JPH07179646A - Resin particle for production of flame retardant foam of good dimensional stability and its production - Google Patents
Resin particle for production of flame retardant foam of good dimensional stability and its productionInfo
- Publication number
- JPH07179646A JPH07179646A JP5347418A JP34741893A JPH07179646A JP H07179646 A JPH07179646 A JP H07179646A JP 5347418 A JP5347418 A JP 5347418A JP 34741893 A JP34741893 A JP 34741893A JP H07179646 A JPH07179646 A JP H07179646A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- sop
- parts
- styrene
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、発泡性樹脂粒子に関
するものであり、とくに寸法安定性がよくて耐衝撃性に
富んだ難燃性発泡体を作るに適した発泡性粒子、及びそ
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to expandable resin particles, and particularly to expandable particles suitable for producing a flame-retardant foam having good dimensional stability and impact resistance, and the production thereof. It is about the method.
【０００２】[0002]
【従来の技術】発泡性樹脂粒子としては、樹脂としてポ
リスチレンを使用したものが知られている。ポリスチレ
ンを材料とした発泡性粒子は、発泡剤の保留性がよく、
これに水蒸気を接触させると容易に高倍率に発泡し、粒
子同士が強く融着して良好な発泡体を与えるので、発泡
体の製造に広く利用されている。2. Description of the Related Art As expandable resin particles, those using polystyrene as a resin are known. Expandable particles made of polystyrene have good retention of the foaming agent,
When it is contacted with water vapor, it is easily foamed at a high magnification, and the particles are strongly fused to each other to give a good foam, which is widely used in the production of foams.
【０００３】ところが、ポリスチレン製の発泡性粒子か
ら作られた発泡体は、燃え易いという欠点を持ってい
る。そこで、これを難燃化しようとする試みがなされ
た。その試みは、ポリスチレンに難燃剤を加えて発泡体
を難燃性にしようとするものであった。ところが、一般
に難燃剤を加えると、粒子の融着が悪くなったり、発泡
体の耐熱性が劣ることとなったり、寸法安定性が悪くな
ったりした。However, a foam made of expandable polystyrene particles has a drawback of being easily burned. Therefore, an attempt was made to make it flame-retardant. The attempt was to add flame retardants to polystyrene to render the foam flame retardant. However, in general, when a flame retardant is added, the fusion of particles becomes poor, the heat resistance of the foam becomes poor, and the dimensional stability becomes poor.
【０００４】例えば、特開平３−１２４７４４号公報
は、スチレン系樹脂粒子を難燃化するのに、融点７０〜
１２０℃の臭素含有芳香族系化合物とテトラブロモシク
ロオクタンとを重量比で、前者２〜９０に対し後者９８
〜１０の割合で混合して用いることを提案している。し
かし、このように臭素含有芳香族化合物を加えたので
は、樹脂の軟化点が低下し、また発泡倍率が低下し、さ
らに得られた発泡体が寸法安定性の悪いものとなる。従
って、この発泡性粒子は寸法安定性と耐熱性とが要求さ
れる分野では満足なものとなり得なかった。For example, Japanese Patent Application Laid-Open No. 3-124744 discloses a styrene resin particle having a melting point of 70 to 70 in order to make it flame-retardant.
The bromine-containing aromatic compound at 120 ° C. and tetrabromocyclooctane were used in a weight ratio of the former 2 to 90 to the latter 98.
It is proposed to mix them at a ratio of 10 to 10. However, when the bromine-containing aromatic compound is added in this way, the softening point of the resin is lowered, the expansion ratio is lowered, and the resulting foam has poor dimensional stability. Therefore, the expandable particles could not be satisfied in the fields where dimensional stability and heat resistance are required.
【０００５】また、特開平３−１２４７４４号公報で
は、難燃化に使用できる樹脂がスチレン系樹脂と記載さ
れているが、その実体はスチレン、α−メチルスチレン
などの単独重合体が主体とされていた。そこでは、単独
重合体のほか、少量の他の単量体が含まれたスチレンの
共重合体も使用できると説明されているが、他の単量体
としてはブタジエン、メチルメタクリレート、アクリロ
ニトリル、臭素化スチレン、無水マレイン酸、イタコン
酸が例示されるに過ぎなかった。だから、その共重合体
は結局単量体同士を混合して共重合させることのできる
ものが使用できるとされたに過ぎなかった。Further, in JP-A-3-124744, a resin which can be used for flame retardation is described as a styrene resin, but the substance is mainly a homopolymer such as styrene or α-methylstyrene. Was there. It is described that, in addition to homopolymers, styrene copolymers containing small amounts of other monomers can also be used, but other monomers include butadiene, methyl methacrylate, acrylonitrile, and bromine. Styrene styrene, maleic anhydride, and itaconic acid are merely examples. Therefore, it was only said that the copolymer could eventually be used as a copolymer that can be mixed with each other and copolymerized.
【０００６】他方、ポリスチレンの代わりにスチレン改
質ポリエチレンを発泡性粒子として用いることが知られ
ていた。スチレン改質ポリエチレンは、スチレンとエチ
レンを混合して共重合させて得られるものではなくて、
既に重合したポリエチレンにスチレンを吸収させ、ポリ
エチレンにスチレンをグラフト重合させて得られたもの
である。また、スチレン改質ポリエチレンは、その中に
大量のエチレンを含んでいるものもある。従って、スチ
レン改質ポリエチレンは前述のスチレン系樹脂とは異な
っている。On the other hand, it has been known to use styrene-modified polyethylene as expandable particles instead of polystyrene. Styrene-modified polyethylene is not obtained by mixing styrene and ethylene and copolymerizing them,
It is obtained by absorbing styrene into already polymerized polyethylene and graft-polymerizing styrene onto polyethylene. In addition, some styrene-modified polyethylene contains a large amount of ethylene therein. Therefore, styrene-modified polyethylene is different from the above-mentioned styrene resin.
