JP3947619B2 - Method for producing phosphorescent molded body - Google Patents
Method for producing phosphorescent molded body Download PDFInfo
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- JP3947619B2 JP3947619B2 JP16683998A JP16683998A JP3947619B2 JP 3947619 B2 JP3947619 B2 JP 3947619B2 JP 16683998 A JP16683998 A JP 16683998A JP 16683998 A JP16683998 A JP 16683998A JP 3947619 B2 JP3947619 B2 JP 3947619B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、蓄光性成形体及びその製造方法に関し、さらに詳しくは、不純物の混入、特に成形時における不純物の混入による蓄光性の低下が抑制された蓄光性成形体、及びこのものを効率よく製造する方法に関するものである。
【０００２】
【従来の技術】
蓄光顔料は、光を受け発光し、光を取り除いた後も発光するといった残光性を有する蛍光体である。近年、このような蓄光顔料の特性を利用して、蓄光インキが開発され、夜光時計を始め、携帯電話、携帯ラジオ、携帯電灯、リモコン、照明器具などに使われるようになってきた。また、最近では、蓄光顔料を含有する樹脂成形体が開発され、用途開発が進められている。
この蓄光顔料としては、従来硫化物系顔料、例えば硫化亜鉛・銅蛍光体（ＺｎＳ：Ｃｕ）などが用いられてきた。しかしながら、この硫化物系蓄光顔料は残光強度が低く、かつ残光時間も短いなどの欠点を有しており、したがって、例えば残光性を高めるために、放射性同位元素を添加することが試みられたが、この場合、人体や環境に対する影響が問題となっていた。
近年、新規な蓄光顔料として、アルミン酸塩系蓄光顔料が開発され、注目されている。このアルミン酸塩系蓄光顔料は、従来の硫化物系蓄光顔料に比べて、残光強度が高く、かつ残光時間が長いなど、優れた残光特性を有する上、耐候性にも優れることから、塗料、インキ、成形体など、種々の用途が検討されている。
一般に顔料を樹脂に練り込み、成形体を製造する場合、予め樹脂と顔料を混合したのち、押出機で混練して成形する方法が用いられている。しかしながら、上記アルミン酸塩系蓄光顔料は、従来の蓄光顔料に比べて硬度が高いため、混練中に押出機内のシリンダーやスクリューなどが摩耗しやすく、その結果、得られた成形体には、摩耗により生じた鉄や鉄化合物が混入し、色がくすみ、かつ蓄光性が低下するのを免れないという問題が生じる。
【０００３】
【発明が解決しようとする課題】
本発明は、このような事情のもとで、不純物の混入、特に成形時における不純物の混入による蓄光性の低下が抑制された蓄光性成形体、及びこのものを効率よく製造する方法を提供することを目的としてなされたものである。
【０００４】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、熱可塑性樹脂とアルミン酸塩系蓄光顔料とを含有し、かつ鉄及び／又は鉄化合物の含有量が特定の値以下の成形体が、蓄光性の低下が抑制され、その目的に適合しうること、そして、このものは、予め溶融した熱可塑性樹脂にアルミン酸塩系蓄光顔料を分散させ、成形することにより、効率よく製造しうることを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
（１）熱可塑性樹脂４０〜９９重量部とアルミン酸塩系蓄光顔料６０〜１重量部とを含有する蓄光性成形体の製造方法であって、押出機において、熱可塑性樹脂を溶融させたのち、これにアルミン酸塩系蓄光顔料をサイドフィード方式で添加して、アルミン酸塩系蓄光顔料を均質に分散させ、アルミン酸塩系蓄光顔料の０ . １０重量％以下の鉄を含有するペレットを形成して、該ペレットを用いて成形し、アルミン酸塩系蓄光顔料に対して０ . １０重量％以下の鉄を含有する成形体を形成することを特徴とする蓄光性成形体の製造方法、
を提供するものである。
【０００５】
【発明の実施の形態】
本発明の蓄光性成形体は、熱可塑性樹脂及びアルミン酸塩系蓄光顔料を含有するものであって、上記熱可塑性樹脂については特に制限はなく、従来公知のものの中から、該成形体の用途などに応じて適宜選択することができる。この熱可塑性樹脂の例としては、エチレンビニルアルコール共重合体、ポリエチレン、ポリプロピレン、ポリスチレン、ＡＢＳ樹脂、アクリル樹脂、ポリカーボネート、ポリアセタール樹脂、ポリブチレンテレフタレート、ポリアミド、ポリウレタンなど、又はこれらのポリマーアロイ、あるいはポリウレタン系やポリエチレン系などの熱可塑性エラストマーが挙げられる。
一方、蓄光顔料としては、アルミン酸塩系蓄光顔料が使用される。このアルミン酸塩系蓄光顔料の代表的なものとしては、一般式［１］
ＭＡｌ2Ｏ4 …［１］
で表される化合物を挙げることができる。一般式［１］において、Ｍはカルシウム、ストロンチウム、バリウムなどの金属である。
上記化合物には、必要に応じ、賦活剤としてユーロピウム（Ｅｕ）、ランタン（Ｌａ）、セリウム（Ｃｅ）、プラセオジウム（Ｐｒ）、ジスプロシウム（Ｄｙ）、ネオジム（Ｎｄ）などのランタン系金属元素を添加してもよい。このようなアルミン酸塩系蓄光顔料の例としては、ＣａＡｌ2Ｏ4：Ｅｕ2+、Ｎｄ3+（発光色：紫青、発光ピーク波長：４４０ｎｍ）、ＳｒＡｌ2Ｏ4：Ｅｕ2+、Ｄｙ3+（発光色：黄緑、発光ピーク波長：５２０ｎｍ）、ＳｒＡｌ2Ｏ4：Ｅｕ2+（発光色：黄緑、発光ピーク波長：５２０ｎｍ）などが挙げられる。この他、Ｓｒ4Ａｌ14Ｏ25：Ｅｕ2+、Ｄｙ3+（発光色：青緑、発光ピーク波長：４９０ｎｍ）なども用いることができる。
このようなアルミン酸塩系蓄光顔料は、従来の硫化物系蓄光顔料、例えばＣａＳｒＳ：Ｂｉ、ＺｎＳ：Ｃｕ、ＺｎＳ：Ｃｕ、Ｃｏなどに比べて残光輝度が高く、かつ残光時間が長いなど、優れた残光特性を有している。
本発明においては、前記アルミン酸塩系蓄光顔料は１種用いてもよいし、２種以上を組み合わせて用いてもよい。また、本発明の蓄光性成形体における前記熱可塑性樹脂とアルミン酸塩系蓄光顔料の含有割合は、重量比で９９：１ないし４０：６０の範囲にあるのが好ましい。アルミン酸塩系蓄光顔料の含有割合が上記範囲より少ないと残光強度が小さく、蓄光性成形体としての機能が十分に発揮されないし、上記範囲より多いと成形時における摩耗が激しく、くすみが大きくなると共に、蓄光性が低下するおそれがある。残光強度及び摩耗などを考慮すると、熱可塑性樹脂とアルミン酸塩系蓄光顔料のより好ましい含有割合は、重量比で９５：５ないし５０：５０の範囲である。
【０００６】
本発明の蓄光性成形体においては、鉄及び／又は鉄化合物の含有量が、鉄として、アルミン酸塩系蓄光顔料に対し、０.１０重量％以下であることが必要である。この含有量が０.１０重量％を超えると成形体の残光強度が低下し、かつくすみが生じる。残光強度の低下及びくすみの発生を効果的に抑制するには、この鉄及び／又は鉄化合物の含有量は、鉄として、アルミン酸塩系蓄光顔料に対し、０.０８重量％以下が好ましく、特に０.０６重量％以下が好適である。
本発明の蓄光性成形体には、本発明の効果が損なわれない範囲で、所望により各種添加剤、例えば他の顔料、酸化防止剤、熱安定剤、紫外線吸収剤、光安定剤、難燃剤、滑剤、フィラー、帯電防止剤などを適宜添加することができる。
このような本発明の蓄光性成形体は、以下に示す本発明方法によれば、効率よく製造することができる。
本発明方法においては、予め熱可塑性樹脂を溶融させ、この溶融状態の粘度が低い熱可塑性樹脂に、所定量のアルミン酸塩系蓄光顔料を加え、均質に分散させたのち、成形する。この方法により、鉄及び／又は鉄化合物の含有量が、鉄として、アルミン酸塩系蓄光顔料に対し、０.１０重量％以下、好ましくは０.０８重量％以下、より好ましくは０.０６重量％以下の蓄光性成形体を効率よく製造することができる。通常使用されている方法、すなわち、予め熱可塑性樹脂とアルミン酸塩系蓄光顔料とを混合したのち、押出機で混練して成形する方法では、混練中に押出機内のシリンダーやスクリューなどがアルミン酸塩系蓄光顔料により摩耗し、この摩耗により生じた鉄や鉄化合物が混入するため、所望の蓄光性成形体が得られない。
本発明方法を具体的に示すと、押出機において、まず熱可塑性樹脂を溶融させたのち、これに、アルミン酸塩系蓄光顔料をサイドフィード方式で添加し、均質に分散させ、次いで成形すればよい。成形方法としては特に制限はなく、従来熱可塑性樹脂の成形において慣用されている方法、例えば押出成形、射出成形、ブロー成形などの方法の中から、適宜選択して用いることができる。
【０００７】
【実施例】
次に、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
実施例１
低密度ポリエチレンを、１５０〜２３０℃に加熱した押出機に仕込み、溶融させたのち、これに、アルミン酸塩系蓄光顔料［根本特殊化学社製、商品名：Ｇ−３００Ｍ］を、顔料／樹脂重量比が１０／９０になるようにサイドフィード方式で添加し、混練して押出されたストランドを冷却後、ペレットにした。このペレットに含まれる鉄分は、蓄光顔料の０.０２０重量％であった。
得られたペレットを板状に成形し、諸特性を評価した。結果を第１表に示す。
実施例２〜６
第１表に示す種類の熱可塑性樹脂を用い、かつ蓄光顔料／樹脂重量比が第１表に示す値になるような条件で、実施例１と同様にしてペレットを作製し、板状に成形した。結果を第１表に示す。
比較例１
低密度ポリエチレンと蓄光顔料［根本特殊化学社製、商品名：Ｇ−３００Ｍ］を、顔料／樹脂重量比が２０／８０になるように混合したのち、１７０〜２３０℃に加熱した押出機に仕込み、溶融混練して押出されたストランドを冷却後、ペレットにした。このペレットに含まれる鉄分は、蓄光顔料の０.１３０重量％であった。
得られたペレットを板状に成形し、諸特性を評価した。結果を第１表に示す。
【０００８】
【表１】
［注］
１）ＬＤＰＥ：低密度ポリエチレン
ＰＰ ：ポリプロピレン
ＨＩＰＳ：高耐衝撃性ポリスチレン
ＡＢＳ ：アクリロニトリル・ブタジエン・スチレン樹脂
ＰＭＭＡ：ポリメチルメタクリレート
２）成形品に含まれる鉄及び鉄化合物を鉄に換算した対蓄光顔料含有量。
３）成形品に４００ルックスの蛍光灯を３０分間照射し、常温の暗室中で６０分間放置後の輝度。ミノルタ製ＬＳ−１００輝度計で測定。
【００１０】
【発明の効果】
本発明によれば、不純物の混入、特に成形時における不純物の混入による蓄光性の低下が抑制され、残光強度が高く、かつ残光時間が長い上、色のくすみのない蓄光性成形体を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a phosphorescent molded body and a method for producing the same, and more specifically, a phosphorescent molded body in which deterioration of phosphorescence due to contamination of impurities, in particular, mixing of impurities during molding is suppressed, and this product is efficiently produced. It is about how to do.
[0002]
[Prior art]
A phosphorescent pigment is a phosphor having an afterglow property that emits light after receiving light and emits light even after the light is removed. In recent years, phosphorescent inks have been developed by utilizing such characteristics of phosphorescent pigments, and have been used for night clocks, mobile phones, portable radios, portable electric lights, remote controllers, lighting fixtures, and the like. Recently, resin molded products containing phosphorescent pigments have been developed, and application development has been promoted.
Conventionally, sulfide pigments such as zinc sulfide / copper phosphor (ZnS: Cu) have been used as the phosphorescent pigment. However, this sulfide-based phosphorescent pigment has drawbacks such as low afterglow intensity and short afterglow time. Therefore, for example, in order to enhance afterglow, it is attempted to add a radioisotope. However, in this case, the influence on the human body and the environment has been a problem.
In recent years, aluminate-based phosphorescent pigments have been developed and attracted attention as new phosphorescent pigments. This aluminate-based phosphorescent pigment has excellent afterglow characteristics such as higher afterglow intensity and longer afterglow time than conventional sulfide-based phosphorescent pigments, and also has excellent weather resistance. Various uses such as paints, inks and molded articles have been studied.
In general, when a molded body is produced by kneading a pigment into a resin, a method is used in which the resin and the pigment are mixed in advance and then kneaded and molded by an extruder. However, since the aluminate-based phosphorescent pigment has higher hardness than conventional phosphorescent pigments, the cylinders and screws in the extruder are easily worn during kneading. The problem arises that iron and iron compounds produced by the above are mixed, the color is dull, and the phosphorescence is unavoidable.
[0003]
[Problems to be solved by the invention]
Under such circumstances, the present invention provides a phosphorescent molded body in which deterioration of phosphorescence due to mixing of impurities, particularly mixing of impurities during molding, is suppressed, and a method for efficiently manufacturing the same. It was made for the purpose.
[0004]
[Means for Solving the Problems]
As a result of intensive studies in order to achieve the above object, the inventors of the present invention contain a thermoplastic resin and an aluminate phosphorescent pigment, and the content of iron and / or iron compound is below a specific value. It is possible to reduce the phosphorescent deterioration of the molded product and meet its purpose, and this can be achieved by dispersing and molding the aluminate phosphorescent pigment in a previously melted thermoplastic resin. Based on this finding, the present invention has been completed.
That is, the present invention
(1) A method for producing a phosphorescent molded article containing 40 to 99 parts by weight of a thermoplastic resin and 60 to 1 part by weight of an aluminate phosphorescent pigment, after melting the thermoplastic resin in an extruder To this, an aluminate phosphorescent pigment is added in a side-feed manner, the aluminate phosphorescent pigment is uniformly dispersed, and pellets containing 0.10% by weight or less of iron of the aluminate phosphorescent pigment are obtained . formed and was molded by using the pellet, 0.10 method of manufacturing a phosphorescent molded body, which comprises forming a shaped body containing a weight% iron relative aluminate phosphorescent pigments,
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The phosphorescent molded article of the present invention contains a thermoplastic resin and an aluminate phosphorescent pigment, and the thermoplastic resin is not particularly limited, and the use of the molded article from conventionally known ones It can be appropriately selected according to the above. Examples of this thermoplastic resin include ethylene vinyl alcohol copolymer, polyethylene, polypropylene, polystyrene, ABS resin, acrylic resin, polycarbonate, polyacetal resin, polybutylene terephthalate, polyamide, polyurethane, or a polymer alloy or polyurethane thereof. And thermoplastic elastomers such as polyethylene and polyethylene.
On the other hand, as the phosphorescent pigment, an aluminate phosphorescent pigment is used. As typical examples of the aluminate phosphorescent pigment, the general formula [1]
MAl 2 O 4 [1]
The compound represented by these can be mentioned. In the general formula [1], M is a metal such as calcium, strontium or barium.
If necessary, lanthanum metal elements such as europium (Eu), lanthanum (La), cerium (Ce), praseodymium (Pr), dysprosium (Dy), neodymium (Nd) are added to the above compounds as an activator. May be. Examples of such aluminate-based phosphorescent pigments include CaAl 2 O 4 : Eu 2+ , Nd 3+ (emission color: purple blue, emission peak wavelength: 440 nm), SrAl 2 O 4 : Eu 2+ , Dy 3+ (emission color: yellow-green, emission peak wavelength: 520 nm), SrAl 2 O 4 : Eu 2+ (emission color: yellow-green, emission peak wavelength: 520 nm), and the like. In addition, Sr 4 Al 14 O 25 : Eu 2+ , Dy 3+ (emission color: blue-green, emission peak wavelength: 490 nm) can also be used.
Such aluminate-based phosphorescent pigments have higher afterglow luminance and longer afterglow time than conventional sulfide-based phosphorescent pigments such as CaSrS: Bi, ZnS: Cu, ZnS: Cu, Co, etc. Has excellent afterglow characteristics.
In the present invention, one kind of the aluminate phosphorescent pigment may be used, or two or more kinds may be used in combination. The content ratio of the thermoplastic resin and the aluminate phosphorescent pigment in the phosphorescent molded article of the present invention is preferably in the range of 99: 1 to 40:60 by weight. When the content ratio of the aluminate phosphorescent pigment is less than the above range, the afterglow intensity is small, the function as a phosphorescent molded article is not sufficiently exhibited, and when it exceeds the above range, wear during molding is severe and dullness is large. At the same time, there is a risk that the phosphorescent property is lowered. Considering afterglow intensity, wear, and the like, a more preferable content ratio of the thermoplastic resin and the aluminate phosphorescent pigment is in the range of 95: 5 to 50:50 by weight.
[0006]
In the luminous composition of the present invention, the iron and / or iron compound content needs to be 0.10% by weight or less based on the aluminate phosphorescent pigment as iron. When this content exceeds 0.10% by weight, the afterglow intensity of the molded product is lowered, and a dullness occurs. In order to effectively suppress the decrease in afterglow intensity and the generation of dullness, the iron and / or iron compound content is preferably 0.08% by weight or less based on the aluminate phosphorescent pigment as iron. In particular, 0.06% by weight or less is preferable.
In the phosphorescent molded article of the present invention, various additives such as other pigments, antioxidants, thermal stabilizers, ultraviolet absorbers, light stabilizers, flame retardants may be used as long as the effects of the present invention are not impaired. A lubricant, a filler, an antistatic agent and the like can be appropriately added.
Such a phosphorescent molded article of the present invention can be efficiently produced according to the method of the present invention shown below.
In the method of the present invention, a thermoplastic resin is melted in advance, and a predetermined amount of an aluminate-based phosphorescent pigment is added to the thermoplastic resin having a low viscosity in the molten state, and then uniformly molded, and then molded. By this method, the content of iron and / or iron compound is not more than 0.10% by weight, preferably not more than 0.08% by weight, more preferably 0.06% by weight based on the aluminate phosphorescent pigment as iron. % Or less phosphorescent molded body can be produced efficiently. In a method that is normally used, that is, a method in which a thermoplastic resin and an aluminate phosphorescent pigment are mixed in advance and then kneaded with an extruder, the cylinder or screw in the extruder is mixed with aluminate during kneading. Abraded by the salt-based phosphorescent pigment, and iron and iron compounds generated by this abrasion are mixed in, so a desired phosphorescent molded article cannot be obtained.
Specifically illustrating the method of the present invention, in an extruder, after the thermoplastic resin is first melted, an aluminate-based phosphorescent pigment is added to this in a side-feed manner, dispersed uniformly, and then molded. Good. There is no restriction | limiting in particular as a shaping | molding method, It can select and use suitably from methods, such as extrusion molding, injection molding, blow molding, etc. conventionally used in shaping | molding of a thermoplastic resin conventionally.
[0007]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
Low density polyethylene was charged in an extruder heated to 150 to 230 ° C. and melted, and then aluminate-based phosphorescent pigment [manufactured by Nemoto Special Chemical Co., Ltd., trade name: G-300M] was added to the pigment / resin. The strands added by the side feed method so as to have a weight ratio of 10/90, kneaded and extruded were cooled and then pelletized. The iron content in the pellets was 0.020% by weight of the phosphorescent pigment.
The obtained pellets were molded into a plate shape and various properties were evaluated. The results are shown in Table 1.
Examples 2-6
Pellets were produced in the same manner as in Example 1 using the thermoplastic resin of the type shown in Table 1 and the phosphorescent pigment / resin weight ratio being the value shown in Table 1, and molded into a plate shape. did. The results are shown in Table 1.
Comparative Example 1
Low density polyethylene and phosphorescent pigment [manufactured by Nemoto Special Chemical Co., Ltd., trade name: G-300M] are mixed so that the pigment / resin weight ratio is 20/80, and then charged into an extruder heated to 170 to 230 ° C. The melt-kneaded and extruded strands were cooled and made into pellets. The iron content in the pellets was 0.130% by weight of the phosphorescent pigment.
The obtained pellets were molded into a plate shape and various properties were evaluated. The results are shown in Table 1.
[0008]
[Table 1]
[note]
1) LDPE: Low density polyethylene PP: Polypropylene HIPS: High impact polystyrene ABS: Acrylonitrile butadiene styrene resin PMMA: Polymethylmethacrylate 2) Containing phosphorescent pigment in which iron and iron compounds contained in molded products are converted to iron amount.
3) Luminance after the molded article was irradiated with a 400-lux fluorescent lamp for 30 minutes and left in a dark room at room temperature for 60 minutes. Measured with a Minolta LS-100 luminance meter.
[0010]
【The invention's effect】
According to the present invention, it is possible to suppress a phosphorescent deterioration due to contamination of impurities, particularly, contamination during molding, a high afterglow intensity, a long afterglow time, and a phosphorescent molded body having no dull color. Obtainable.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16683998A JP3947619B2 (en) | 1998-06-15 | 1998-06-15 | Method for producing phosphorescent molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16683998A JP3947619B2 (en) | 1998-06-15 | 1998-06-15 | Method for producing phosphorescent molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000001569A JP2000001569A (en) | 2000-01-07 |
| JP3947619B2 true JP3947619B2 (en) | 2007-07-25 |
Family
ID=15838619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16683998A Expired - Fee Related JP3947619B2 (en) | 1998-06-15 | 1998-06-15 | Method for producing phosphorescent molded body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3947619B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102313244B1 (en) * | 2020-12-18 | 2021-10-14 | 주식회사 아트스페이스이엔지 | Manufacturing method of phosphorescent material with excellent phosphorescence effect |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930733B2 (en) * | 1982-01-29 | 1984-07-28 | サンケン商事株式会社 | Molding composition with phosphorescence |
| JP3260995B2 (en) * | 1994-12-28 | 2002-02-25 | ワイケイケイ株式会社 | Luminescent synthetic resin material, method for producing the same, and molded article |
| JPH1017743A (en) * | 1996-07-01 | 1998-01-20 | Mitsubishi Chem Mkv Co | Production of vinyl chloride-based resin composition |
| JP3747348B2 (en) * | 1997-07-11 | 2006-02-22 | リケンテクノス株式会社 | Method for producing thermoplastic resin composition containing phosphorescent phosphor |
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1998
- 1998-06-15 JP JP16683998A patent/JP3947619B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000001569A (en) | 2000-01-07 |
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