 0.5 mol% and other co-activator: 0.5 mol%, and after 10 minutes the luminance and after 30 minutes The brightness and the brightness after 100 minutes were measured. The result is 6- (1)
~ ( 7 ) are shown in Table 14.

[0077]

[Table 14]

[0078] From this measurement result, in a co-activator to be added together with neodymium, those afterglow luminance particularly excellent, dysprosium, ho Rumiumu, be an erbium or the like was confirmed. Therefore, Eu: 0.5 mol%, Nd: 0.
The experiment was conducted by changing the concentration of dysprosium from 0.1 mol% to 10 mol% after the concentration was 5 mol%. The result is
6- ( 8 ) to ( 13 ) are shown in Table 15 .

[0079]

[Table 15]

Eu: 0.5 mol%, Nd: 0.5 mol%, and the holmium concentration was changed from 0.1 mol% to 10 mol%.
Experiment was carried out by changing to. The results are shown in Table 16 as 6- ( 14 ) to ( 18 ).

[0081]

[Table 16]

Eu: 0.5 mol%, Nd: 0.5 mol%, and the erbium concentration was changed from 0.1 mol% to 5 mol%.
Experiment was carried out by changing to. The results are shown in Table 17 as 6- ( 19 ) to ( 24 ).

[0083]

[Table 17]

From the above measurement results, it was confirmed that when a plurality of coactivators were mixed, the afterglow brightness was improved. Furthermore, in that case, Eu: 0.5 mol%, N
d: 0.5 mol% and other co-activators 0.5 mol%
It was also confirmed that the best afterglow characteristics were exhibited when the content was added to some extent. Then using barium as the metal element (M), using a europium as an activator and further the phosphorescent phosphor in the case of using a neodymium or samarium as the co-activator will be described as Example 6. Example 6 . BaAl ₂ O ₄ : Eu-based phosphor In this case, after adding 0.5 mol% of Eu and further adding 0.5 mol% of Nd or Sm respectively, 7- (1)
, (2).

[0085] Of the present phosphors in FIG. 13, but using neodymium as a co-activator, showing an emission spectrum of afterglow after a lapse of 30 minutes after stopping the excitation spectrum and irritation. Further, FIG. 14 shows the excitation spectrum and the afterglow emission spectrum after 30 minutes from the stop of stimulation, although samarium was used as a co-activator.

Since the peak wavelengths of the emission spectra are all about 500 nm and green light is emitted, Table 18 shows
The afterglow property was compared with that of a commercially available ZnS: Cu phosphorescent phosphor that emits green light (manufactured by Nemoto Special Chemical Co., Ltd .: product name GSS, emission peak wavelength: 530 nm).
The afterglow intensity after minutes, 30 minutes, and 100 minutes was shown as a relative value.

[0087]

[Table 18]

From Table 18 , BaAl ₂ O ₄ : Eu,
Nd is 30 after stimulation is stopped as compared with ZnS: Cu phosphorescent phosphor.
It can be seen that afterglow is excellent in afterglow brightness. Also Ba
The result was that Al ₂ O ₄ : Eu, Sm was slightly inferior in afterglow brightness to the ZnS: Cu phosphorescent phosphor. However, without adding Eu or other co-activator, BaAl ₂ O ₄
As a result of an experiment conducted only with crystals, it was confirmed that fluorescence and afterglow were not observed at all, so it is clear that the activation effect can be obtained by adding Eu and Nd or Sm.

Since the BaAl ₂ O ₄ : Eu phosphor is an oxide phosphor, it is chemically stable and excellent in light resistance as compared with the conventional sulfide phosphorescent phosphor. Yes (see Tables 21 and 22 ). Next, a case where a mixture of calcium and strontium is used as the metal element (M) will be described as Example 7 . Example 7 . Synthesis of Sr _X Ca _1-X Al ₂ O ₄ -based phosphorescent phosphor and its characteristic reagent Special grade strontium carbonate and calcium carbonate were mixed in different proportions, alumina was added to the sample, and europium was added as an activator. Ne o as a co-activator
Jim, samarium, dysprosium, holmium, erbium, thulium, ytterbium, to that was added Izu <br/> Re of elements Rutechiu arm, as for example, boric acid flux 5 g (0.08 mol) was added, the above in was synthesized _{Sr X Ca 1-X Al 2} O 4 phosphorescent phosphor samples in the method.