【０００７】上述のスチレン改質ポリエチレンを使用し
て作った発泡体を難燃化することも既に提案された。そ
れは特願平４−１０７２９７号明細書に記載されてい
る。しかし、この難燃性のスチレン改質ポリエチレン発
泡体は、難燃剤を用いたものではなくて、発泡剤残存量
と発泡倍率とを特定の関係に維持することによって、発
泡体を難燃性にしたに過ぎない。すなわち、成形倍数が
３５倍以下のスチレン改質ポリエチレン発泡体であっ
て、成形倍数をＹ倍とし、成形体中に残存する可燃性発
泡剤の量をＸ重量％とした場合に Ｘ2 ・Ｙ≦５ となるように調節すると、発泡体が難燃性になると云う
のである。しかし、成形倍数が３５倍を越えると、Ｘと
Ｙとが上記の式を満たしても発泡体は難燃性にはならな
い。従って、この難燃性スチレン改質ポリエチレン発泡
体は、難燃性であるとは云っても、充分なものではなか
った。It has already been proposed to make foams made using the above-mentioned styrene-modified polyethylene flame-retardant. It is described in Japanese Patent Application No. 4-107297. However, this flame-retardant styrene-modified polyethylene foam does not use a flame retardant, but maintains the foaming agent flame-retardant by maintaining the remaining amount of the foaming agent and the expansion ratio in a specific relationship. I just did it. That is, in the case of a styrene-modified polyethylene foam having a molding multiple of 35 times or less, when the molding multiple is Y times and the amount of the combustible foaming agent remaining in the molded body is X% by weight, X 2 · Y It is said that the foam becomes flame-retardant when it is adjusted so that ≦ 5. However, when the molding multiple exceeds 35 times, the foam does not become flame retardant even if X and Y satisfy the above formula. Therefore, this flame-retardant styrene-modified polyethylene foam is not sufficient, although it is flame-retardant.
【０００８】[0008]
【発明が解決しようとする課題】この発明は、発泡性粒
子を難燃化して、これを発泡させたとき、どのような倍
率に発泡させても満足な難燃性を示すような発泡性粒子
を提供しようとするものである。それとともに、この発
明は、発泡性粒子として発泡が容易であり、発泡によっ
て得られた発泡体がすぐれた物性を持ったものとなるよ
うな発泡性粒子を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention provides an expandable particle which is made flame-retardant and has satisfactory flame resistance when expanded by any expansion ratio. Is to provide. At the same time, the present invention intends to provide expandable particles which are easy to expand as expandable particles and which make the expanded product obtained by expansion have excellent physical properties.
【０００９】[0009]
【課題を解決するための手段】この発明者は、ポリスチ
レンの代わりにスチレンの共重合体を用い、これに難燃
剤と発泡剤を含ませて、上述の要求を満たすような発泡
性粒子を作ろうと企てた。The inventor of the present invention uses a copolymer of styrene instead of polystyrene, and includes a flame retardant and a foaming agent to produce expandable particles satisfying the above-mentioned requirements. I planned to do it.
【００１０】この発明者は、スチレンの色々な共重合体
を作り、これに色々な難燃剤を加えて組成物を作り、こ
の組成物に色々な発泡剤を含浸させて発泡性樹脂粒子を
作った。さらに、この発明者は、こうして得られた発泡
性粒子に水蒸気を接触させて発泡体を作り、その際の発
泡性能と得られた発泡体の物性とを測定した。その結
果、この発明者は、ポリエチレンの粒子にスチレン系単
量体を特定の割合にグラフト重合させて得られたグラフ
ト重合体を用い、またこれに難燃剤としてテトラブロモ
シクロオクタンを特定量だけ含ませて組成物とするのが
よいことを見出した。このような組成物を用いると、あ
とは常法に従ってブタンのような発泡剤を含ませるだけ
で、上に述べた要求を満たす発泡性樹脂粒子の得られる
ことを見出した。この発明は、このような知見に基づい
て完成されたものである。The present inventor has prepared various copolymers of styrene, added various flame retardants to the composition to make compositions, and impregnated the compositions with various foaming agents to form expandable resin particles. It was Further, the present inventor made a foam by bringing the expandable particles thus obtained into contact with water vapor, and measured the foaming performance at that time and the physical properties of the obtained foam. As a result, the inventor has used a graft polymer obtained by graft-polymerizing a styrene-based monomer to a particle of polyethylene in a specific ratio, and also contains tetrabromocyclooctane as a flame retardant in a specific amount. It was found that the composition should be used. It has been found that, when such a composition is used, the expandable resin particles satisfying the above-mentioned requirements can be obtained by only adding a foaming agent such as butane according to a conventional method. The present invention has been completed based on such knowledge.
【００１１】この発明は、発泡性粒子の発明と、その発
泡性粒子を製造する方法の発明とを含んでいる。そのう
ち、発泡性粒子の発明は、重量でオレフィン系樹脂１に
対し、０．５〜５倍量のスチレン系単量体をグラフト重
合させて得られたグラフト重合体１００重量部に、テト
ラブロモシクロオクタン５〜２０重量部と、上記グラフ
ト重合体の軟化点より低い沸点を持った脂肪族又は環式
脂肪族炭化水素を２重量部以上含浸させたことを特徴と
するものである。The present invention includes the invention of expandable particles and the invention of a method of making the expandable particles. Among them, the invention of the expandable particles is 100 parts by weight of a graft polymer obtained by graft-polymerizing a styrene-based monomer in an amount of 0.5 to 5 times the weight of the olefin-based resin 1 by weight, and tetrabromocyclo It is characterized by being impregnated with 5 to 20 parts by weight of octane and 2 parts by weight or more of an aliphatic or cycloaliphatic hydrocarbon having a boiling point lower than the softening point of the graft polymer.
【００１２】また、製造方法に関する発明は、重量でオ
レフィン系樹脂１に対し０．５〜５倍量のスチレン系単
量体をグラフト重合させ、得られたグラフト重合体粒子
１００重量部を耐圧密閉型の回転混合機に入れ、これに
上記グラフト重合体の軟化点より低い沸点を持った脂肪
族炭化水素又は環式脂肪族炭化水素を２重量部以上と、
テトラブロモシクロオクタン５〜２０重量部とを加え、
回転混合機を密閉して回転させながら７０〜８５℃の温
度に１時間以上保持することを特徴とするものである。In the invention relating to the production method, 0.5 to 5 times by weight of styrene-based monomer is graft-polymerized with respect to 1 weight of olefin resin, and 100 parts by weight of the resulting graft polymer particles are pressure-tightly sealed. In a rotary mixer of the type described above, and 2 parts by weight or more of an aliphatic hydrocarbon or a cycloaliphatic hydrocarbon having a boiling point lower than the softening point of the graft polymer,
5 to 20 parts by weight of tetrabromocyclooctane is added,
The rotary mixer is hermetically sealed and rotated, and the temperature is maintained at 70 to 85 ° C. for 1 hour or more.
