JP2004035744A - Luminous polyolefin open-cell foam and its manufacturing process - Google Patents

Luminous polyolefin open-cell foam and its manufacturing process Download PDF

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Publication number
JP2004035744A
JP2004035744A JP2002195478A JP2002195478A JP2004035744A JP 2004035744 A JP2004035744 A JP 2004035744A JP 2002195478 A JP2002195478 A JP 2002195478A JP 2002195478 A JP2002195478 A JP 2002195478A JP 2004035744 A JP2004035744 A JP 2004035744A
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Japan
Prior art keywords
luminous
foam
polyolefin
open
foaming
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JP2002195478A
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Japanese (ja)
Inventor
Masaaki Sawara
佐原 正明
Choji Obara
小原 長二
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Sanwa Kako Co Ltd
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Sanwa Kako Co Ltd
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Filing date
Publication date
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Priority to JP2002195478A priority Critical patent/JP2004035744A/en
Publication of JP2004035744A publication Critical patent/JP2004035744A/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminous polyolefin foam that emits light in the dark and the luminescent of which persists for more than one hour after the light is off and its manufacturing method. <P>SOLUTION: A polyolefin is blended with 2-20 wt.pts. of a luminous pigment containing an expander, a crosslinking agent, 60-70% aluminum chloride, 20-30% strontium chloride and 1-5% antimony trioxide. The blend is packed into the mold in a press. The mold is tightly sealed under pressure and heated to decompose the expander for a specific period of time. The pressure is relieved. The blend is put in an unsealed mold and heated to obtain a foam. The cells of the foam is mechanically made open. <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、玩具、カタログ等に使用される蓄光性ポリオレフィン連続気泡発泡体及びその製造方法に関するものである。
【0002】
【従来の技術】
ポリオレフィン発泡体は、断熱性、耐候性、弾性等に優れ、断熱材、土木建築用目地材、玩具、包装材、スポーツ用品等に使用されている。ポリオレフィン発泡体を着色する方法としては、ポリオレフィン樹脂に顔料、有機発泡剤を混練りし、長尺に加熱発泡させる方法又は加圧一段発泡、二段発泡(特公平2−42649号公報参照)でブロック状に加熱発泡させる方法が一般的であり、明るい場所では、色を識別できるが、暗い場所では、発泡体の存在及び色を識別することができなかった。
【0003】
最近、本出願人は、燐光性硫化亜鉛(ZnS:Cu)を主成分とする蓄光顔料を混和した蓄光性ポリオレフィン発泡体及びその製造方法を提案した(特開2000−336201号公報)。しかしながら、この発明で使用された蓄光性蛍光粉は、蓄光、発光は出来るが、発光時間は1〜2時間程度に過ぎず、化学安定性は低く、耐水性に劣り、老化しやすいため、悪条件下では、発光能力は急激に低下し、使用寿命が短いなどの欠点があった。
