JP2000198938A - Phosphorescent-material-containing resin bead and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide phosphorescent-material-containing resin beads each of which is composed of a resin bead and a phosphorescent material contained within it and a process for producing them. SOLUTION: The beads are produced by dispersing a monomer capable of oil-in-water polymerization or a prepolymer or a resin solution capable of oil-in-water crosslinking and phosphorescent material particles in water containing a suspension stabilizer under agitation, effecting suspension polymerization of suspension crosslinking by heating to form resin beads, and subjecting the mixture to solid/liquid separation followed by washing and drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphorescent resin-containing resin bead having high luminance and long afterglow, excellent in water resistance and dispersibility, and low in contamination, and a method for producing the same.

[0002]

2. Description of the Related Art As a phosphorescent material, there are known a conventional sulfide-based material and a recently reported oxide-based strontium aluminate. The sulfide includes, for example, a ZnS afterglow phosphor activated with Cu, which lacks water resistance and afterglow, but is inexpensive, so it can be used indoors such as a clock face or an evacuation guidance sign. It is used. On the other hand, oxide-based phosphorescent materials include strontium aluminate activated with divalent Eu. For example, Japanese Patent No. 2543825 discloses SrAl ₂ O ₄ : Eu, Dy, and Japanese Patent No. 2697688. Has SrOa (Al, B) ₂ O
₃ : Eu, Dy (1.5 ≦ a ≦ 3.0) and the like are disclosed.

[0003] These phosphorescent materials are produced by pulverizing and classifying a sintered body obtained by sintering a raw material at a high temperature. Since the particles have a high hardness and an irregular shape, the phosphorescent material is directly added to a paint or a resin material. In this case, the processing equipment is abraded and worn, causing damage to the equipment, and at the same time, foreign substances that have been abraded and worn are mixed into the base material, leading to discoloration and deterioration of the base material itself, and further to a decrease in the luminous performance of the phosphorescent material. . In addition, since the luminous material has an irregular shape and a high specific gravity, when mixed with various materials, the luminous material may be poorly dispersed or agglomerated, which adversely affects the appearance, performance and light emission of the final product.

[0004]

The technical problem to be solved by the present invention is basically to include a luminous material containing the luminous material in a resin bead so as to solve the above-mentioned problems at once. An object of the present invention is to provide a resin bead and a method for producing the same. A more specific technical problem of the present invention is to have high luminance and long afterglow, excellent in water resistance and dispersibility, and further,
An object of the present invention is to provide a phosphorescent material-containing resin bead having less contamination and a method for producing the same.

Another technical problem of the present invention is that the oil-in-water polymerization (hereinafter referred to as "suspension polymerization") or the oil-in-water crosslinking reaction (hereinafter referred to as "suspension cross-linking") can be used to produce the compound by simple means. It is an object of the present invention to provide a phosphorescent material-containing resin bead formed into a substantially spherical shape having a particle diameter of 0.5 μm or more. Another technical problem of the present invention is that when resin beads containing a phosphorescent material are added to a paint or a resin material, the processing equipment is abraded and worn without damaging the equipment. An object of the present invention is to provide a phosphorescent material-containing resin bead capable of preventing discoloration and deterioration caused by the above, and further preventing a decrease in light emitting performance of the phosphorescent material.

Another technical problem of the present invention is that the particle size of the obtained phosphorescent material-containing resin beads can be easily adjusted by adjusting the concentration of the suspending agent and the number of rotations of the stirring, and the size of the resin beads containing the phosphorescent material is changed from large to small. It is an object of the present invention to provide a method for producing a phosphorescent material-containing resin bead that can be produced stably with good reproducibility. Another technical object of the present invention is to provide a method for producing resin beads containing a phosphorescent material, which has a wide variety of resins to be used and can be applied to various uses.

[0007]

According to the present invention, there is provided a light-storing material-containing resin bead for solving the above-mentioned problems, which comprises a highly hard and irregularly shaped light-storing material particle formed by pulverizing and classifying a sintered body. The present invention is characterized in that at least one resin is contained in the substantially spherical resin. In addition, a method for producing a resin bead of the present invention for solving the above-mentioned problem is characterized in that a highly hard and irregularly shaped phosphorescent particles formed by crushing and classifying a sintered body in water containing a suspension stabilizer. And a monomer capable of oil-in-water polymerization, a prepolymer capable of oil-in-water cross-linking reaction, or a resin solution, and stirred to form a suspension. The present invention is characterized in that light-storing material-containing resin beads containing at least one or more light-storing material particles are formed inside a substantially spherical resin. The particle size of the resin beads can be adjusted by the type of suspension stabilizer, its concentration, or the stirring speed for obtaining a suspension.