【００１３】この発明では、樹脂として重量でオレフィ
ン系樹脂１に対し、０．５〜５倍量のスチレン系単量体
をグラフト重合させて得られたグラフト重合体（以下、
これをＳＯＰという）を用いる。この重合体を作るに
は、オレフィン系樹脂の粒子１００重量部を水性媒体中
に分散させ、これに５０〜５００重量部のスチレン系単
量体を加え、重合開始剤の存在下に懸濁重合させて、得
られたグラフト重合体をそのまま粒子の状態で用いるこ
とが好ましい。In the present invention, a graft polymer obtained by graft-polymerizing 0.5 to 5 times the amount of the styrene-based monomer with respect to the olefin-based resin 1 by weight as the resin (hereinafter, referred to as
This is called SOP). To make this polymer, 100 parts by weight of olefin resin particles are dispersed in an aqueous medium, 50 to 500 parts by weight of a styrene monomer is added thereto, and suspension polymerization is performed in the presence of a polymerization initiator. Then, the obtained graft polymer is preferably used as it is in the form of particles.
【００１４】上述のオレフィン系樹脂としては、低密度
ポリエチレン、中密度ポリエチレン、高密度ポリエチレ
ン、エチレン・酢酸ビニル共重合体等を用いることがで
きる。As the above-mentioned olefin resin, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene / vinyl acetate copolymer and the like can be used.
【００１５】上述のスチレン系単量体としては、スチレ
ンのほかにα−メチルスチレン、ビニルトルエン、クロ
ロスチレンのようなスチレン誘導体を用いることができ
る。また、スチレン系単量体としては、スチレン系単量
体だけでなく、アクリロニトリル、ブチルアクリレート
などのようなスチレン系単量体と共重合できる他の単量
体と、スチレン系単量体との混合物を含んでいてもよ
い。As the above-mentioned styrene-based monomer, styrene derivatives such as α-methylstyrene, vinyltoluene and chlorostyrene can be used in addition to styrene. As the styrene-based monomer, not only the styrene-based monomer, but also other monomers that can be copolymerized with the styrene-based monomer such as acrylonitrile and butyl acrylate, and the styrene-based monomer It may contain a mixture.
【００１６】グラフト重合させるときの水性媒体は、水
と適当量の分散剤とで構成される。分散剤としては、部
分鹸化ポリビニルアルコール、ポリアクリル酸塩、ポリ
ビニルピロリドン、カルボキシメチルセルロース、メチ
ルセルロース、ステアリン酸カルシウム、エチレンビス
ステアロアミド等の有機化合物のほか、ピロ燐酸カルシ
ウム、燐酸カルシウム、炭酸カルシウム、炭酸マグネシ
ウム、燐酸マグネシウム、ピロ燐酸マグネシウム、酸化
マグネシウム等の水に難溶性の微粉末からなる無機化合
物を用いることができる。この発明において、分散剤と
して無機化合物を用いる場合には、ドデシルベンゼンス
ルホン酸ナトリウムのような界面活性剤を併用すること
が好ましい。これらの分散剤は、一般に水に対して０．
０１ないし５重量％添加して使用される。The aqueous medium for the graft polymerization is composed of water and an appropriate amount of dispersant. Examples of the dispersant include partially saponified polyvinyl alcohol, polyacrylic acid salts, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, calcium stearate, ethylenebisstearoamide, and other organic compounds, as well as calcium pyrophosphate, calcium phosphate, calcium carbonate, magnesium carbonate. Inorganic compounds such as magnesium phosphate, magnesium pyrophosphate, and magnesium oxide, which are fine powders which are hardly soluble in water, can be used. In the present invention, when an inorganic compound is used as the dispersant, it is preferable to use a surfactant such as sodium dodecylbenzenesulfonate together. These dispersants are generally 0.
It is used by adding 01 to 5% by weight.
【００１７】グラフト重合体を作るには、上述のオレフ
ィン系樹脂の粒子を水性媒体中に分散させ、これに重合
開始剤を含んだスチレン系単量体を加えることが必要で
ある。重合開始剤としては、一般にスチレン系単量体を
重合させるに用いられているものが使用できる。例え
ば、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシ
ベンゾエートなどを使用することができる。そのほか架
橋剤として、ジクミルパーオキサイドを使用することも
できる。In order to make a graft polymer, it is necessary to disperse the above-mentioned olefin resin particles in an aqueous medium and add a styrene monomer containing a polymerization initiator to the dispersion. As the polymerization initiator, those generally used for polymerizing styrene monomers can be used. For example, benzoyl peroxide, t-butyl peroxybenzoate, etc. can be used. In addition, dicumyl peroxide can be used as a crosslinking agent.
【００１８】グラフト重合体を作るには、スチレン系単
量体がオレフィン系樹脂に一様に吸収されるようにして
重合させることが好ましい。また重合を促進するために
加温するがその温度は６０〜１２０℃とすることが好ま
しい。この温度に２〜１２時間保持してスチレン系単量
体をオレフィン系樹脂の粒子の中で重合させる。その後
に架橋を完結させるために、さらに温度を高めて１００
〜１５０℃の温度に１〜１０時間維持することが好まし
い。In order to prepare the graft polymer, it is preferable to polymerize the styrene-based monomer so that it is uniformly absorbed by the olefin-based resin. Further, it is heated to accelerate the polymerization, but the temperature is preferably 60 to 120 ° C. The temperature is maintained at this temperature for 2 to 12 hours to polymerize the styrene monomer in the particles of the olefin resin. Then, in order to complete the crosslinking, the temperature is further increased to 100
It is preferable to maintain the temperature at 150 ° C for 1 to 10 hours.
【００１９】こうしてＳＯＰ樹脂粒子を得る。この粒子
は初めに用いたオレフィン系樹脂粒子が核となって成長
したものである。従って、微細なＳＯＰ樹脂粒子を得る
ためには初めに投入するオレフィン系樹脂粒子を微細な
ものとして用いることが必要である。Thus, SOP resin particles are obtained. These particles are grown using the olefin resin particles used at the beginning as cores. Therefore, in order to obtain fine SOP resin particles, it is necessary to use the olefin resin particles initially charged as fine particles.
【００２０】この発明では、上述のようにして得られた
ＳＯＰに、テトラブロモシクロオクタン（以下、これを
ＴＢＯという）を用いる。ＴＢＯは難燃剤として知られ
ている。また、ＴＢＯは、前述のように、特別な融点を
持った臭素含有芳香族化合物と特定の割合で混合して、
発泡スチレン系樹脂粒子を難燃化するのに用いられて来
た。しかし、ＴＢＯは、オレフィンとスチレンとの共重
合体、とくにＳＯＰに対してはまだ使用されなかった。
実際に、ＴＢＯをＳＯＰに対して使用すると、意外にも
これまで併用が必要とされて来た臭素含有芳香族化合物
が不必要となり、ＴＢＯだけでＳＯＰを難燃化できるこ
とが判明した。In the present invention, tetrabromocyclooctane (hereinafter referred to as TBO) is used for the SOP obtained as described above. TBO is known as a flame retardant. Further, TBO is mixed with a bromine-containing aromatic compound having a special melting point in a specific ratio as described above,
It has been used for flame retarding expanded styrenic resin particles. However, TBO has not yet been used for copolymers of olefins and styrene, especially SOPs.