As a typical characteristic of the obtained phosphor, Sr _0.5
FIG. 15 shows the result of investigating the afterglow emission spectrum of the Ca _0.5 Al ₂ O ₄ : Eu, Dy phosphor (Eu _0.5 mol% and Dy _0.5 mol% added). From the figure, when a part of Sr is replaced by Ca, the emission spectrum shifts to the short wavelength side, and the emission by the SrAl ₂ O ₄ -based phosphor and CaAl
It was revealed that the afterglow of the intermediate color of the emission of the ₂ O ₄ system phosphor can be obtained.

Then, Sr _x Ca _1-x containing 0.5 mol% of Eu and Dy as activators and co-activators, respectively.
The results of investigating the afterglow characteristics of the Al ₂ O ₄ based phosphor sample are shown in FIG. It can be seen from FIG. 16 that for any of the phosphors, a highly practical phosphorescent phosphor having excellent afterglow characteristics equivalent to or higher than that of the commercial standard product shown by the broken line in the drawing can be obtained.

Next, in the case where a mixture of strontium and barium was used as the metal element (M),
8 will be described. Example 8 . Synthesis of Sr _X Ba _1-X Al ₂ O ₄ system phosphorescent phosphor and its characteristic reagent Special grade strontium carbonate and barium carbonate were mixed in different proportions, alumina was added to the sample, and europium was added as an activator. Ne o di as a co-activator
Arm, samarium, dysprosium, holmium, erbium, thulium, ytterbium, the material obtained by adding any element of Rutechiu beam, 5 g (0.08 mol) as for example boric acid flux was added, Sr _X by the method described above
A Ba _1-X Al ₂ O ₄ -based phosphor sample was synthesized.

As typical characteristics of the obtained phosphor, S adjusted by adding 0.5 mol% of Eu and 0.5 mol% of Dy
FIG. 17 shows the result of investigation on the afterglow characteristics of the r _X Ba _{1 -X} Al ₂ O ₄ -based phosphor sample. It can be seen from FIG. 17 that for any of the phosphors, it is possible to obtain a highly practical phosphorescent phosphor having excellent afterglow characteristics equivalent to or higher than those of the commercial standard product indicated by the broken line in the figure.

A case in which a plurality of metal elements are used as the metal element (M), europium is used as the activator, and two kinds of co-activators are used will be described as Example 9 . Example 9 Ca _1-X Sr _X Al ₂ O ₄ : Eu, Nd, X
Phosphor Synthesis and properties special grade of strontium carbonate and calcium carbonate were blended with different ratios respectively alumina was added to the sample, neodymium 0 europium 0.5 mol%, as a co-activator as further activator. 5 mol% was added, as a yet another co-activator, dysprosium, one of the elements holmium to those added 0.5 mol%, as for example, boric acid flux 5 g (0.08 mol) was added, the above By the method, Ca _1-X Sr _X Al ₂ O ₄ : Eu, Nd, X-based phosphor samples 11- (1) to ( 6 ) were synthesized, and their afterglow characteristics were investigated.

First, reagent grade strontium carbonate and calcium carbonate were mixed in different proportions, alumina was added to the sample, and europium 0.5 was added as an activator.
The mole%, neodymium 0.5 mol% was added as a co-activator, as yet another co-activator, dysprosium 0.5
Table 19 shows that the addition of mol% was 11- ( 1 ) to ( 3 ).
Shown in.

[0096]

[Table 19]

Further, reagent grade strontium carbonate and calcium carbonate were mixed in different proportions, alumina was added to the sample, and europium 0.5 was added as an activator.
The mole%, neodymium 0.5 mol% was added as a co-activator, as yet another co-activator, a material obtained by adding holmium 0.5 mol% 11- (4) to (6), Table 20 Shown in.