The luminous material in the luminous material-containing resin beads is a strontium aluminate-based luminous material having Eu ²⁺ as an emission center, and Sr (Al _{1 -Z} Si _{3/4 Z} ) ₂ O ₄ : Eu , Dy, Y (Sr, Bi ) (Al 1-Z Si 3/4 Z) 3 O 5 OH: E
u, Dy, Y (Sr, Bi) 2 (Al 1-Z Si 3/4 Z) 6 O 11: E
_{u, Dy, Y Sr 2 (} Al 1-Z Ge 3/4 Z) 6 O 11: Eu, Dy, Y Sr (Al, B) 2 O 4: Eu, Dy, and Sr ₄ (Al, B) ₁₄ O ₂₅ : It is preferable to use one containing one or more of Eu and Dy. Further, as the resin containing the phosphorescent material, any one of acrylic, styrene, polyurethane, polyester, epoxy, and silicone resins, or a copolymer or a mixture of a plurality of these resins can be used.

According to the phosphorescent material-containing resin beads and the method for producing the same of the present invention, the resin beads have high brightness and long afterglow,
It is excellent in water resistance and dispersibility, and furthermore, the phosphorescent material-containing resin beads with little contamination can be easily produced by a simple means of suspension polymerization or suspension crosslinking, whereby the particle diameter is 0.5 μm. Not only can the above-described phosphorescent material-containing resin beads formed in a substantially spherical shape be obtained, but also the particle size of the resin beads can be easily adjusted, and stable and reproducible from large particles to small particles. Can be manufactured.

[0010] The resin beads containing a luminous material of the present invention are:
By means of suspension polymerization or suspension crosslinking, high-hardness, irregularly shaped phosphorescent particles formed by crushing and classifying the sintered body are encapsulated in a substantially spherical shape by the resin, Due to the resin, the surface of the resin beads has a moderate hardness that does not cause abrasion and wear in various equipment, and when it is added to paints and resin materials,
It is possible to prevent discoloration and deterioration due to the mixing of the foreign material that has been abraded and worn, and also prevent the light emission performance of the phosphorescent material from deteriorating, without causing the processing equipment to be abraded and worn to damage the equipment.

[0011]

Embodiments of the present invention will be described below in detail. In the production of the phosphorescent material-containing resin beads according to the present invention, in water containing a suspension stabilizer, a highly hard and irregularly shaped phosphorescent particles formed by crushing and classifying a sintered body of the phosphorescent material, A monomer capable of suspension polymerization, a prepolymer capable of suspension crosslinking, or a resin solution (hereinafter, referred to as a resin) is added and stirred to form a suspension in which phosphorescent material particles are mixed and dispersed. At this time, the stirring speed is adjusted to obtain a suspension having a desired particle size, and then the reaction is started by heating, and thereafter, resin beads are generated by suspension polymerization or suspension crosslinking, and then this is solid-liquid A method is used in which the beads are separated, washed to remove the suspension stabilizer adhering to the beads, and dried, whereby a substantially spherical particle having an arbitrary particle diameter and containing at least one phosphorescent material therein is used. Resin beads are obtained. The particle size can be set to any size depending on the amount and type of the suspension stabilizer,
After drying, the resin beads are pulverized, classified if necessary, and provided for various uses.

In the production of the resin beads according to the present invention, if 100 parts by weight of the mixture of the resin and the phosphorescent material is used, the suspension stabilizer is used in an amount of 0.01 to 200 parts by weight with respect to 100 to 1000 parts by weight of water. Dissolve or disperse parts by weight,
100 parts by weight of the mixture is charged into the liquid, and the mixture is stirred while adjusting the stirring speed so that the dispersed particles have a predetermined particle size. After adjusting the particle size, the liquid temperature is raised to 30 to 90 ° C. Warm and react for 1-8 hours.

The above-mentioned resin suitable for use in the resin beads containing a luminous material of the present invention includes a polyisocyanate prepolymer, an acrylic monomer, a styrene monomer, a polyester resin, an epoxy resin, or a silicone resin, or a plurality thereof. There are copolymers or mixtures.

The phosphorescent material used in the present invention is a strontium aluminate phosphorescent material activated with divalent europium (a high-brightness and long-lasting phosphorescent phosphor composed of strontium aluminum oxide having Eu ²⁺ as a luminescent center). Material), and in particular, those represented by the following composition formula are more suitable. Sr (Al _{1 -Z} Si _{3/4 Z} ) ₂ O ₄ : Eu, Dy, Y (1) (Sr, Bi) (Al _{1 -Z} Si _{3/4 Z} ) ₃ O ₅ OH: Eu, Dy, Y (2) (Sr, Bi) ₂ (Al _{1 -Z} Si _{3/4 Z} ) ₆ O ₁₁ : Eu, Dy, Y (3) Sr ₂ (Al _{1 -Z} Ge _{3/4 Z} ) ₆ O ₁₁ : Eu , Dy, Y (4) Sr (Al, B) ₂ O ₄ : Eu, Dy (5) Sr ₄ (Al, B) ₁₄ O ₂₅ : Eu, Dy (6)

That is, the phosphorescent material contains a compound containing an Sr element, a compound containing an Al element, a compound containing a Y element, a compound containing a Bi element, a compound containing a Ge element, and a compound containing a B element. The compounds are weighed so as to have a predetermined molar ratio determined by any of the above formulas (1) to (6), mixed well, and then under weak reducing conditions at 1100 ° C to 1600 ° C for 1 to 5 hours. By firing reaction or using autoclave, 18
The phosphorescent materials of the above formulas (1) to (6) obtained by hydrothermal synthesis at 0 ° C. to 500 ° C. for 2 to 6 hours are crushed and classified,
Thereby, a particle size of 0.3 μm to 300 μm is obtained. The content of the luminous material in the present invention varies depending on the resin used, but the luminous material is preferably 0.1 to 400 parts by weight based on 100 parts by weight of the resin. More preferably, it is 50 to 400 parts by weight.