【0004】
また、今までの蓄光性ポリオレフィン発泡体は、独立気泡でありクッション性に劣っていた。
【0005】
【発明が解決しようとする課題】
従って、本発明の目的は、前記従来技術の欠点を解消し、暗い場所で発色し、発光強度が強く、発光時間が長く、耐水性に優れかつクッション性にも優れる、玩具、誘導標識、広告用品等に有用な蓄光性ポリオレフィン連続気泡体及びその製造方法を提供することにある。
【0006】
【課題を解決するための手段】
本発明の蓄光性ポリオレフィン連続気泡体は、前記目的を達成するため、ポリオレフィン樹脂に塩化アルミニウム、塩化ストロンチウム及び三酸化アンチモンを含有する蓄光顔料を混和したことを特徴とするものである。
【0007】
本発明において、蓄光顔料が、塩化アルミニウム60〜70%、塩化ストロンチウム20〜30%、三酸化アンチモン1〜5%を含有する混合物であることが好ましく、この範囲外の場合、発光強度、発光時間が劣ることになる。
【0008】
本発明の蓄光性ポリオレフィン連続気泡体の製造方法は、ポリオレフィン樹脂に発泡剤、架橋剤及び、塩化アルミニウム、塩化ストロンチウム、三酸化アンチモンを含有する蓄光顔料を混和し、加熱発泡させた後、機械的変形を加えて、気泡を連通化させることを特徴とするものである。
【0009】
本発明の製造方法において、蓄光顔料が、塩化アルミニウム60〜70%、塩化ストロンチウム20〜30%、三酸化アンチモン1〜5%を含有する混合物であることが好ましく、この範囲外の場合、発光強度、発光時間が劣ることになる。
【0010】
本発明において使用される蓄光性顔料は、元素「Sb」を含むことにより、焼成時の結晶の粒成長を抑制する働きがある。その結果、微小単位(nm単位)の粒子において蓄光性を有するので、微粒子より成る蓄光顔料を使用でき、樹脂、発泡剤との相溶性に優れ、得られる発泡体の気泡が均一微細である。
【0011】
本発明において、ポリオレフィン樹脂100重量部に対し、このような蓄光顔料を2〜20重量部添加することが好ましい。蓄光顔料が2重量部未満であると、発色現象が弱く、20重量部を超えると、発泡に悪影響をおよぼす。
【0012】
本発明の製造方法において適用される発泡方法としては、無架橋押出発泡、化学架橋又は電子線架橋による長尺シート発泡又はブロック発泡があり、特に限定されないが、下記の発泡方法が好ましい。
【0013】
【発明の実施の形態】
以下、本発明に係る蓄光性ポリオレフィン発泡体の製造方法についてその好適な態様を具体的に説明する。
【0014】
ポリオレフィンに蓄光顔料、発泡剤、発泡助剤、架橋剤及び必要に応じて充填剤を配合し、これを加熱したミキシングロール、加圧式ニーダー、押出機等によって混和する。上記のように混和して得られた発泡性架橋性組成物を金型に充填し、これを加圧下に密閉して、115〜155℃、好ましくは120〜150℃において加熱整形する。この加熱整形工程において、発泡性架橋性組成物をゲル分率ゼロの状態に維持して整形することが、連続気泡率100%に近い連続気泡体を得る条件である。
【0015】
上記のようにして整形された発泡性架橋性組成物は、次いで、常圧下にて加熱することによって、架橋剤及び発泡剤の分解を同時進行的に行わしめられる。この発泡・架橋工程は、例えば整形されたポリオレフィン組成物を所望の断面形状、寸法を有する気密でない、即ち密閉されていない金型中に入れ、金型に設けたジャケットに熱媒を通して加熱し、140〜210℃、好ましくは150〜190℃で、30〜150分間、好ましくは60〜120分間加熱せしめることにより、物性の均一な気泡体を得る。以上のようにして得られた気泡体を、例えば等速二本ロール等により圧縮変形を加えることによって気泡膜は破壊され、気泡が連通化されて連続気泡体が得られる。
【0016】
本発明において使用されるポリオレフィン樹脂とは、例えば、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)、高密度ポリエチレン(HDPE)、エチレン・酢酸ビニル共重合体等のエチレン系樹脂、及び、プロピレン単独重合、プロピレン・α―オレフィンランダム共重合体、プロピレン・α―オレフィンブロック共重合体等のプロピレン系樹脂、並びに、その他のオレフィン系重合体及び共重合体樹脂等のいわゆる汎用ポリオレフィン系樹脂が挙げられる。
【0017】
本発明で使用しうる発泡剤は、ポリエチレン系樹脂の溶融温度以上の分解温度を有する化学発泡剤であり、例えばアゾ系化合物のアゾジカルボンアミド、バリウムアゾジカルボキシレート等;ニトロソ系化合物のジニトロソメチレンペンタテトラミン、トリニトロトリメチルトリアミン等;ヒドラジッド系化合物のp,p‘−オキシビスベンゼンスルホニルヒゾラジッド等;スルホニルセミカルバジッド系化合物p,p‘−オキシビスベンゼンスルホニルセミカルバジッド、トルエンスルホニルセミカルバジッド等がある。
【0018】
本発明において架橋剤とは、樹脂中において少なくとも樹脂の流動開始温度以上の分解温度を有するものであって、加熱により分解され、遊離ラジカルを発生してその分子間もしくは分子内に架橋結合を生じせしめるラジカル発生剤であるところの有機過酸化物、例えばジクミルパーオキサイド、1,1−ジターシャリーブチルパーオキシー3,3,5−トリメチルシクロヘキサン、2,5−ジメチルー2,5−ジターシャリーブチルパーオキシヘキサン、2,5−ジメチルー2,5−ジターシャリーブチルパーオキシヘキシン、α、α―ジターシャリーブチルパーオキシイソプロピルベンゼン、ターシャリーブチルパーオキシケトン、ターシャリーブチルパーオキシベンゾエートなどがあるが、その時に使用される樹脂によって最適な有機過酸化物を選択しなければならない。