[0098]

[Table 20]

From these measurement results, the metal element (M)
However, even when a plurality of metal elements (M) composed of calcium and strontium are used, europium is added as an activator, and a plurality of coactivators are added, 1
It was confirmed that it was superior to CaSrS: Bi including the brightness after 0 minutes. Example 10 . Moisture resistance property test Table 21 shows the results of investigation of the moisture resistance property of the phosphorescent phosphor obtained according to the present invention.

[0100] In this investigation, 40
The sample was left for 500 hours in a thermo-hygrostat controlled at 95 ° C. and 95% RH, and the change in brightness before and after that was measured. From the table, it can be seen that the phosphors of any composition are stable and hardly affected by humidity.

[0101]

[Table 21]

Example 11 Results of light resistance test The results of light resistance test of the phosphorescent phosphor obtained according to the present invention are shown in Table 22 in comparison with the results of the zinc sulfide-based phosphor. In this test, according to JIS standard, the sample was placed in a transparent container whose humidity was adjusted to 30% under a 300 W mercury lamp.
Light was irradiated at the position of cm for 3 hours, 6 hours, and 12 hours, and the change in luminance after that was measured.

From the table, it can be seen that it is extremely stable as compared with the conventional zinc sulfide-based phosphor.

[0104]

[Table 22]

Although this phosphorescent phosphor is shown as MAl ₂ O ₄ , it is not limited to the case where the composition of M, Al and O is completely 1: 2: 4.
By chance, this ratio may slightly shift due to various conditions. Of course, it goes without saying that such a slight deviation belongs to the technical range of the above-mentioned application as long as the above-mentioned effects are achieved.

Therefore, the Applicant consciously measured the brightness of the phosphorescent phosphors having the above ratios changed. Then, it was found that there was a case where the afterglow brightness was more excellent when there was a slight deviation in the ratio. Below, M _1-x
Sr is a phosphorescent phosphor represented by a composition of Al ₂ O _4-x , in which strontium is used as a metal element (M), europium is used as an activator, and dysprosium is further used as a coactivator. _1-x Al ₂ O _4-x :
Eu and Dy will be described as an example.

Here, the concentration of Eu and Dy is 0.005 mol added to strontium. Further, as the ratio of strontium to aluminum at the time of the experiment, the value of X, and the phosphorescent phosphor at that time, those shown as samples (1) to (8) were used as follows. (1) Sr: Al = 1: 1.5 X = -0.33 Sr _1.33 Al ₂ O
_4.33 : Eu, Dy (2) Sr: Al = 1: 1.9 X = -0.05 Sr _1.05 Al ₂ O
_4.05 : Eu, Dy (3) Sr: Al = 1: 2.0 X = 0 Sr _1.00 Al ₂ O
_4.00 : Eu, Dy (4) Sr: Al = 1: 2.1 X = 0.05 Sr _0.95 Al ₂ O
_3.95 : Eu, Dy (5) Sr: Al = 1: 2.5 X = 0.20 Sr _0.80 Al ₂ O
_3.80 : Eu, Dy (6) Sr: Al = 1: 3.0 X = 0.33 Sr _0.67 Al ₂ O
_3.67 : Eu, Dy (7) Sr: Al = 1: 4.0 X = 0.50 Sr _0.50 Al ₂ O
_3.50 : Eu, Dy (8) Sr: Al = 1: 5.0 X = 0.60 Sr _0.40 Al ₂ O
_3.40 : Eu, Dy Then, these samples (1) to (8) were once put into a state where there was no afterglow, then allowed to stand in the room for 20 minutes, and the brightness after 3 minutes was visually confirmed. Then, the afterglow luminance when X = 0 was set to 100 was measured. The values are shown in Table 23 .

[0108]

[Table 23]

From this table, SrAl ₂ O with X = 0
₄ : Compared with the sample (3) showing Eu and Dy, the sample (1),
Samples (4) to (6) are samples (2) with poor afterglow brightness.
Some of them have afterglow characteristics that are almost the same as or slightly higher than (3). From this, a phosphorescent phosphor using strontium as the metal element (M), europium as the activator, and dysprosium as the coactivator was added to Sr _1-x Al ₂ O _4-x : Eu, Dy When expressed as, the range showing the practical afterglow brightness is −0.33.
It was confirmed that the range was ≦ X ≦ 0.60. Furthermore,
It was confirmed that the range is preferably 0 ≦ X ≦ 0.33.