The resin beads containing a luminous material of the present invention are obtained by subjecting a mixture of any of the above-mentioned resins and any of the luminous materials to an organic solvent, if necessary, to suspension polymerization or suspension crosslinking. Can also be obtained. The viscosity of the resin to be charged can be adjusted by the diluted organic solvent. The diluting organic solvent used here may be any as long as it dissolves the resin and does not inhibit the reaction.
Examples thereof include hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as ethylene glycol diethyl ether. However, it is not limited to these. These organic solvents can be used alone or in combination of two or more.

The stability of the suspension system is determined by the type and amount of the suspension stabilizer and the type of the resin used. Generally, as the amount of the suspension stabilizer increases, the stability increases but the particle size tends to decrease. In addition, the viscosity of the suspension increases, and solid-liquid separation and washing become difficult. When the amount of the suspension stabilizer is small and the viscosity of the suspension system is low, the phosphorescent material does not easily enter the resin, but a large particle size can be obtained. Therefore, the concentration of the suspension stabilizer varies depending on the suspension stabilizer used,
0.1 to 20 parts by weight based on 100 parts by weight of water is preferred.

Particularly typical examples of the suspension stabilizer which can be used in the present invention include polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, polyethylene glycol, and polyacrylamide. And water-soluble polymers such as gelatin, polyacrylic acid and polyacrylate, and inorganic suspending agents such as calcium phosphate, titanium oxide, calcium carbonate and silicon dioxide.
However, it is not limited to these. These suspension stabilizers can be used alone or in combination of two or more.

It is also possible to use a suspension aid in combination with the above-mentioned suspension stabilizer. As this suspension aid,
Commonly known cationic, anionic or nonionic surfactants can be used. The amount added depends on the suspension aid used, but is preferably 0.001 to 10 parts by weight per 100 parts by weight of water.

After the completion of the reaction, a cellulose-decomposing enzyme for decomposing the suspension stabilizer is used to lower the viscosity of the suspension to facilitate the solid-liquid separation operation and to facilitate the washing of the resin beads.
The suspension may be treated with an enzyme such as polyvinyl alcohol decomposing enzyme, a reagent such as hypochlorite, or the like.

The particle size of the obtained resin beads can also be changed by adjusting the number of revolutions of stirring before the reaction of suspension polymerization or suspension crosslinking. In general, when the viscosity of the suspension system is the same, resin beads having a large particle diameter can be obtained by lowering the stirring rotation speed, and resin beads having a small particle diameter can be obtained by increasing the stirring rotation speed. However, if the stirring rotation speed is too low, the phosphorescent material may separate from the resin and sink to the bottom of the reaction system. Also, if the stirring rotation speed is too high, there is a possibility that beads containing no phosphorescent material can be increased. Therefore, it is important to select an appropriate stirring rotation speed.

Next, the type of the resin used in the present invention will be described in detail. Acrylic monomers that can be used in the present invention, more specifically, particularly typical examples of radically polymerizable acrylic unsaturated monomers include acrylic acid, derivatives of acrylic acid, such as methyl acrylate, acrylic Ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, acrylic acid Propoxyethyl, butoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, methoxy acrylate Dipropylene glycol, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, acrylonitrile, acrylamide, N-
Methylol acrylamide, or methacrylic acid, derivatives of methacrylic acid, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, Decyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, Methoxydipropylene glycol methacrylate, cyclohexyl methacrylate, methacrylate Le acid tetrahydrofurfuryl, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methacrylonitrile, methacrylamide, N- methylol methacrylamide, and the like. However, it is not limited to these. These acrylic unsaturated monomers include:
Species or a combination of two or more can be used.

Styrene monomers that can be used in the present invention, more specifically, radically polymerizable styrene-based unsaturated monomers, include, for example, styrene, α-methylstyrene, o-methylstyrene. , M-methylstyrene, p-methylstyrene, ethylstyrene, dimethylstyrene, butylstyrene, and other alkylstyrenes, and p-chlorostyrene.
However, it is not limited to these. These styrenic unsaturated monomers can be used alone or in combination of two or more.