【0019】
本発明においては、発泡助剤を発泡剤の種類に応じて添加することができる。発泡助剤としては尿素を主成分とした化合物、酸化亜鉛、酸化鉛等の金属酸化物、サリチル酸、ステアリン酸等を主成分とする化合物、即ち高級脂肪酸あるいは高級脂肪酸の金属化合物などがある。
【0020】
本発明においては、使用する組成物の物性の改良或いは価格の低下を目的として、架橋結合に著しい悪影響を与えない配合剤(充填剤)、例えば酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化ケイ素等の金属酸化物、炭酸マグネシウム、炭酸カルシウム等の炭酸塩、あるいはパルプ等の繊維物質、又は各種染料並びに顔料、その他常用のゴム配合剤等を必要に応じて添加することができる。
【0021】
本発明で得られる蓄光性発泡体の残光輝度は以下の方法で測定される。
【0022】
24時間光を遮断して、15Wの卓上蛍光灯にて40cmの距離から20min照射する。その後、400mmの距離から輝度計(LS−100輝度計、ミノルタ株式会社製)にて残光輝度を測定する。
【0023】
【実施例】
以下、実施例を示して本発明を更に具体的に説明するが、本発明は下記実施例により何等限定されるものではない。
【0024】
実施例1
エチレン−酢酸ビニル共重合体(商品名:ノバテックLV540、密度0.942g/cm、メルトフローレート2.5g/10分、酢酸ビニル含有量20重量%、三菱化学株式会社製)70重量部、低密度ポリエチレン(商品名:ノバテックLE425、密度0.923g/cm、メルトフローレート2.0g/10分、三菱化学株式会社製)30重量部と、蓄光顔料(商品名:イージーブライト、組成:塩化アルミニウム60〜70%、塩化ストロンチウム20〜30%、三酸化アンチモン1〜5%、イージーブライト株式会社製)10.0重量部、アゾジカルボンアミド(商品名:ビニホールAC#3、永和化成工業株式会社製)18重量部、活性亜鉛華0.1重量部、ジクミルパーオキサイド0.7重量部からなる組成物を100℃のニーダーにて混練し、130℃に加熱されたプレス内の金型(28×195×385)に練和物を充填し、60分間加圧下で加熱し、発泡性架橋組成物を成形した。
【0025】
該成形物の発泡倍率は1.1倍、ゲル分率は0であった。
【0026】
次いで、該成型物を加熱水蒸気の流路を周囲に設けた気密でない開閉式金属金型(100×500×1000mm)の略中央に載置し、6.5kg/cmの加熱水蒸気を該流路に流して180分間加熱して残存する発泡剤及び架橋剤を分解して冷却後、発泡体得た。
【0027】
得られた発泡体をロール間隔20mmに設定した等速二本ロールの間を5回通化させて気泡膜を破壊させ、気泡の連通化を行った。得られた連続気泡体は、見掛け密度32kg/m、連続気泡率100%であった。
【0028】
残光輝度を測定したところ、90分経過後においても2mcd/mの輝度を示し、暗闇の中でも発泡体を確認できた。
【0029】
実施例2
実施例1において、蓄光顔料を5.0重量部に変えた以外は、実施例1と同じ配合及び同じ条件で連続気泡率100%、見掛け密度32kg/mの連続気泡体を製造した。連続気泡体の残光輝度を測定した結果、90分経過後、1.8mcd/mの輝度を示し、暗闇の中でも発泡体を確認できた。
【0030】
実施例3
実施例1において、蓄光顔料を15.0重量部に変えた以外は、実施例1と同じ配合及び同じ条件で連続気泡率100%、見掛け密度32kg/mの連続気泡体を製造した。連続気泡体の残光輝度を測定した結果、90分経過後、2.5mcd/mの輝度を示し、暗闇の中でも発泡体を確認できた。
【0031】
比較例1
実施例1において、蓄光顔料を成分として塩化アルミニウム、塩化ストロンチウム、三酸化アンチモンを含まないもの(商品名:GSS、主成分 ZnS,Cu、根本特殊化学株式会社製)に変えた以外は、実施例1と同じ配合及び同じ条件で発泡させ、発泡体を得た。
【0032】
得られた発泡体の見掛け密度は31kg/m、60分経過後の輝度は1mcd/mであり、暗闇の中で発泡体を確認できなかった。
【0033】
比較例2
実施例1において、蓄光顔料を1.0重量部に変えた以外は、実施例1と同じ配合及び同じ条件で連続気泡率100%、見掛け密度32kg/mの連続気泡体を製造した。連続気泡体の残光輝度を測定したが、ほとんど発光しなかった。
【0034】
比較例3
実施例1において、蓄光顔料を25重量部に変えた以外は、実施例1と同じ配合及び同じ条件で発泡させたが、多量の蓄光顔料が発泡を阻害し、連続気泡体を製造することが出来なかった。
【0035】
【表1】

Figure 2004035744
【0036】
【発明の効果】
以上のように、本発明によれば、塩化アルミニウム、塩化ストロンチウム、三酸化アンチモンを含有した混合物である蓄光顔料を使用して蓄光性ポリオレフィン連続気泡体を製造することより、暗い場所で発色し、電気を消した後の残光時間が1時間以上であり、蓄光顔料と樹脂、発泡剤との相溶性に優れ、発光強度、発光時間、耐水性、クッション性に優れ、玩具、誘導標識、広告用品等に有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a luminous polyolefin open-cell foam used for toys, catalogs, and the like, and a method for producing the same.