Next, the phosphorescent phosphor represented by the composition of M _1-x Al ₂ O _4-x was prepared by using calcium as the metal element (M), europium as the activator, and dysprosium as the coactivator. C which is a phosphorescent phosphor using
A _1-x Al ₂ O _4-x : Eu, Dy will be described as an example.
The concentration of Eu and Dy is 0.005 mol with respect to calcium.

Further, as the ratio of calcium to aluminum in the experiment, the value of X, and the phosphorescent phosphor at that time, those shown as samples (1) to (8) were used as follows. . (1) Ca: Al = 1: 1.5 X = -0.33 Ca _1.33 Al ₂ O
_4.33 : Eu, Dy (2) Ca: Al = 1: 1.9 X = -0.05 Ca _1.05 Al ₂ O
_4.05 : Eu, Dy (3) Ca: Al = 1: 2.0 X = 0 Ca _1.00 Al ₂ O
_4.00 : Eu, Dy (4) Ca: Al = 1: 2.1 X = 0.05 Ca _0.95 Al ₂ O
_3.95 : Eu, Dy (5) Ca: Al = 1: 2.5 X = 0.20 Ca _0.80 Al ₂ O
_3.80 : Eu, Dy (6) Ca: Al = 1: 3.0 X = 0.33 Ca _0.67 Al ₂ O
_3.67 : Eu, Dy (7) Ca: Al = 1: 4.0 X = 0.50 Ca _0.50 Al ₂ O
_3.50 : Eu, Dy (8) Ca: Al = 1: 5.0 X = 0.60 Ca _0.40 Al ₂ O
_3.40 : Eu, Dy Then, these samples (1) to (8) were once put into a state where there was no afterglow, then allowed to stand in the room for 20 minutes, and the brightness after 3 minutes was visually confirmed. Then, the afterglow luminance when X = 0 was set to 100 was measured. The values are shown in Table 24 .

[0112]

[Table 24]

From this table, CaAl ₂ O with X = 0
₄ : Compared with the sample (3) showing Eu and Dy, the sample (1),
All of (2) and (4) to (6) were inferior in afterglow brightness, but were sufficiently durable to use. From this, a phosphorescent phosphor using Ca as a metal element (M), europium as an activator, and dysprosium as a coactivator was prepared as Ca _1-x Al ₂ O _4-x : Eu, Dy.
When expressed as, the range showing practical afterglow brightness is −
It was confirmed that the range was 0.33 ≦ X ≦ 0.60. Furthermore, it has been confirmed that the range is preferably −0.33 ≦ X ≦ 0.05.

Furthermore, a phosphorescent phosphor represented by the composition M _1-x Al ₂ O _4-x was used, barium was used as the metal element (M), europium was used as the activator, and dysprosium was used as the co-activator. Ba which is the phosphorescent phosphor used
_1-x Al ₂ O _4-x : Eu, Dy will be described as an example. The concentration of Eu and Dy is 0.005 mol with respect to barium.

Further, as the ratio of barium to aluminum at the time of the experiment, the value of X, and the phosphorescent phosphor at that time, those shown as samples (1) to (7) were used as follows. . (1) Ba: Al = 1: 1.5 X = -0.33 Ba _1.33 Al ₂ O
_4.33 : Eu, Dy (2) Ba: Al = 1: 1.9 X = -0.05 Ba _1.05 Al ₂ O
_4.05 : Eu, Dy (3) Ba: Al = 1: 2.1 X = 0.05 Ba _0.95 Al ₂ O
_3.95 : Eu, Dy (4) Ba: Al = 1: 2.5 X = 0.20 Ba _0.80 Al ₂ O
_3.80 : Eu, Dy (5) Ba: Al = 1: 3.0 X = 0.33 Ba _0.67 Al ₂ O
_3.67 : Eu, Dy (6) Ba: Al = 1: 4.0 X = 0.50 Ba _0.50 Al ₂ O
_3.50 : Eu, Dy (7) Ba: Al = 1: 5.0 X = 0.60 Ba _0.40 Al ₂ O
_3.40 : Eu, Dy Then, these samples (1) to (7) were once kept in a state of no afterglow, and then left in a room for 20 minutes, and the brightness after 3 minutes was visually confirmed. Then, the afterglow luminance when X = 0 was set to 100 was measured. The values are in Table 25 .