In fact, when TBO was used for SOP, it was surprisingly found that the bromine-containing aromatic compound, which had been required to be used in combination until now, becomes unnecessary, and that TBO alone can make SOP flame-retardant.
【００２１】この発明では、１００重量部のＳＯＰに、
５〜２０重量部のＴＢＯを含ませることが必要である。
なぜならば、ＴＢＯが５重量部未満では得られた組成物
が充分な難燃性を示さないからであり、逆にＴＢＯが２
０重量部を越えると、得られた組成物を発泡させたとき
発泡体の寸法安定性が劣るものとなるからである。In the present invention, in 100 parts by weight of SOP,
It is necessary to include 5 to 20 parts by weight of TBO.
This is because when the TBO content is less than 5 parts by weight, the composition obtained does not show sufficient flame retardancy, and conversely, when the TBO content is 2 or more.
This is because if the amount exceeds 0 parts by weight, the dimensional stability of the foam will be poor when the obtained composition is foamed.
【００２２】この発明では、ＳＯＰとＴＢＯとからなる
組成物の粒子を発泡性にするために、これに発泡剤を含
ませる。発泡剤は、これまでスチレン系樹脂に発泡性を
与えるために使用して来たものを使用することができ
る。その発泡剤はＳＯＰの軟化点より低い沸点を持った
脂肪族又は環式脂肪族炭化水素である。例を挙げると、
脂肪族炭化水素に属するものとしては、プロパン、イソ
ブタン、ｎ−ブタン、ペンタン等であり、環式脂肪族炭
化水素に属するものとしては、シクロペンタン、シクロ
ヘキサン等である。これらは単独で又は混合して用いる
ことができる。In the present invention, in order to make the particles of the composition composed of SOP and TBO expandable, a foaming agent is included therein. As the foaming agent, those which have been used so far for imparting foamability to the styrene resin can be used. The blowing agent is an aliphatic or cycloaliphatic hydrocarbon having a boiling point below the softening point of SOP. For example,
Those belonging to the aliphatic hydrocarbons are propane, isobutane, n-butane, pentane and the like, and those belonging to the cycloaliphatic hydrocarbons are cyclopentane, cyclohexane and the like. These can be used alone or in combination.
【００２３】この発明では発泡剤をＳＯＰ１００重量部
に対し２重量部以上含ませる。２重量部以上とする理由
は、２重量部未満では、これを含んだＳＯＰを加熱して
も満足に発泡しないからである。また、発泡剤量に格別
上限を設けない理由は、発泡剤が多くなるにつれて高倍
率に発泡する傾向を示し、或る限度以上になるとそれ以
上は高倍率に発泡しなくなるが、その限度に明確な限界
が認められないからである。In the present invention, the foaming agent is contained in an amount of 2 parts by weight or more per 100 parts by weight of SOP. The reason why the amount is 2 parts by weight or more is that if the amount is less than 2 parts by weight, even if the SOP containing this is heated, it will not satisfactorily foam. The reason why there is no special upper limit for the amount of blowing agent is that it tends to foam at a high ratio as the amount of the blowing agent increases, and when it exceeds a certain limit, it will not foam at a higher ratio, but it is clear to that limit. This is because no limit is recognized.
【００２４】ＳＯＰにＴＢＯと発泡剤とを含ませるに
は、耐圧密閉型の回転混合機をを用いる。まず、この混
合機中に１００重量部のＳＯＰを入れ、次いで５〜２０
重量部のＴＢＯと２重量部以上の発泡剤とを加え、混合
機を密閉する。このとき、ＴＢＯを先に入れ混合機を回
転させてよく攪拌してのち、発泡剤を入れてもよいが、
発泡剤が液状を呈しているときには、ＴＢＯを発泡剤に
溶解し、得られた溶液を混合機に入れてもよい。また、
このとき、ＳＯＰを溶解する溶剤を少量だけ混合機中に
加えることが好ましい。この溶剤は、例えば、ベンゼ
ン、トルエン、キシレンのような芳香族炭化水素、酢酸
メチル、酢酸エチルのようなエステルである。この溶剤
はＴＢＯと発泡剤とがＳＯＰに含浸されるのを促進する
働きをする。In order to include TBO and the foaming agent in the SOP, a pressure tight sealed rotary mixer is used. First, 100 parts by weight of SOP was put into this mixer, and then 5 to 20
Add 1 part by weight of TBO and 2 parts by weight or more of a foaming agent, and close the mixer. At this time, TBO may be added first, the mixer may be rotated to stir well, and then the foaming agent may be added.
When the foaming agent is in a liquid state, TBO may be dissolved in the foaming agent and the resulting solution may be put in a mixer. Also,
At this time, it is preferable to add only a small amount of a solvent that dissolves SOP into the mixer. This solvent is, for example, an aromatic hydrocarbon such as benzene, toluene or xylene, or an ester such as methyl acetate or ethyl acetate. This solvent serves to promote the impregnation of TBO and blowing agent into the SOP.
【００２５】ＳＯＰとＴＢＯと発泡剤とを混合機に入
れ、密閉したのち、混合機を回転させる。回転を続けな
がら、混合機を７０〜８５℃の温度に加熱する。この回
転と加熱とを１時間以上継続する。その後冷却して混合
機からＳＯＰを取り出す。ここに取り出されたものが、
この発明に係る発泡性粒子である。The SOP, TBO, and foaming agent are put into a mixer and sealed, and then the mixer is rotated. While continuing to rotate, heat the mixer to a temperature of 70-85 ° C. This rotation and heating are continued for 1 hour or more. Then, it cools and takes out SOP from a mixer. What was taken out here,
The expandable particles according to the present invention.
【００２６】上述の操作において、混合機の温度を７０
〜８５℃とする理由は、以下に述べるような実験の結果
から来ている。すなわち、混合機の温度が７０℃より低
いと、得られる発泡性粒子の難燃性が不充分であり、逆
に８５℃より高いと、得られる発泡性粒子が融着し合っ
て団塊を生じ、これを発泡させるとゴルフボールのよう
な大きな塊となって、あとの成形を円滑に行うことがで
きなくなるからである。In the above operation, the temperature of the mixer was set to 70
The reason why the temperature is set to ˜85 ° C. comes from the results of experiments as described below. That is, when the temperature of the mixer is lower than 70 ° C, the flame retardancy of the obtained expandable particles is insufficient, and conversely, when the temperature of the mixer is higher than 85 ° C, the obtained expandable particles are fused and form a nodule. This is because if this is foamed, it becomes a large mass like a golf ball, and the subsequent molding cannot be performed smoothly.