[0002]
[Prior art]
BACKGROUND ART Polyolefin foams have excellent heat insulating properties, weather resistance, elasticity, and the like, and are used for heat insulating materials, joint materials for civil engineering and construction, toys, packaging materials, sporting goods, and the like. As a method of coloring a polyolefin foam, a method of kneading a pigment and an organic foaming agent with a polyolefin resin and heating and foaming it in a long length, or pressure one-stage foaming or two-stage foaming (see Japanese Patent Publication No. 2-42649). A method of heating and foaming in a block shape is generally used. In a bright place, the color can be identified, but in a dark place, the presence and color of the foam cannot be identified.
[0003]
Recently, the present applicant has proposed a luminous polyolefin foam containing a luminous pigment containing phosphorescent zinc sulfide (ZnS: Cu) as a main component and a method for producing the same (Japanese Patent Application Laid-Open No. 2000-336201). However, the luminous phosphor powder used in the present invention can luminesce and emit light, but the luminescence time is only about 1 to 2 hours, the chemical stability is low, the water resistance is poor, and the aging is apt to occur. Under the conditions, there were drawbacks such as a rapid decrease in light emitting ability and a short service life.
[0004]
Further, the conventional phosphorescent polyolefin foams are closed cells and have poor cushioning properties.
[0005]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to solve the above-mentioned drawbacks of the prior art, to produce a color in a dark place, to have a strong luminous intensity, a long luminous time, excellent in water resistance and excellent in cushioning property, toys, guide signs, advertisements. An object of the present invention is to provide a luminous polyolefin open cell useful for articles and the like and a method for producing the same.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the luminous polyolefin open cell of the present invention is characterized in that a luminous pigment containing aluminum chloride, strontium chloride and antimony trioxide is mixed with a polyolefin resin.
[0007]
In the present invention, the luminous pigment is preferably a mixture containing 60 to 70% of aluminum chloride, 20 to 30% of strontium chloride, and 1 to 5% of antimony trioxide. Will be inferior.