[0116]

[Table 25]

From this table, Ba _0.95 with X = 0.05
Compared with the sample (3) showing Al ₂ O _3.95 : Eu, Dy,
Samples (1) and (2) have poor afterglow brightness, but samples (4) and (2)
(5) shows slightly higher afterglow characteristics than sample (3).
Samples (6) and (7) were also durable enough to be used. From this, a phosphorescent phosphor using barium as the metal element (M), europium as the activator, and dysprosium as the coactivator was prepared as follows.
When expressed as a _1-x Al ₂ O _4-x : Eu, Dy, the range showing practical afterglow luminance is -0.33 ≦ X ≦ 0.6.
It was confirmed that the range was 0. Further, it was confirmed that the range is preferably 0.05 ≦ X ≦ 0.50.

[0118] In each of the above embodiments, europium as an activator, even by changing the ratio of dysprosium as a co-activator, that is the same trend that has been confirmed by the applicant.

[0119] In addition, as a co-activator, in addition to the above-mentioned dysprosium, the value Oh gym, samarium, ho Rumiumu,
Erbium, thulium, ytterbium, in the case where at least one or more elements of one Rutechiu arm <br/> Ranaru group, was added 10% 0.001% or more by mol% relative to the metal element expressed by M, M ₁ Regarding the compound represented by _-x Al ₂ O _4-x , it was confirmed that when X was set in the range of -0.33 ≤ X ≤ 0.60, a sufficiently practical afterglow luminance was exhibited.

Such a phosphorescent phosphor can be used by coating it on the surface of various products, or by sticking a sheet-shaped product, and using it, plastic, rubber or glass. It can also be used by mixing it with the like.

Next, a textile product having the phosphorescent fluorescent substance of the present invention, which is an application of such a phosphorescent fluorescent substance, will be described.

Example 1 of Textile Product Having Phosphorescent Fluorescence SrAl ₂ O as M _1-x Al ₂ O _4-x phosphorescent phosphor
₄ : Polypropylene containing 20% by weight of Eu and Dy as a core component, melt index (190 ° C.) 24 (g
/ 10 min) high density polyethylene as a sheath component, and a composite ratio (volume ratio) of 50/50 as composite spinning, and a fiber diameter of 25
A composite fluorescent fiber having a micrometer and a fiber length of 5 mm was obtained.

[0123] Polypropylene (core) and high-density polyethylene (sheath) known polyolefin emissions based heat-adhesive composite fiber comprising (3d / f, 5 mm) The Papermaking by a wet method basis weight 24 g / m ² (after drying) A sheet of bamboo grass, which occupies 30% of the sheet area, is used to form a sheet, and a liquid in which the above-mentioned composite fluorescent fiber is suspended is layered on the sheet to form a 20 g / m ² composite parallel fiber layer. Then dry and continue to 14
Heat-treated with a 5 ° C calender roll, basis weight 30g / m2
A thin non-woven fabric having a thickness of 0.13 mm was obtained.

This non-woven fabric exhibited the same strength and texture as the conventionally known non-woven fabric composed of the polyolefin-based heat-adhesive conjugate fiber, and the pattern portion was brightly fluorescent yellow-green in the dark for about 500 minutes. This non-woven fabric is effective for wallpaper, shoji paper, dress and the like. Example 2 of textile product having phosphorescent fluorescence CaAl ₂ O as M _1-x Al ₂ O _4-x phosphorescent phosphor
₄ : Polypropylene with Eu and Nd added at 30 wt% (first component) and melt index (190 ° C) 24
Composite spinning a parallel composite ratio (volume ratio) of 50/50 and a high-density polyethylene (second component) (g / 10 min), fiber diameter 30 [mu] m, fiber length 64 mm, the first component is a fiber cross section circumferential A composite fluorescent fiber having a ratio of 23% was obtained.