In the present invention, a particularly typical example of a polyfunctional unsaturated monomer that can be used as a crosslinking agent with a radically polymerizable acrylic unsaturated monomer or a styrene unsaturated monomer is divinylbenzene. , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, the reaction product of glycol with methacrylic acid or acrylic acid, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,
Examples thereof include 3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol methacrylate, 1,6-hexanediol diacrylate, and neopentyl glycol dimethacrylate. However, it is not limited to these.

These polyfunctional unsaturated monomers (crosslinking agents)
Can be used alone or in combination of two or more. The proportion of the polyfunctional unsaturated monomer (crosslinking agent) used is preferably 0.1 to 40 parts by weight based on 100 parts by weight of the radically polymerizable acrylic unsaturated monomer or styrene unsaturated monomer.

Polymerization of the radically polymerizable acrylic unsaturated monomer or copolymerization of the acrylic unsaturated monomer with a polyfunctional unsaturated monomer (crosslinking agent), and polymerization of the styrene unsaturated monomer or styrene unsaturated For the copolymerization of the monomer and the polyfunctional unsaturated monomer (crosslinking agent), a generally used radical polymerization initiator can be used.

The radical polymerization initiator that can be used in the present invention includes peroxide and azo compound initiators generally used for radical polymerization. More specifically, peroxide initiators include benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxide. Isobutylate, tert-butyl peroxy neodecanoate, isobutyryl peroxide, di-3-
Examples include methoxybutyl peroxydicarbonate, methyl ethyl ketone peroxide, methyl isobutyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, lauroyl peroxide and the like.

As the azo compound initiator, 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2-methylpropionitrile), 2,
2′-azobis (2-methylbutyronitrile), 1,
1′-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-methoxy-2,
4-dimethylvaleronitrile) and the like. However, it is not limited to these.

These radical polymerization initiators may be used alone or in combination.
More than one species can be used in combination. The ratio of the radical polymerization initiator used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the radical polymerizable unsaturated monomer.

The polyisocyanate prepolymer that can be used in the present invention refers to a reactant having a terminal isocyanate group of a diisocyanate and a polyol generally used as a raw material for isocyanurate, buret, and polyurethane resin. The content may be any of polyester type, polyether type, acrylic polyol type, and isocyanate type,
Yellowing type, non-yellowing type, non-yellowing type does not matter.
Furthermore, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, m-phenylene diisocyanate, or p-phenylene diisocyanate,
4,4′-diphenylmethane diisocyanate, 2,
4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-
4,4'-biphenylene diisocyanate, 3,3'-
Dichloro-4,4'-biphenylenediisocyanate,
Or, including various aromatic diisocyanates such as 1,5-naphthalenediisocyanate,
1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, or isophorone diisocyanate 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, trimethyl hexamethylene diisocyanate, hydrogenated xylylene diisocyanate,
Various aliphatic diisocyanates or alicyclic diisocyanates such as 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate or dimer acid diisocyanate may be used. When a bifunctional terminal isocyanate urethane prepolymer is used, thermoplastic urethane beads are obtained, and when a difunctional or higher terminal isocyanate urethane prepolymer is used, three-dimensionally crosslinked urethane beads are obtained. These isocyanates can be used alone or in combination of two or more.

In the present invention, the isocyanate and the polyol can be combined and reacted. Particularly typical examples of polyols that can be used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, and neopentyl glycol. Such as 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-dimethanol, 1,4-bis (hydroxyethyl) cyclohexane, and hydrogenated bisphenol A Various diol compounds, or polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene tetramethylene glycol, or polyoxyethylene / polyoxypropylene / polyol. Sheet such as tetramethylene glycol, may be mentioned various polyether glycols.

The opening of various polyhydric alcohols as described above with ethylene oxide, propylene oxide, tetrahydrofuran ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether. So-called modified ether polyols in the form obtained by a ring polymerization reaction, or at least one of various polyhydric alcohols as described above, and ε-caprolactone, γ-valerolactone, or 3-methyl-γ- So-called lactone-modified polyester polyols obtained by a polycondensation reaction with various lactones such as valerolactone. 3 hydroxyl groups
Particularly typical examples of the polyol having functionalities or more include glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, and trishydroxyethyl isocyanurate. However, it is not limited to these.

These polyols can be used alone or in combination of two or more. In addition, the proportion of the polyols used is 100% of the polyisocyanate prepolymer.
It is preferably 0.1 to 50 parts by weight based on parts by weight.

Particularly representative catalysts used for the reaction between isocyanate and hydroxyl group which can be used in the present invention are, for example, dibutyltin dilaurate, dibutyltin di (2-ethylhexoate), tetra-n- Butyltin, stannous chloride, stannic chloride, iron chloride, lead 2-ethylhexoate, zinc octenoate, 2-ethylhexyl titanate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, etc. Is mentioned. However, it is not limited to these.