【００２７】上述のように、耐圧密閉型の回転混合機を
用い、これに１００重量部のＳＯＰと、５〜２０重量部
のＴＢＯと２重量部以上の発泡剤とを入れ、混合機を回
転させながら７０〜８５℃の温度に１時間以上保持する
と、ＴＢＯと発泡剤とはＳＯＰ中に一様に含浸され、ま
たＳＯＰはそのままの粒の形を保って、ここに所望の形
状大きさの発泡性粒子が容易に得られる。この発明方法
はこのように発泡性粒子の製造が容易であるという利益
を与える。As described above, a pressure-tight sealed rotary mixer was used, in which 100 parts by weight of SOP, 5-20 parts by weight of TBO and 2 parts by weight or more of a foaming agent were added, and the mixer was rotated. When the temperature is kept at 70 to 85 ° C. for 1 hour or more while being kept, the TBO and the foaming agent are uniformly impregnated in the SOP, and the SOP keeps the shape of the grain as it is, and here, the desired shape and size are obtained. Effervescent particles are easily obtained. The method of the invention thus offers the advantage that the expandable particles are easy to manufacture.
【００２８】こうして得られた発泡性粒子は、これを水
蒸気に接触させて加熱すると、発泡剤の含有量に比例し
てよく高倍率に発泡する。この発泡した粒子を数日間室
温に放置したのち、これを成形用の孔あき金型に入れ、
金型内に水蒸気を吹き込んで加熱すると粒子はさらに発
泡して互いに融着して、発泡成形体となる。When the expandable particles thus obtained are brought into contact with steam and heated, the expandable particles are well expanded in proportion to the content of the foaming agent. After leaving the foamed particles at room temperature for several days, put them in a perforated mold for molding,
When steam is blown into the mold and heated, the particles are further foamed and fused to each other to form a foamed molded body.
【００２９】この発泡成形体は、その中で粒子が互いに
強く融着し合っており、表面は金型の表面に密着した形
状となり、金型通りの大きさ形状を呈している。またこ
の発泡成形体は耐衝撃性が大きく、この上に金属塊を落
下させても容易に破壊されない。また、この成形体は難
燃性を示し、これに着火してのち、燃焼を続ける距離を
測定するという方法で難燃度を計ると、難燃性は充分で
ある。さらに驚くべきことは、難燃剤を加えているにも
拘らず寸法安定性が大きくて成形後の収縮が小さい。こ
のために運搬用箱、自動車のバンパー、ドアパッドなど
の構造材としての使用に向いている。この点でこの発明
の効果は大きい。In this foamed molded product, the particles are strongly fused to each other in the foamed product, and the surface has a shape in which it is in close contact with the surface of the mold, and has the size and shape as the mold. Further, this foamed molded article has a high impact resistance and is not easily broken even if a metal block is dropped on it. Further, this molded article exhibits flame retardancy, and after igniting this, the flame retardancy is measured by measuring the distance over which combustion continues, the flame retardancy is sufficient. What is more surprising is that the dimensional stability is high and the shrinkage after molding is small despite the addition of the flame retardant. Therefore, it is suitable for use as a structural material for transport boxes, automobile bumpers, door pads, etc. In this respect, the effect of the present invention is great.
【００３０】次に、実施例と比較例とを挙げて、この発
明の効果を具体的に明らかにする。以下で単に部という
のは重量部のことである。また、実施例及び比較例中で
難燃性、ビーズ結合、成形品の寸法安定性、及び耐衝撃
性を測定したが、それは次のような方法で測定したもの
である。 （ａ）難燃性はＦＭＶＳＳ ３０２（米国自動車安全基
準）の定める方法によって１分間の燃焼速度（長：ｍ
ｍ）を測定した。８０ｍｍ／分以下は良好とされる。 （ｂ）ビーズ結合は、発泡成形体における発泡粒子同士
の結合の良否を表す。 （ｃ）成形品の寸法安定性に、発泡成形後発泡体を７０
℃に４日間放置したときの収縮割合を測定した。 （ｄ）耐衝撃性は、２１５×４０×２０ｍｍの大きさの
発泡成形体上に３２１ｇの鋼球を落下させて４０ｍｍ以
上の長さの切れ目が生じたときに破断したと見做して、
破断時の高さを測定した。（ＪＩＳ−Ｋ ６７４５準
拠）Next, the effects of the present invention will be concretely clarified with reference to Examples and Comparative Examples. In the following, simply “part” means “part by weight”. In addition, flame retardancy, bead bonding, dimensional stability of molded products, and impact resistance were measured in Examples and Comparative Examples, which were measured by the following methods. (A) Flame retardancy is determined by the method specified by FMVSS 302 (US automobile safety standard) for a burning rate of 1 minute (long: m
m) was measured. 80 mm / min or less is considered good. (B) The bead bond represents the quality of the bond between the expanded particles in the expanded molded article. (C) For the dimensional stability of the molded product, the foam after foam molding should be 70
The shrinkage ratio when left at 4 ° C. for 4 days was measured. (D) The impact resistance was considered to be fractured when a 321 g steel ball was dropped onto a foamed molded body having a size of 215 × 40 × 20 mm and a break having a length of 40 mm or more was generated,
The height at break was measured. (JIS-K 6745 compliant)
【００３１】[0031]
【実施例１】内容積１００リットルのオートクレーブ
に、水性媒体として純水１００部、ピロ燐酸マグネシウ
ム０．４５部、ドデシルベンゼンスルホン酸ソーダ０．
０２部の混合物を入れ、これにポリエチレン樹脂粒子
（住友化学社製、商品名 エバテート Ｄ−１０４２）
３０部を加え、回転数２５０ｒｐｍで攪拌して水性媒体
中に懸濁させた。Example 1 In an autoclave having an internal volume of 100 liters, 100 parts of pure water as an aqueous medium, 0.45 part of magnesium pyrophosphate, sodium dodecylbenzenesulfonate of 0.
Add 02 parts of the mixture, and add polyethylene resin particles (Sumitomo Chemical Co., Ltd., trade name Evatate D-1042) to the mixture.
30 parts was added, and the mixture was stirred at 250 rpm and suspended in an aqueous medium.