This composite fluorescent fiber was passed through a card machine to give a web having a basis weight of 150 g / m ² , and then heat-treated by passing through a suction drum dryer at 145 ° C. to give a nonwoven fabric. The obtained non-woven fabric has the same flexibility and strength as a non-woven fabric made of polypropylene fibers having a monofilament fineness of 3 denier by a thermal bonding method (Basis weight 150 g / m ² ),
It glowed bright blue in the dark, and the brilliance was such that a piece of cloth measuring 10 cm × 10 cm could be easily visually recognized from the distance of 50 m at night. Moreover, the fluorescent agent was not removed at all.

Such non-woven fabric is useful as a material for flags and safety signs. Example 3 of a textile product having phosphorescent fluorescence As a M _1-x Al ₂ O _4-x phosphorescent phosphor, Ca _0.1 Sr was used.
_0.9 Al ₂ O ₄ : Polypropylene containing 30% by weight of Eu and Dy as the first component and having a melt index of 24
(G / 10 min) high density polypropylene as the second component, both components were composite-spun in parallel type at a composite ratio (volume ratio) of 50/50, fiber diameter 25 μm, fiber length 64 mm, first component was fiber cross section. A composite fluorescent fiber having a occupying ratio of 19% was obtained, and a web having a basis weight of 150 g / m ^{2 was made} through a card machine, and then a maple leaf pattern patch was made from this web by a punching method.

A maple leaf-shaped patch made of the above-mentioned composite fluorescent fiber was formed on a web having a basis weight of 150 g / m ^{2 made} of a conventionally known heat-adhesive composite fiber containing polypropylene as a core component and high-density polyethylene as a sheath component. Are heat-treated by passing them through a suction drum dryer at 145 ° C., the nonwoven fabric has the same strength and texture as the nonwoven fabric composed of only the heat-adhesive conjugate fiber, and in the dark. In, the green glow of the pattern portion lasted for about 500 minutes. In addition, no loss of the fluorescent substance was observed. Such a non-woven fabric is useful for wallpaper, lamp shades and the like. Example 4 of textile product having phosphorescent fluorescence As a M _1-x Al ₂ O _4-x phosphorescent phosphor, Ca _0.1 Sr
_0.9 Al ₂ O ₄ : polypropylene containing 30 wt% of Eu and Dy as the first component, and a melt index of 4 (g
/ High density polyethylene 10 minutes) and the second component, conjugated spinning in parallel both components in the composite ratio (volume ratio) of 50/50, fiber diameter 25 [mu] m, fiber length 64 mm, the first component is a fiber cross section circumferential A composite fluorescent fiber having a ratio of 71% was obtained.

A nonwoven fabric having a pattern of emitting fluorescence using this composite fluorescent fiber in the same manner as in Example 3 had a rough texture in the pattern portion, and the falling of the fluorescent agent was recognized by friction, and the maintenance of fluorescence was maintained. The time was just under 400 minutes. As Example _{5 M 1-x Al 2 O} 4-x phosphorescent phosphors textile with phosphorescent, CaAl ₂ O
₄ : Polypropylene containing 30 wt% of Eu and Nd as a core component, polypropylene having a melt flow rate of 10 (g / 10 min) as a sheath component, and a composite ratio (volume ratio) of 50 /
Composite spinning with 50, fiber diameter 52 μm, fiber length 51 mm
The composite fluorescent fiber of was obtained and passed through a card machine to give a sliver of 5 g / m ² .