The polyester resin usable in the present invention includes:
It refers to a general saturated polyester resin or unsaturated polyester resin, regardless of the type. The polyester resin used in the present invention is preferably soluble in an organic solvent, more preferably a cross-linkable resin, and further preferably has transparency. It is also preferable to crosslink in combination with a general curing agent. The general curing agent is an isocyanate-based curing agent or a melamine-based curing agent, but is not limited thereto. As a catalyst for the reaction between the polyester resin and the curing agent,
The catalyst used for the reaction between the isocyanate and the hydroxyl group described above may be used. These polyester resins are
One type or a combination of two or more types can be used.

The epoxy resin that can be used in the present invention refers to a general epoxy resin, and specifically, a glycidyl ether of a phenol such as bisphenol A, bisphenol F or phenol novolak, or a glycidyl ether of an alcohol that is hardly soluble in water. And homopolymers and copolymers polymerized from glycidyl ethers such as phthalic acid and the like, or a mixture thereof, but are not limited thereto. Preferably, a crosslinked epoxy resin is used in combination with these resins and a general curing agent. Common curing agents include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, aromatic polyamines such as diaminodiphenylmethane, polyamideamines,
Acid anhydrides and the like, but are not limited thereto. As the catalyst for the reaction between the epoxy resin and the curing agent, the above-mentioned catalyst used for the reaction between the isocyanate and the hydroxyl group may be used.

The silicone resin that can be used in the present invention includes a silicone resin obtained by hydrolysis and condensation of chlorosilanes, a resin generally called liquid silicone rubber, a raw rubber (or millable silicone rubber), or It is a silicone polymer cross-linked with a modified product thereof and a curing agent.

[0038]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited by these.

Example 1 A 2.0% aqueous solution of Poval 220 manufactured by Kuraray Co., Ltd. was used as a suspension stabilizer solution.
As the resin particle composition, methyl methacrylate / ethylene glycol dimethacrylate / phosphorescent material / ABN-V = 60
/ 30/30/2 parts by weight of a monomer mixture. The phosphorescent material used here was Sr _0.982 Eu _0.005 D
y _0.008 Y _0.005 Al _1.98 Si _0.015 O ₄ . ABN-V is an azo compound initiator manufactured by Nippon Hydrazine Co., Ltd.

Hereinafter, a synthesis method using the above monomer mixture will be described. 600 g of the above suspension stabilizer solution was charged into a glass 2L four-necked round-bottomed flask equipped with a stirrer, and at 30 ° C,
While stirring at 250 rpm with a stainless steel stirring blade, 300 g of the above monomer mixture was charged to form a suspension. After stirring the mixture at 30 ° C. for 10 minutes, the temperature inside the reaction system was raised to 60 ° C. with continuous stirring, and the reaction was kept constant for 2 hours. Thereafter, 5 g of sodium hypochlorite was added, and the mixture was stirred for 0.5 hour to decompose Povar 220 to lower the viscosity, and then cooled to room temperature (about 25 ° C.). Then
The reaction product was subjected to solid-liquid separation, washed sufficiently with water, and then dried at 70 ° C. for 12 hours using a drier to obtain an average particle size of 100 μm.
Of acrylic resin beads containing a phosphorescent material.

The resulting beads were evaluated for emission luminance and afterglow. In this evaluation, 2 g of beads were uniformly mixed with 3 g of polyester resin, and the mixture was molded into a luminous resin sheet and cured, and after 24 hours of light blocking, in a dark room, at a distance of 100 mm using a 15 W tabletop white fluorescent lamp. After irradiating the sample for 30 minutes, the change with time of the emission luminance was measured. For comparison, the phosphorescent material before beading was mixed with the polyester resin in a weight ratio of polyester resin: phosphorescent material = 3: 0.41 so that the content of the phosphorescent material in the sheet was attained. , Molded into a phosphorescent resin sheet,
The change with time of the light emission luminance was measured under the above measurement conditions.

Further, in order to investigate the effect of metal wear and tear, the resin beads obtained as described above were used.
After milling for 30 minutes with a stainless steel ball mill,
A luminous resin sheet was prepared in the same manner as described above, and the time-dependent change in light emission luminance was measured in the same manner. As a comparative test of the effect of abrasion and abrasion of metal, a phosphorescent material without resin beads was also milled with a stainless steel ball mill for 30 minutes, and the time-dependent change in the luminescence intensity was measured in the same manner.

[0043]

[Table 1]

[0044]

[Table 2]

In Table 1, the luminous intensity of the luminous material is set to 100,
The relative light emission luminance of the beads obtained in this example is shown. From Table 1, it was found that the resin beads had an emission luminance about 1.2 times higher than that of the luminous material as the starting material. Table 2
Shows the change in emission intensity due to abrasion and wear of the metal when mixed with a stainless steel ball mill. These are the relative luminous intensity values of the phosphorescent material and the resin beads before and after the stainless steel ball mill for 30 minutes, with the light emission luminance before the stainless steel ball mill being 100%. From Table 2,
It can be seen that, by converting the phosphorescent material into resin beads, a decrease in luminance due to abrasion and abrasion of metal during mixing is extremely small.