[0008]
The method for producing a luminous polyolefin open-cell body of the present invention is a method for mixing a luminous pigment containing a foaming agent, a crosslinking agent, and aluminum chloride, strontium chloride, and antimony trioxide with a polyolefin resin, and heating and foaming the mixture. The present invention is characterized in that bubbles are made open by deformation.
[0009]
In the production method of the present invention, the phosphorescent pigment is preferably a mixture containing 60 to 70% of aluminum chloride, 20 to 30% of strontium chloride, and 1 to 5% of antimony trioxide. The light emission time is inferior.
[0010]
The luminous pigment used in the present invention has a function of suppressing crystal grain growth during firing by containing the element “Sb”. As a result, the particles having a small unit (nm unit) have luminous properties, so that a luminous pigment composed of fine particles can be used, the compatibility with the resin and the foaming agent is excellent, and the bubbles of the obtained foam are uniform and fine.
[0011]
In the present invention, it is preferable to add 2 to 20 parts by weight of such a luminous pigment to 100 parts by weight of the polyolefin resin. When the amount of the luminous pigment is less than 2 parts by weight, the coloring phenomenon is weak, and when it exceeds 20 parts by weight, the foaming is adversely affected.
[0012]
The foaming method applied in the production method of the present invention includes non-crosslinking extrusion foaming, long sheet foaming or block foaming by chemical crosslinking or electron beam crosslinking, and is not particularly limited, but the following foaming methods are preferred.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a preferred embodiment of the method for producing a phosphorescent polyolefin foam according to the present invention will be specifically described.
[0014]
A luminous pigment, a foaming agent, a foaming aid, a crosslinking agent and, if necessary, a filler are blended with the polyolefin, and the resulting mixture is mixed with a heated mixing roll, a pressure kneader, an extruder, or the like. A mold is filled with the foamable crosslinkable composition obtained by mixing as described above, and the mold is sealed under pressure and shaped by heating at 115 to 155 ° C, preferably 120 to 150 ° C. In this heating shaping step, shaping while maintaining the foamable crosslinkable composition at a gel fraction of zero is a condition for obtaining an open-cell body having an open-cell ratio close to 100%.
[0015]
The foamable crosslinkable composition shaped as described above is then heated under normal pressure to simultaneously decompose the crosslinking agent and the foaming agent. In the foaming / crosslinking step, for example, the shaped polyolefin composition is placed in a non-hermetic, that is, unsealed mold having a desired cross-sectional shape and dimensions, and heated by passing a heat medium through a jacket provided in the mold, By heating at 140 to 210 ° C., preferably 150 to 190 ° C., for 30 to 150 minutes, preferably 60 to 120 minutes, a foam having uniform physical properties is obtained. The foam obtained as described above is subjected to compressive deformation by, for example, a constant-speed double roll or the like, so that the foam film is broken, and the bubbles are communicated to obtain a continuous foam.
[0016]
The polyolefin resin used in the present invention includes, for example, ethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and ethylene / vinyl acetate copolymer; And propylene-based resins such as propylene homopolymerization, propylene / α-olefin random copolymer, propylene / α-olefin block copolymer, and so-called general-purpose polyolefins such as other olefin-based polymers and copolymer resins Resins.
[0017]
The blowing agent that can be used in the present invention is a chemical blowing agent having a decomposition temperature equal to or higher than the melting temperature of the polyethylene resin, such as azo compounds such as azodicarbonamide and barium azodicarboxylate; and nitroso compounds such as dinitroso. Methylenepentatetramine, trinitrotrimethyltriamine and the like; hydrazide-based compounds such as p, p'-oxybisbenzenesulfonylhydrazide; and sulfonylsemicarbazide-based compounds p, p'-oxybisbenzenesulfonylsemicarbazide and toluenesulfonylsemi Carbazide and the like.
[0018]
In the present invention, the cross-linking agent is a resin having a decomposition temperature at least equal to the flow start temperature of the resin, and is decomposed by heating to generate free radicals to generate cross-links between or within the molecules. Organic peroxides which are radical generators, such as dicumyl peroxide, 1,1-ditert-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di-tert-butylperoxide Oxyhexane, 2,5-dimethyl-2,5-ditert-butylperoxyhexyne, α, α-di-tert-butylperoxyisopropylbenzene, tert-butylperoxyketone, tert-butylperoxybenzoate, and the like, Depending on the resin used at that time, the optimal organic An oxide must be chosen.