Single fiber fineness 18 denier, fiber length 51 mm
Blue polypropylene fiber is passed through a card machine and the basis weight is 50.
A web having a weight per unit area of 0 g / m ² and a basis weight of 100 g / m ^{2 was formed.} The sliver made of the composite fluorescent fiber was arranged between the two webs in a standing pattern with an average interval of 50 mm, and needle punched to obtain a nonwoven fabric. . The obtained non-woven fabric has the same strength and texture as the non-woven fabric having a basis weight of 600 g / m ² produced by the needle punching method using only the above polypropylene fibers, and is alive, and the pattern portion shines a pale green color for about 500 minutes in a dark room. Was there. Such non-woven fabrics can be used in carpets. Example 6 of textile product having phosphorescent fluorescence SrAl ₂ O as M _1-x Al ₂ O _4-x phosphorescent phosphor
₄ : Polypropylene containing 20% by weight of Eu and Dy as a core component and a melt flow rate of 14.4 (g / 10
Min) polypropylene as the sheath component and the composite ratio (volume ratio)
Composite fine fiber (long fiber) with a total fineness of 2600d / 100f obtained by composite spinning at 50/50 and sublimation processing, and a total fineness of 2600d / 10 consisting only of green polypropylene
A tufted carpet was prepared by using as a pile yarn together with 0f sublimated long fibers, and by tufting piles of composite fluorescent fibers in a stripe pattern having a width of 15 mm at intervals of 85 mm.

The obtained carpet has the same strength and texture as a tufted carpet made of ordinary polypropylene fiber, and the striped pattern continues to shine yellow green for about 300 minutes in a dark room, and the carpet is used as an evacuation route at the time of power failure. It is useful for disaster prevention such as display.

[0131]

As described above, the phosphorescent phosphor used in the present invention relates to a novel phosphorescent phosphor material which is completely different from conventionally known sulfide phosphors, and is commercially available. In comparison with the sulfide-based phosphor described above, the phosphor has a long-lasting high-luminance afterglow characteristic, and since it is an oxide-based phosphor, it is chemically stable and has excellent light resistance. Therefore, the textile product having a phosphorescent fluorescent substance of the present invention using such a phosphorescent fluorescent substance exhibits a high-luminance fluorescent color for a long time even when it is used outdoors or in a humid place.

[Brief description of drawings]

FIG. 1 is an XR crystal structure of a SrAl ₂ O ₄ : Eu phosphor.
It is a graph which showed the result analyzed by D.

FIG. 2 is a graph showing an excitation spectrum of an SrAl ₂ O ₄ : Eu phosphor and an emission spectrum after 30 minutes have passed since the stimulation was stopped.

FIG. 3 shows the afterglow characteristics of a SrAl ₂ O ₄ : Eu phosphor as Zn.
It is the graph which showed the result of having compared with the afterglow characteristic of S: Cu fluorescent substance.

FIG. 4 is a graph showing thermoluminescence characteristics of SrAl ₂ O ₄ : Eu phosphor.

FIG. 5 is a graph showing the result of comparison of the afterglow characteristics of the SrAl ₂ O ₄ : Eu, Dy phosphor with the afterglow characteristics of the Zn S: Cu phosphor.

FIG. 6 is a graph showing thermoluminescence characteristics of a SrAl ₂ O ₄ : Eu, Dy phosphor.

FIG. 7 is a graph showing thermoluminescence characteristics of SrAl ₂ O ₄ : Eu, Nd phosphor.

FIG. 8 shows a crystal structure of a CaAl ₂ O ₄ : Eu-based phosphor X
It is a graph which showed the result analyzed by RD.

[9] CaAl ₂ O _4: is a graph showing the heat emission characteristics of the phosphor with neodymium or samarium as of which co-activators Eu phosphor.

[10] CaAl ₂ O _4: it is a graph showing the heat emission characteristics of dysprosium or tools potassium and phosphor used as internal co activators Eu phosphor.

FIG. 11 is a graph showing an emission spectrum of a CaAl ₂ O ₄ : Eu-based phosphor after 5 minutes have elapsed since the stimulation was stopped.

FIG. 12: CaAl ₂ O ₄ : Eu, Sm phosphor and Ca
The afterglow characteristics of the Al2 O4: Eu, Nd phosphor are ZnS : C.
It is the graph which showed the result of having compared with the afterglow characteristic of u fluorescent substance.

FIG. 13 is a graph showing an excitation spectrum of a BaAl ₂ O ₄ : Eu, Nd phosphor and an emission spectrum after 30 minutes have passed since the stimulation was stopped.