【００３２】別に、重合用触媒としてベンゾイルパーオ
キサイド０．３部とｔ−ブチルパーオキシベンゾエート
０．０１部と、また、架橋剤としてジクミルパーオキサ
イド０．２５部を７０部のスチレン単量体に溶解させて
単量体溶液を作り、この溶液を前記水性媒体中に加え
て、ポリエチレン樹脂粒子に吸収させ、８５℃の温度に
４時間保持して重合を行った。その後、１４３℃に昇温
して、この温度に３時間保持して重合を完結させ、その
後冷却してＳＯＰの粒子を得た。Separately, 0.3 part of benzoyl peroxide and 0.01 part of t-butyl peroxybenzoate were used as a polymerization catalyst, and 70 parts of styrene monomer of 0.25 part of dicumyl peroxide was used as a crosslinking agent. To prepare a monomer solution, which was added to the aqueous medium to be absorbed by polyethylene resin particles, and maintained at a temperature of 85 ° C. for 4 hours for polymerization. Then, the temperature was raised to 143 ° C., the temperature was maintained for 3 hours to complete the polymerization, and then the mixture was cooled to obtain SOP particles.
【００３３】次いで内容積が４０リットルの耐圧密閉型
の回転混合機に上記ＳＯＰの粒子１００部を入れ、また
難燃剤としてＴＢＯ（第一工業製薬社製、商品名 ＦＲ
２００）１０部を入れ、混合機を回転させた。その
後、混合機を回転させながら溶剤としてトルエン１．５
部と、発泡剤としてブタン１４部を順次圧入した。さら
に混合機を回転させながら、７０℃の温度で３時間混合
して発泡剤を含浸させた。その後、冷却して難燃性の発
泡性粒子を得た。このとき、粒子はもとの形を保持して
いて、塊となったものが全くなかった。Next, 100 parts of the above-mentioned SOP particles were put into a pressure-tight rotary mixer having an internal volume of 40 liters, and TBO (manufactured by Daiichi Kogyo Seiyaku Co., trade name FR) was used as a flame retardant.
200) 10 parts were added and the mixer was rotated. Then, while rotating the mixer, toluene 1.5 as a solvent.
Part and 14 parts of butane as a foaming agent were sequentially pressed. Further, while rotating the mixer, the mixture was mixed at a temperature of 70 ° C. for 3 hours to impregnate the foaming agent. Then, it cooled and obtained the flame-retardant expandable particle. At this time, the particles retained their original shape, and no lumps were formed.
【００３４】その後、上で得た難燃性の発泡性粒子を嵩
倍率５５倍に予備発泡させた。得られた予備発泡粒子を
７日間室温に放置した後、４００×３００×１００ｍｍ
の大きさの成形用金型内に入れ、ゲージ圧０．５ｋｇ／
ｃｍ2 の水蒸気を１分間導入して加熱し、その後２０分
間冷却して発泡成形体を取り出した。Thereafter, the flame-retardant expandable particles obtained above were pre-expanded at a bulk ratio of 55 times. After leaving the obtained pre-expanded particles for 7 days at room temperature, 400 × 300 × 100 mm
In a molding die of the size
cm 2 of water vapor was introduced for 1 minute and heated, then cooled for 20 minutes and the foamed molded product was taken out.
【００３５】上で得た発泡成形体を５０℃の乾燥室で３
日間乾燥したのち、これをＦＭＶＳＳ No. ３０２に規
定される方法で燃焼試験を行ったところ燃焼速度は７６
ｍｍ／分で、８０ｍｍ／分以下を合格とする難燃性を示
すものであることが確認された。また、この発泡成形体
は、ビーズの結合が良好であった。さらにこの発泡成形
体について７０℃に４日間放置して収縮率を調べたとこ
ろ収縮率０．５％であって少ないことを認めた。また、
この発泡成形体の落球値は３５．５ｃｍであって、耐衝
撃性は良好であった。こうして、この発泡成形体は難燃
性であるだけでなく、耐衝撃性に富み寸法安定性がよ
く、発泡成形が容易でさらに外観も良好であるために、
自動車のバンパー、ドアパッドのような構造材として用
いるのに適していることが確認された。The foamed molded product obtained above was dried in a drying chamber at 50 ° C. for 3 hours.
After being dried for a day, a combustion test was carried out by the method specified in FMVSS No. 302.
It was confirmed that the material exhibited flame retardancy of 80 mm / min or less at mm / min. Also, this foamed molded product had good bead binding. Further, this foamed molded product was allowed to stand at 70 ° C. for 4 days and examined for shrinkage, and it was found that the shrinkage was 0.5%, which was small. Also,
The foamed article had a falling ball value of 35.5 cm and good impact resistance. Thus, this foamed molded article is not only flame-retardant, but also has good impact resistance, good dimensional stability, easy foaming, and a good appearance,
It was confirmed that it is suitable for use as structural materials such as automobile bumpers and door pads.
【００３６】[0036]
【実施例２〜５】この実施例２〜５は、実施例１と同様
に実施したが、ただＴＢＯの使用量をＳＯＰ１００部に
対し、それぞれ５、１０、１５、２０部にするととも
に、耐圧密閉型の回転混合機内で発泡剤を含浸させる時
の温度をそれぞれ８５℃、８５℃、７０℃、及び７０℃
に維持して実施し、何れも難燃性の発泡性粒子を得た。[Examples 2 to 5] Examples 2 to 5 were carried out in the same manner as Example 1 except that the amount of TBO used was changed to 5, 10, 15, and 20 parts per 100 parts of SOP, respectively, and the pressure resistance was increased. The temperature at which the foaming agent is impregnated in the closed rotary mixer is 85 ° C, 85 ° C, 70 ° C, and 70 ° C, respectively.
Was carried out, and flame retardant expandable particles were obtained.
【００３７】得られた発泡性粒子を使用して、あとは実
施例１と全く同様にして発泡成形体を作った。この発泡
成形体の性質を調べたところ、ＦＭＶＳＳ No. ３０２
の難燃性試験では、８０、６０、６９、６５ｍｍ／分の
燃焼速度を示したので良好な難燃性を示すと判断され
た。ビーズ結合の状態は何れも良好であり、また寸法安
定性は何れも良好であり、落球値は高さがそれぞれ３
４．５、４０．５、３７．５、３８．５ｃｍであって耐
衝撃性に富んでいた。従って、良好な発泡体を与えるも
のと認められた。Using the expandable particles thus obtained, a foamed molded product was produced in exactly the same manner as in Example 1. When the properties of this foamed molded product were investigated, it was found that FMVSS No. 302
In the flame retardancy test of No. 3, the burning rate was 80, 60, 69, and 65 mm / min. The bead-bound state was good, the dimensional stability was good, and the falling ball value was 3 in height.
It was 4.5, 40.5, 37.5, 38.5 cm, and was excellent in impact resistance. Therefore, it was recognized that it gave a good foam.