Example 2 As a suspension stabilizer solution, BA
Using a 2.5% aqueous solution of PVP K-90 manufactured by SF Company,
As the resin particle composition, a monomer mixture composed of styrene / divinylbenzene / phosphorescent material / Niper BW = 65/5/30/3 parts by weight was used. The phosphorescent material used here is
Sr _0.99 Eu _0.005 Dy _0.005 Al _1.9 B _0.1 O ₄ . The niper BW is a peroxide-based polymerization initiator manufactured by NOF Corporation.

Hereinafter, a synthesis method using the above monomer mixture will be described. 600 g of the above suspension stabilizer solution was charged into a glass 2L four-necked round-bottomed flask equipped with a stirrer, and at 30 ° C,
While stirring at 200 rpm with a stirring blade made of stainless steel, 300 g of the above monomer mixture was charged to prepare a suspension. After stirring at 30 ° C. for 10 minutes, the inside of the reaction system was heated to 75 ° C. under continuous stirring, and kept constant for 2 hours to react, and then cooled to room temperature (about 25 ° C.). Next, the reaction product was subjected to solid-liquid separation, washed sufficiently with water, and then dried at 70 ° C. for 12 hours using a drier to obtain an average particle size of 80 μm.
m of polystyrene beads containing a phosphorescent material were obtained.

The light emission luminance and the afterglow of the obtained beads were evaluated in the same manner as in Example 1. Table 3 shows the relative luminous intensity of the beads obtained in this example, and Table 4 shows the relative luminous intensity of the beads obtained in this example as 100. Shows the change in intensity.

[0049]

[Table 3]

[0050]

[Table 4]

Example 3 A 1.0% aqueous solution of Marpolose 90MP-4000 manufactured by Matsumoto Yushi Seiyaku Co., Ltd. was used as a suspension stabilizer solution, and the resin particle composition was toluene / Desmodur N3400 / Placcel 312 / luminous. A prepolymer mixture consisting of material / BT-11 = 20/40/10/50 / parts by weight was used. Here, Desmodur N3400 is an isocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd., and Praxel 312 is a polyol manufactured by Daicel Chemical Co., Ltd., and the phosphorescent material is (Sr
_0.982 Eu _0.005 Dy _0.008 Y _0.005 ) ₂ (Al _0.97 S
i _0.0225 ) ₆ O ₁₁ was used. BT-11 is a catalyst, which is dibutyltin dilaurate manufactured by ADEKA CORPORATION.

Hereinafter, a synthesis method using the above prepolymer mixture will be described. 600 g of the above suspension stabilizer solution was charged into a glass 2L four-necked round bottom flask equipped with a stirrer,
Then, 350 g of the above prepolymer mixture was charged while stirring at 250 rpm with a stainless steel stirring blade to form a suspension. After stirring the mixture at 30 ° C. for 60 minutes, the temperature inside the reaction system was raised to 60 ° C. with continuous stirring, and kept constant for 2 hours. Further, the temperature of the reaction solution was raised to 100 ° C., and toluene was removed by azeotropic distillation, and then cooled to room temperature (about 25 ° C.). Next, the reaction product was subjected to solid-liquid separation, washed sufficiently with water, and dried at 70 ° C. for 12 hours using a drier to obtain polyurethane beads containing a luminous material having an average particle diameter of 60 μm.

With respect to the obtained beads, emission luminance and afterglow were evaluated in the same manner as in Example 1. Table 5 shows the relative luminous intensity of the beads obtained in this example, and Table 6 shows the relative luminous intensity of the beads obtained in this example as 100. Shows the change in intensity.

[0054]

[Table 5]

[0055]

[Table 6]

Example 4 As a suspension stabilizer solution, Shin-Etsu
3.0% of Metrose 90SH-100 manufactured by Chemical Co., Ltd.
Using an aqueous solution, as the resin particle composition, toluene / MEK
/ Byron-200 / Coronate HX / Luminescent material / BT-
11 = 48/12/40/10/20 / 0.0005 weight
A prepolymer mixture consisting of parts by weight was used. Where
IRON-200 is a polyester manufactured by Toyobo Co., Ltd.
Coronate HX is manufactured by Nippon Polyurethane Co., Ltd.
Aneto, the phosphorescent material used was Sr _0.982 Eu_0.005 D
y_0.008 Y_0.005 Al_Three O_Five (OH). Also, M
EK is methyl ethyl ketone. Also, BT-
Reference numeral 11 denotes a catalyst, dibutyltin dilauray manufactured by Adeka Corporation.
It is.

Hereinafter, a synthesis method using the above prepolymer mixture will be described. 600 g of the above suspension stabilizer solution was charged into a glass 2L four-necked round bottom flask equipped with a stirrer,
While stirring at 250 rpm with a stainless steel stirring blade, 400 g of the above resin mixture was charged to form a suspension. After stirring at 30 ° C. for 60 minutes, the temperature inside the reaction system was raised to 60 ° C. with continuous stirring and kept constant for 2 hours. Furthermore, the temperature of the reaction solution was raised to 100 ° C., and after removing toluene and MEK by azeotropic distillation, the reaction solution was cooled to room temperature (about 25 ° C.).

Next, the reaction product was subjected to solid-liquid separation, washed thoroughly with water, and dried at 70 ° C. for 12 hours using a drier.
Luminescent material-containing polyester resin beads having an average particle diameter of 80 μm were obtained.

[0059]

[Table 7]

[0060]

[Table 8]

With respect to the obtained beads, the luminous luminance and the afterglow were evaluated in the same manner as in Example 1. Table 7 shows the relative luminescence intensity of the beads obtained in this example, and Table 8 shows the relative luminescence intensity of the beads obtained in this example as 100. Shows the change in intensity.

Example 5 As a suspension stabilizer solution, 3.0% of Metrolose 90SH-100 manufactured by Shin-Etsu Chemical Co., Ltd. was used.
Using an aqueous solution, as a resin particle composition, bisphenol A
A mixture consisting of mold liquid epoxy / aliphatic polyamine curing agent / phosphorescent material / toluene / MIBK = 50/16/40/10/10 parts by weight was used. The phosphorescent material used here is
(Sr _0.982 Eu _0.005 Dy _0.008 Y _0.005 ) ₂ (Al
_0.97 Ge _0.0225 ) ₆ O ₁₁ . The bisphenol A type liquid epoxy and the aliphatic polyamine curing agent are Sumi-Epoxy ELA115 and Sumicure-AF manufactured by Sumitomo Chemical Co., Ltd., and MIBK is methyl isobutyl ketone.

Hereinafter, a synthesis method using the above resin mixture will be described. 600 g of the above suspension stabilizer solution was charged into a glass 2-L four-necked round-bottomed flask equipped with a stirrer, and 300 g of the above resin mixture was charged at 30 ° C. while stirring at 250 rpm with a stainless steel stirring blade. A suspension was made.
After stirring at 30 ° C. for 10 minutes, the temperature of the reaction system was raised to 60 ° C. with continuous stirring, and the reaction was kept constant for 6 hours. Furthermore, the temperature of the reaction solution was raised to 100 ° C., and after removing toluene and MIBK by azeotropic distillation, the reaction solution was cooled to room temperature (about 25 ° C.). Next, the reaction product was subjected to solid-liquid separation, washed sufficiently with water, and then dried at 70 ° C. for 12 hours using a dryer.
Luminescent material-containing epoxy resin beads having an average particle diameter of 120 μm were obtained.

With respect to the obtained beads, the luminance and the afterglow were evaluated in the same manner as in Example 1. Table 9 shows the relative luminescence intensity of the beads obtained in this example, and Table 10 shows the relative luminescence intensity of the beads obtained in this example as 100,
5 shows a change in light emission intensity due to abrasion and abrasion of metal after 30 minutes in a stainless steel mill.

[0065]

[Table 9]

[0066]

[Table 10]

Example 6 As a suspension stabilizer solution, a 2.0% aqueous solution of Poval 220 manufactured by Kuraray Co., Ltd. was used.
As the resin particle composition, liquid silicone rubber / silicone rubber curing agent / phosphorescent material / toluene = 60/6/30/20
A resin mixture consisting of parts by weight was used. The phosphorescent material used here is (Sr _0.9 Eu _0.005 Dy _0.005 ) ₄ (Al
_0.8 B _0.2 ) ₁₄ O ₂₅ . The liquid silicone rubber is TSE3032A manufactured by Toshiba Silicone Co., Ltd. The silicone rubber curing agent is TSE3032 manufactured by Toshiba Silicone Co., Ltd.
32B.

Hereinafter, a synthesis method using the above resin mixture will be described. 600 g of the above suspension stabilizer solution was charged into a glass 2-L four-necked round-bottomed flask equipped with a stirrer, and 300 g of the above resin mixture was charged at 30 ° C. while stirring at 250 rpm with a stainless steel stirring blade. A suspension was made.
After stirring at 30 ° C. for 10 minutes, the temperature of the inside of the reaction system was raised to 60 ° C. with continuous stirring, and the reaction was maintained at a constant temperature for 5 hours. Then, 5 g of sodium hypochlorite was added,
After stirring for 5 hours, Povar 220 was decomposed to lower the viscosity, and then cooled to room temperature (about 25 ° C.).

Next, the reaction product was subjected to solid-liquid separation, washed thoroughly with water, and dried at 70 ° C. for 12 hours using a drier.
Luminescent material-containing silicone rubber beads having an average particle diameter of 150 μm were obtained.

[0070]

[Table 11]

With respect to the obtained beads, the luminance and the afterglow were evaluated in the same manner as in Example 1. Table 11 shows the relative luminous intensity of the beads obtained in this example.
In addition, the relative luminescence intensity of the beads obtained in this example was 100
And the change in luminescence intensity due to abrasion and wear of the metal after 30 minutes of the stainless steel mill.

[0072]

[Table 12]

As is clear from the above examples, when the resin beads containing the luminous material are added to the paint or the resin material, the processing equipment is not damaged by abrasion and wear of the processing equipment.
At the same time, discoloration, deterioration,
Further, it is possible to prevent the light emission performance of the light storage material from being lowered.

[0074]

As described above in detail, according to the present invention, a resin bead having a particle diameter of 0.5 μm or more, and a substantially spherical light-storing material containing at least one light-storing material particle therein. Beads can be produced by a simple means of oil-in-water polymerization (suspension polymerization) or oil-in-water crosslinking reaction (suspension crosslinking).

Further, according to the method for producing the phosphorescent material-containing resin beads of the present invention, the particle size of the resulting phosphorescent material-containing resin beads can be easily adjusted by adjusting the concentration of the suspending agent, the number of rotations, and the like. Large to small particles can be produced stably with good reproducibility. In addition, the types of resins used are abundant, and can be applied to various uses.

Further, when the resin beads containing a luminous material of the present invention are added to a paint or a resin material, the processing equipment is worn and worn without damaging the equipment. It is possible to prevent discoloration and deterioration due to mixing, and furthermore, a decrease in the light emission performance of the phosphorescent material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 11/64 CPJ C09K 11/64 CPJ CQE CQE 11/66 CQE 11/66 CQE (72) Inventor Sumida Yukio Nakahara 55-520 Yoshida, Watari-cho, Watari-gun, Miyagi-ken YA39 YA63 YA66 4J002 BC021 BG001 CD001 CF001 CK001 CP031 DE096 FA081 FD206 4J011 JA02 JA04 JA06 JA07 JA08 JA13 JB26 PA02 PB06 PB40 4J037 AA08 CC13 CC16 CC23 CC26 CC28 DD05 DD19 DD24 EE08 EE12 EE25 EE15 EE25 EE25 EE26 EE25

Claims (7)

[Claims] 1. A phosphorescent material characterized in that at least one or more highly rigid and irregularly shaped phosphorescent particles formed by crushing and classifying a sintered body are contained in a substantially spherical resin. Material-containing resin beads. 2. A strontium aluminate phosphorescent material having Eu ²⁺ as an emission center, wherein the phosphorescent material according to claim 1 is Sr (Al _{1 -Z} Si _{3/4 Z} ) ₂ O ₄ : Eu, Dy. , Y (Sr, Bi) ( Al 1-Z Si 3/4 Z) 3 O 5 OH: E
u, Dy, Y (Sr, Bi) 2 (Al 1-Z Si 3/4 Z) 6 O 11: E
_{u, Dy, Y Sr 2 (} Al 1-Z Ge 3/4 Z) 6 O 11: Eu, Dy, Y Sr (Al, B) 2 O 4: Eu, Dy, and Sr ₄ (Al, B) ₁₄ O ₂₅ : a phosphorescent material-containing resin bead comprising one or more of Eu and Dy. 3. The resin containing the luminous material according to claim 1 or 2 is selected from the group consisting of acrylic, styrene, polyurethane, polyester, epoxy, and silicone resins, and a plurality of copolymers or a combination thereof. A phosphorescent material-containing resin bead, which is a mixture. 4. A sinter is pulverized in water containing a suspension stabilizer.
Highly hard, irregularly shaped phosphorescent particles formed by classification, and a monomer capable of oil-in-water polymerization, a prepolymer capable of oil-in-water crosslinking reaction, or a resin liquid,
Agitating to form a suspension, and by generating oil-in-water droplet polymerization or oil-in-water cross-linking reaction, resin beads containing at least one phosphorescent material containing at least one phosphorescent particle are generated inside a substantially spherical resin. A method for producing a phosphorescent material-containing resin bead. 5. A strontium aluminate phosphorescent material having Eu ²⁺ as a luminescent center, wherein the phosphorescent material is Sr (Al _{1 -Z} Si _{3/4 Z} ) ₂ O ₄ : Eu, Dy, Y (Sr _{, Bi) (Al 1-Z} Si 3/4 Z) 3 O 5 OH: E
u, Dy, Y (Sr, Bi) 2 (Al 1-Z Si 3/4 Z) 6 O 11: E
_{u, Dy, Y Sr 2 (} Al 1-Z Ge 3/4 Z) 6 O 11: Eu, Dy, Y Sr (Al, B) 2 O 4: Eu, Dy, and Sr ₄ (Al, B) ₁₄ 5. The method for producing resin beads containing a luminous material according to claim 4, wherein one or more of O ₂₅ : Eu, Dy are contained. 6. A resin containing a phosphorescent material is an acrylic monomer, a styrene monomer, a polyisocyanate prepolymer, a polyester resin, an epoxy resin, and a silicone resin, or a copolymer or a mixture of a plurality of them. The method for producing resin beads containing a luminous material according to claim 4 or 5, wherein 7. The method according to claim 4, wherein the particle size of the resin beads is adjusted by the kind of the suspension stabilizer, its concentration, or the stirring speed for obtaining the suspension. A method for producing the phosphorescent material-containing resin beads according to the above.