[0019]
In the present invention, a foaming aid can be added according to the type of the foaming agent. Examples of the foaming aid include compounds mainly containing urea, metal oxides such as zinc oxide and lead oxide, compounds mainly containing salicylic acid, stearic acid and the like, that is, higher fatty acids and metal compounds of higher fatty acids.
[0020]
In the present invention, for the purpose of improving the physical properties of the composition to be used or lowering the price, a compounding agent (filler) that does not significantly affect cross-linking, for example, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, oxide Metal oxides such as silicon, carbonates such as magnesium carbonate and calcium carbonate, fiber materials such as pulp, various dyes and pigments, and other commonly used rubber compounding agents can be added as necessary.
[0021]
The afterglow luminance of the luminous foam obtained in the present invention is measured by the following method.
[0022]
The light is blocked for 24 hours, and irradiation is performed with a 15-W table lamp from a distance of 40 cm for 20 minutes. Thereafter, the afterglow luminance is measured from a distance of 400 mm using a luminance meter (LS-100 luminance meter, manufactured by Minolta Co., Ltd.).
[0023]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.
[0024]
Example 1
70 parts by weight of an ethylene-vinyl acetate copolymer (trade name: Novatec LV540, density 0.942 g / cm 3 , melt flow rate 2.5 g / 10 minutes, vinyl acetate content 20% by weight, manufactured by Mitsubishi Chemical Corporation), 30 parts by weight of low-density polyethylene (trade name: Novatec LE425, density 0.923 g / cm 3 , melt flow rate 2.0 g / 10 min, manufactured by Mitsubishi Chemical Corporation) and a luminous pigment (trade name: Easy Bright, composition: Aluminum chloride 60 to 70%, strontium chloride 20 to 30%, antimony trioxide 1 to 5%, 10.0 parts by weight, manufactured by Easy Bright Co., Ltd., 10.0 parts by weight, azodicarbonamide (trade name: Vinylol AC # 3, Eiwa Chemical Co., Ltd.) 1 part by weight of active zinc white and 0.7 part by weight of dicumyl peroxide The mixture was kneaded in a kneader at 00 ° C., and the kneaded product was filled in a mold (28 × 195 × 385) in a press heated to 130 ° C., and heated under pressure for 60 minutes to form an expandable crosslinked composition. did.
[0025]
The expansion ratio of the molded product was 1.1 times, and the gel fraction was 0.
[0026]
Next, the molded product is placed substantially in the center of a non-hermetic open / close metal mold (100 × 500 × 1000 mm) provided with a heating steam flow path therearound, and 6.5 kg / cm 2 of heating steam is applied to the molding. The mixture was passed through a path and heated for 180 minutes to decompose the remaining foaming agent and cross-linking agent. After cooling, a foam was obtained.
[0027]
The obtained foam was passed between two constant-velocity two rolls set at a roll interval of 20 mm five times to break the bubble film and to communicate the bubbles. The obtained open-cell foam had an apparent density of 32 kg / m 3 and an open-cell ratio of 100%.
[0028]
When the afterglow luminance was measured, the luminance was 2 mcd / m 2 even after 90 minutes had elapsed, and the foam was confirmed even in darkness.
[0029]
Example 2
An open-cell body having an open-cell rate of 100% and an apparent density of 32 kg / m 3 was produced in the same manner as in Example 1 except that the phosphorescent pigment was changed to 5.0 parts by weight in Example 1. As a result of measuring the afterglow luminance of the open-cell foam, it showed a luminance of 1.8 mcd / m 2 after 90 minutes, and the foam was confirmed even in darkness.
[0030]
Example 3
An open-cell foam having an open-cell ratio of 100% and an apparent density of 32 kg / m 3 was produced in the same manner as in Example 1 except that the phosphorescent pigment was changed to 15.0 parts by weight in Example 1. Results afterglow luminance of open-cell foam was measured, after 90 minutes, showed a brightness of 2.5mcd / m 2, it was confirmed foam even in the dark.