FIG. 14 is a graph showing an excitation spectrum of a BaAl ₂ O ₄ : Eu, Sm phosphor and an emission spectrum after 30 minutes have passed since the stimulation was stopped.

FIG. 15 is a graph showing an emission spectrum of a Sr _0.5 Ca _0.5 Al ₂ O ₄ : Eu, Dy phosphor.

FIG. 16 shows the afterglow characteristics of Sr _x Ca _1-x Al ₂ O ₄ : Eu, Dy phosphors as Zn S: Cu phosphor and CaSrS: B phosphor.
It is a graph which compared with the afterglow characteristic of i fluorescent substance.

FIG. 17 is a graph comparing afterglow characteristics of Sr _x Ba _1-x Al ₂ O ₄ : Eu, Dy phosphors with afterglow characteristics of ZnS : Cu phosphors.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takatsugu Matsuzawa Maruzan Building, 1-1-15-1 Kamiogi, Suginami-ku, Tokyo Nemoto Special Chemical Co., Ltd. (56) References Japanese Patent Publication No. 370020 (JP, B2) Japanese Patent 58-22496 (JP, B1) JP-B-52-22836 (JP, B1) Frank C. Pallilla, Fluorescent Properties of Alkaline Earth Aluminates of Type MAl2O4 Act by by Divorent Europium, J. Mol. Electric machine. Soc. , June 1968, Vol. 115, No. 6, 642-644 (58) Fields investigated (Int.Cl. ⁷ , DB name) D03D 1/00-27/18 D04B 1/00-1/28 D04B 21/00 -21/20 D01D 5/34 D01F 8/00-8/18 D04H 1/00-18/00 D06Q 1/10

Claims (5)

(57) [Claims] 1. A fiber product having phosphorescent fluorescence formed by mixing a phosphorescent phosphor with a thermoplastic resin, wherein the phosphorescent phosphor has a composition represented by M _1-X Al ₂ O _4-X. Of the above compound, M is a compound composed of at least one metal element selected from the group consisting of calcium, strontium, and barium as a mother crystal, and X is -0.33 ≦.
X is in the range of 0.60 and euro as an activator.
Pium is 0.00 in mol% with respect to the metal element represented by M.
Add 1% or more and 10% or less, and use neodymium as a co-activator.
Mu, Samarium, Dysprosium, Holmium, Erbi
Consists of um, thulium, ytterbium and lutetium
A metal element in which at least one element of the group is represented by M
A fiber product having phosphorescent fluorescence, characterized by using 0.001% or more and 10% or less by mol% of the above . 2. A first component containing a phosphorescent phosphor and a second component containing substantially no phosphorescent phosphor are arranged in parallel so that the first component occupies 60% or less of the fiber cross-sectional circumference. A fiber product having phosphorescent fluorescence, which is composed of a composite fluorescent fiber having a fiber diameter of 150 μm or less and arranged in a sheath-core type, or is a combination of the composite fluorescent fiber and another fiber. a compound having a composition represented by _{1-X Al 2 O 4-} X, M is calcium, strontium, a compound composed of at least one or more metal element selected from the group consisting of barium and mother crystal, the further X -0.3
Within the range of 3 ≦ X ≦ 0.60, and as an activator,
Uropium was added in an amount of 0.
001% or more and 10% or less are added, and a co-activator is added.
Ozimium, samarium, dysprosium, holmium, d
From rubium, thulium, ytterbium, lutetium
A metal in which at least one element of the group consisting of
Addition of 0.001% or more and 10% or less in mol% with respect to the element
Textiles having a phosphorescent, characterized in that with those. 3. The textile product having phosphorescent fluorescence according to claim 2, wherein the composite fluorescent fiber is formed so as to weave a pattern on a knitted fabric made of another fiber. 4. The textile product having phosphorescent fluorescence according to claim 2, wherein the layer made of the composite fluorescent fiber is laminated on the layer made of another fiber. 5. The textile product having phosphorescent fluorescence according to claim 2, wherein the layer made of the composite fluorescent fiber is laminated between the layers made of other fibers.