【００３８】[0038]
【比較例１〜３】この比較例は、実施例１と同様に実施
したが、ただ難燃剤としてのＴＢＯの使用量を増減し、
また発泡剤の含浸温度を変えて、この発明の規定する範
囲外として実施した。Comparative Examples 1 to 3 This comparative example was carried out in the same manner as in Example 1, except that the amount of TBO used as a flame retardant was increased or decreased.
Further, the impregnation temperature of the foaming agent was changed to carry out the treatment outside the range specified by the present invention.
【００３９】詳述すれば、比較例１は、ＴＢＯの使用量
を４部にし含浸温度を９０℃とした場合であり、比較例
２は、ＴＢＯの使用量を２５部にし含浸温度を６５℃と
した場合であり、比較例３はＴＢＯの使用量を零にして
含浸温度を７０℃とした場合である。More specifically, in Comparative Example 1, the amount of TBO used was 4 parts and the impregnation temperature was 90 ° C., and in Comparative Example 2, the amount of TBO used was 25 parts and the impregnation temperature was 65 ° C. Comparative Example 3 is a case where the amount of TBO used is zero and the impregnation temperature is 70 ° C.
【００４０】得られた難燃性の発泡性粒子を実施例１と
全く同様に処理して発泡成形体を作った。この発泡成形
体についてその物性を実施例１と全く同様にして調べ
た。その結果を比較例１〜３の順に述べると、ＦＭＶＳ
Ｓ No. ３０２の難燃性試験では燃焼速度がそれぞれ８
４、８６、２１５ｍｍ／分で何れも難燃性とは認められ
ず、ビーズ結合の状態は比較例１が悪かったが比較例２
と３とは良好であり、寸法安定性は比較例１と３とは良
好であったが比較例２が悪く、落球値は３２．５、３
０．５、２６．５ｃｍで、比較例１と２とは比較例３の
難燃剤を入れないものよりも良好であった。しかし全体
としては実施例１〜５よりも劣り悪いと認められた。The obtained flame-retardant expandable particles were treated in exactly the same manner as in Example 1 to produce a foamed molded product. The physical properties of this foamed molded product were examined in exactly the same manner as in Example 1. The results will be described in order of Comparative Examples 1 to 3, FMVS.
In the flame retardancy test of S No. 302, the burning rate was 8 each
No flame retardancy was observed at 4, 86 and 215 mm / min, and the state of bead binding was poor in Comparative Example 1, but Comparative Example 2
And 3 were good, and the dimensional stability was good in Comparative Examples 1 and 3, but bad in Comparative Example 2, and the falling ball value was 32.5, 3
At 0.5 and 26.5 cm, Comparative Examples 1 and 2 were better than Comparative Example 3 without the flame retardant. However, it was recognized that it was inferior to Examples 1 to 5 as a whole.
【００４１】[0041]
【比較例４〜９】この比較例は実施例１と同様に実施し
たが、ただ難燃剤としてこの発明で規定するＴＢＯ以外
の難燃剤を用い、その量をＳＯＰ１００部に対して１０
部とし、発泡剤の含浸温度を８０℃とした。Comparative Examples 4 to 9 This comparative example was carried out in the same manner as in Example 1, except that a flame retardant other than TBO specified in the present invention was used as the flame retardant, and the amount thereof was 10 per 100 parts of SOP.
And the impregnation temperature of the foaming agent was 80 ° C.
【００４２】詳述すれば、比較例４では難燃剤としてト
リブロモフェニルアリルエーテルを用い、比較例５では
テトラブロモビスフェノールＡのビスアリルエーテルを
用い、比較例６ではテトラブロモビスフェノールＡのビ
スジブロモプロピルエーテルを用い、比較例７ではヘキ
サブロモシクロドデカンを用い、比較例８ではデカブロ
モジフェニルエーテルを用い、比較例９では塩素化パラ
フィンを用い、何れもその量をＳＯＰ１００部に対し１
０部とし、８０℃で発泡剤を含浸させ、それ以外は実施
例１と全く同様にして難燃性の発泡性粒子を得た。More specifically, in Comparative Example 4, tribromophenyl allyl ether was used as a flame retardant, in Comparative Example 5, tetrabromobisphenol A bisallyl ether was used, and in Comparative Example 6, tetrabromobisphenol A bisdibromopropyl. Ether was used, hexabromocyclododecane was used in Comparative Example 7, decabromodiphenyl ether was used in Comparative Example 8, and chlorinated paraffin was used in Comparative Example 9. In each case, the amount was 1 per 100 parts of SOP.
Flame retardant expandable particles were obtained in the same manner as in Example 1 except that 0 part was used and impregnated with a foaming agent at 80 ° C.
【００４３】得られた発泡性粒子を実施例１と全く同様
に処理して発泡成形体を作った。この発泡成形体につい
てその物性を実施例１と全く同様にして調べた。その結
果を比較例４〜９の順に述べると、ＦＭＶＳＳ No. ３
０２の難燃性試験では燃焼速度がそれぞれ１０５、１０
１、１１８、１０２、１２２、１３０ｍｍ／分で何れも
８０ｍｍ／分の基準に達しなかった。ビーズ結合は何れ
も良好であったが、寸法安定性は比較例４、８、９が悪
くて比較例５〜７が良好であり、落球値はそれぞれ２
９．５、３５．５、２３．５、２１．５、２０．５、１
８．５で、比較例４と５とは良好であったが比較例６〜
９はすべて悪かった。The expandable particles thus obtained were treated in exactly the same manner as in Example 1 to prepare a foamed molded product. The physical properties of this foamed molded product were examined in exactly the same manner as in Example 1. The results will be described in order of Comparative Examples 4 to 9. FMVSS No. 3
In the flame retardancy test of 02, the burning rate was 105 and 10 respectively.
The values of 1, 118, 102, 122, and 130 mm / min did not reach the standard of 80 mm / min. The bead binding was good in all cases, but the dimensional stability was poor in Comparative Examples 4, 8 and 9 and good in Comparative Examples 5 to 7, and the falling ball value was 2 respectively.
9.5, 35.5, 23.5, 21.5, 20.5, 1
At 8.5, Comparative Examples 4 and 5 were good, but Comparative Examples 6 to
All 9 were bad.
【００４４】以上の実施例１〜５及び比較例１〜９の結
果を表にすると下記第１表のとおりとなる。Table 1 below shows the results of Examples 1 to 5 and Comparative Examples 1 to 9 described above.