[0031]
Comparative Example 1
Example 1 is the same as Example 1 except that the phosphorescent pigment was changed to a component not containing aluminum chloride, strontium chloride, and antimony trioxide (trade name: GSS, main component ZnS, Cu, manufactured by Nemoto Special Chemical Co., Ltd.). The mixture was foamed under the same composition and under the same conditions as in Example 1 to obtain a foam.
[0032]
The apparent density of the obtained foam was 31 kg / m 3 , and the luminance after 60 minutes was 1 mcd / m 2 , and the foam could not be confirmed in the dark.
[0033]
Comparative Example 2
An open-cell foam having an open-cell rate of 100% and an apparent density of 32 kg / m 3 was produced in the same manner as in Example 1 except that the phosphorescent pigment was changed to 1.0 part by weight in Example 1. Afterglow luminance of the open-cell foam was measured, but almost no light was emitted.
[0034]
Comparative Example 3
In Example 1, foaming was carried out under the same composition and under the same conditions as in Example 1 except that the luminous pigment was changed to 25 parts by weight. However, a large amount of luminous pigment inhibited foaming, and it was possible to produce an open-cell body. I could not do it.
[0035]
[Table 1]
Figure 2004035744
[0036]
【The invention's effect】
As described above, according to the present invention, aluminum chloride, strontium chloride, by using a phosphorescent pigment that is a mixture containing antimony trioxide to produce a luminous polyolefin open-cell body, color development in a dark place, Afterglow time after turning off electricity is 1 hour or more, excellent compatibility between luminous pigment, resin and foaming agent, excellent luminous intensity, luminous time, water resistance, cushioning property, toys, induction signs, advertising Useful for supplies and the like.

Claims (4)

ポリオレフィン樹脂に塩化アルミニウム、塩化ストロンチウム及び三酸化アンチモンを含有する蓄光顔料を混和したことを特徴とする蓄光性ポリオレフィン連続気泡体。A luminous polyolefin open-cell body comprising a polyolefin resin mixed with a luminous pigment containing aluminum chloride, strontium chloride and antimony trioxide. 蓄光顔料が、塩化アルミニウム60〜70%、塩化ストロンチウム20〜30%、三酸化アンチモン1〜5%を含有する混合物である請求項1記載の蓄光性ポリオレフィン連続気泡体。The luminous polyolefin open cell according to claim 1, wherein the luminous pigment is a mixture containing 60 to 70% of aluminum chloride, 20 to 30% of strontium chloride, and 1 to 5% of antimony trioxide. ポリオレフィン樹脂に発泡剤、架橋剤及び、塩化アルミニウム、塩化ストロンチウム、三酸化アンチモンを含有する蓄光顔料を混和し、加熱発泡させて気泡体を生成させ、次いで機械的変形を加えて気泡を連通化することを特徴とする蓄光性ポリオレフィン連続気泡体の製造方法。A polyolefin resin is mixed with a luminous pigment containing a foaming agent, a cross-linking agent, and aluminum chloride, strontium chloride, and antimony trioxide, and is heated and foamed to form a foam. A method for producing a luminous polyolefin open cell, comprising: 蓄光顔料が、塩化アルミニウム60〜70%、塩化ストロンチウム20〜30%、三酸化アンチモン1〜5%を含有する混合物である請求項3記載の製造方法。The method according to claim 3, wherein the phosphorescent pigment is a mixture containing 60 to 70% of aluminum chloride, 20 to 30% of strontium chloride, and 1 to 5% of antimony trioxide.
JP2002195478A 2002-07-04 2002-07-04 Luminous polyolefin open-cell foam and its manufacturing process Pending JP2004035744A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009255366A (en) * 2008-04-16 2009-11-05 Sanwa Kako Co Ltd Manufacturing method of polyolefin foam hot press-molded product
CN105670325A (en) * 2014-11-18 2016-06-15 镇江三鑫科技信息有限公司 Noctilucent advertising paper

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009255366A (en) * 2008-04-16 2009-11-05 Sanwa Kako Co Ltd Manufacturing method of polyolefin foam hot press-molded product
CN105670325A (en) * 2014-11-18 2016-06-15 镇江三鑫科技信息有限公司 Noctilucent advertising paper

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