【００４５】[0045]
【表１】 [Table 1]
Claims (2)
５〜５倍量のスチレン系単量体をグラフト重合させて得
られたグラフト重合体１００重量部に、テトラブロモシ
クロオクタン５〜２０重量部と、上記グラフト重合体の
軟化点より低い沸点を持った脂肪族又は環式脂肪族炭化
水素を２重量部以上含浸させたことを特徴とする、寸法
安定性のよい難燃性発泡体製造用樹脂粒子。1. The weight ratio of olefin resin 1 to 0.
100 parts by weight of a graft polymer obtained by graft-polymerizing 5 to 5 times the amount of styrene-based monomer, 5 to 20 parts by weight of tetrabromocyclooctane, and a boiling point lower than the softening point of the graft polymer. Resin particles for producing a flame-retardant foam having good dimensional stability, characterized by being impregnated with 2 parts by weight or more of an aliphatic or cycloaliphatic hydrocarbon.
〜５倍量のスチレン系単量体をグラフト重合させ、得ら
れたグラフト重合体粒子１００重量部を耐圧密閉型の回
転混合機に入れ、これに上記グラフト重合体の軟化点よ
り低い沸点を持った脂肪族炭化水素又は環式脂肪族炭化
水素を２重量部以上と、テトラブロモシクロオクタン５
〜２０重量部とを加え、回転混合機を密閉して回転させ
ながら７０〜８５℃の温度に１時間以上保持することを
特徴とする、寸法安定性のよい難燃性発泡体製造用樹脂
粒子の製造方法。2. The weight is 0.5 with respect to 1 of the olefin resin.
Graft polymerize 5 to 5 times the amount of the styrene monomer, and place 100 parts by weight of the obtained graft polymer particles in a pressure-resistant closed type rotary mixer, which has a boiling point lower than the softening point of the graft polymer. 2 parts by weight or more of an aliphatic hydrocarbon or a cycloaliphatic hydrocarbon, and tetrabromocyclooctane 5
Resin particles for producing a flame-retardant foam having good dimensional stability, characterized in that the temperature is maintained at 70 to 85 ° C. for 1 hour or more while the rotary mixer is sealed and rotated. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05347418A JP3093551B2 (en) | 1993-12-24 | 1993-12-24 | Resin particles for producing flame-retardant foam having good dimensional stability and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05347418A JP3093551B2 (en) | 1993-12-24 | 1993-12-24 | Resin particles for producing flame-retardant foam having good dimensional stability and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07179646A true JPH07179646A (en) | 1995-07-18 |
| JP3093551B2 JP3093551B2 (en) | 2000-10-03 |
Family
ID=18390096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05347418A Expired - Fee Related JP3093551B2 (en) | 1993-12-24 | 1993-12-24 | Resin particles for producing flame-retardant foam having good dimensional stability and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3093551B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007231068A (en) * | 2006-02-28 | 2007-09-13 | Sekisui Plastics Co Ltd | Styrene-modified thermoplastic polyurethane resin beads, expandable styene-modified thermoplastic polyurethane resin beads, styrene-modified thermoplastic polyurethane resin expanded beads, and styrene-modified thermoplastic polyurethane resin expansion molded form, and method for producing them |
| JP2009114432A (en) * | 2007-10-19 | 2009-05-28 | Kaneka Corp | Styrene modified polyethylene based resin particle, and prefoamed particle obtained from resin particle thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07179647A (en) * | 1993-12-24 | 1995-07-18 | Sekisui Plastics Co Ltd | Resin particle for production of flame retardant foam of good dimensional stability and its production |
-
1993
- 1993-12-24 JP JP05347418A patent/JP3093551B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07179647A (en) * | 1993-12-24 | 1995-07-18 | Sekisui Plastics Co Ltd | Resin particle for production of flame retardant foam of good dimensional stability and its production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007231068A (en) * | 2006-02-28 | 2007-09-13 | Sekisui Plastics Co Ltd | Styrene-modified thermoplastic polyurethane resin beads, expandable styene-modified thermoplastic polyurethane resin beads, styrene-modified thermoplastic polyurethane resin expanded beads, and styrene-modified thermoplastic polyurethane resin expansion molded form, and method for producing them |
| JP2009114432A (en) * | 2007-10-19 | 2009-05-28 | Kaneka Corp | Styrene modified polyethylene based resin particle, and prefoamed particle obtained from resin particle thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3093551B2 (en) | 2000-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4303757A (en) | Process for producing expandable thermoplastic resin beads using polypropylene as nucleus | |
| US4303756A (en) | Process for producing expandable thermoplastic resin beads | |
| KR101256271B1 (en) | Styrene polymer particle foam materials having reduced thermal conductivity | |
| JP4718645B2 (en) | Styrene modified polypropylene resin particles, expandable styrene modified polypropylene resin particles, styrene modified polypropylene resin foam particles, and method for producing styrene modified polypropylene resin foam molded article | |
| JP3093552B2 (en) | Resin particles for producing flame-retardant foam having good dimensional stability and method for producing the same | |
| JP3093551B2 (en) | Resin particles for producing flame-retardant foam having good dimensional stability and method for producing the same | |
| JP3103283B2 (en) | Expandable particles for producing impact resistant foam and method for producing the same | |
| JPS5858372B2 (en) | Method for producing foamable self-extinguishing thermoplastic resin particles | |
| JPH11255946A (en) | Foamable styrene-based resin particle having flame retardance and its production | |
| US4407979A (en) | Process for forming fast-cool vinyl aromatic expandable polymers | |
| JPS60206845A (en) | Expandable thermoplastic copolymer particle | |
| JPH064717B2 (en) | Method for producing expandable thermoplastic copolymer particles | |
| JPS5940164B2 (en) | Method for producing expandable thermoplastic resin particles | |
| US4430449A (en) | Fast-cool vinyl aromatic expandable polymers | |
| JPS60206848A (en) | Preparation of expandable thermoplastic copolymer particle | |
| JPS5915129B2 (en) | Method for producing thermoplastic resin particles | |
| KR100742946B1 (en) | Foaming styrene resin particles with a good strength, preparation method thereof and molded foam product prepared from the above particles | |
| KR930001945B1 (en) | Process for preparing particles of expandable polystyrene type resin | |
| JPS6140701B2 (en) | ||
| JP3240319B2 (en) | Spherical expandable resin particles and method for producing the same | |
| JPS6337140A (en) | Foamable styrene copolymer particle and production thereof | |
| JPS5915132B2 (en) | Method for producing thermoplastic resin particles | |
| JPS5928582B2 (en) | Method for producing expandable polymer particles | |
| JPH04255732A (en) | Preliminarily expanded beads of thermoplastic resin and production thereof | |
| JPS6337139A (en) | Production of foamable copolymer resin particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20000705 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080728 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090728 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |