JP4729841B2 - Expandable styrenic resin particles and method for producing the same - Google Patents
Expandable styrenic resin particles and method for producing the same Download PDFInfo
- Publication number
- JP4729841B2 JP4729841B2 JP2003298408A JP2003298408A JP4729841B2 JP 4729841 B2 JP4729841 B2 JP 4729841B2 JP 2003298408 A JP2003298408 A JP 2003298408A JP 2003298408 A JP2003298408 A JP 2003298408A JP 4729841 B2 JP4729841 B2 JP 4729841B2
- Authority
- JP
- Japan
- Prior art keywords
- resin particles
- styrene
- polymerization
- amount
- weight
- 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.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerization Catalysts (AREA)
Description
本発明は発泡性スチレン系樹脂粒子中の残存スチレン量が極めて少ない発泡性スチレン系樹脂粒子の製造方法、およびその製造方法により得られる樹脂に関するものである。 The present invention relates to a method for producing expandable styrene resin particles in which the amount of residual styrene in the expandable styrene resin particles is extremely small, and a resin obtained by the method.
近年、シックハウス問題をうけ、多くの樹脂について樹脂中に含まれる揮発性有機物を低減させる検討が進められている。発泡性スチレン系樹脂粒子についても建材用途、食品用トレー、あるいは容器などを中心に、樹脂粒子中の残存スチレン量を下げる検討が進められている。例えば特許文献1、特許文献2においては、可塑剤を不揮発性のものに変えると共に発泡性スチレン系樹脂粒子中に含まれる残存スチレン量を減少させるような発泡性スチレン系樹脂粒子について記されている。特に特許文献3においては残存スチレン量を300ppm以下にする方法が記されている。 In recent years, due to the problem of sick house, many resins have been studied to reduce the volatile organic substances contained in the resin. With regard to expandable styrene resin particles, studies are underway to reduce the amount of residual styrene in resin particles, mainly for building materials, food trays, and containers. For example, Patent Document 1 and Patent Document 2 describe expandable styrene resin particles that change the plasticizer to a non-volatile one and reduce the amount of residual styrene contained in the expandable styrene resin particles. . In particular, Patent Document 3 describes a method for reducing the amount of residual styrene to 300 ppm or less.
一方、特許文献4では、従来のt−ブチルパーオキサイドよりも水素引き抜き力が弱い、t−アルキル部分に少なくとも5個の炭素原子を有するアルキルパーオキサイドもしくはその誘導体が開示されている。
最終的に得られる樹脂粒子中の残存スチレン量を減少させるためには、一般的には重合温度を高くする、あるいは重合時間を長くすることにより、その目的が達成される。しかしながら、炭化水素系発泡剤を用いる重合系、あるいは、難燃性付与のため、発泡性スチレン系樹脂粒子に、例えばハロゲン系難燃剤を用いる重合系においては、開始剤の一次ラジカルが炭化水素系発泡剤、もしくはハロゲン系難燃剤に対して水素引き抜き反応を行うので、上記の従来方法である高温度、長時間重合を実施した場合においても残存スチレン量は減少しにくいという問題があった。例えば、特許文献3においては、発泡剤であるブタン添加後、120℃で6時間にわたり反応させるなど、極めて生産効率が悪い手段を用いて解決している。
In order to reduce the amount of residual styrene in the finally obtained resin particles, the object is generally achieved by increasing the polymerization temperature or extending the polymerization time. However, in a polymerization system using a hydrocarbon-based foaming agent, or in a polymerization system using, for example, a halogen-based flame retardant, in order to impart flame retardancy, the primary radical of the initiator is hydrocarbon-based. Since the hydrogen abstraction reaction is performed on the foaming agent or the halogen-based flame retardant, there is a problem that the amount of residual styrene is difficult to decrease even when the above-described conventional method is performed at a high temperature for a long time. For example, in Patent Document 3, after butane added is foamed agent, such as reacting for 6 hours at 120 ° C., it is solved by using the means extremely production efficiency is poor.
更に、特許文献4に開示され、水素引き抜き力が弱いラジカルを生成することがわかっているt−アルキル部分に少なくとも5個の炭素原子を有するアルキルパーオキサイドもしくはその誘導体を重合開始剤として用いる場合、t−アルキル部分の炭素数が増加するに伴い、その重合開始剤の10時間半減期温度が低下する傾向がある事もわかっている。この傾向に従い重合温度を低下させると、開裂した開始剤の運動性が低下し、スチレンモノマーの低下が遅くなるという問題が発生する。逆に重合温度を低下させなければ、開始剤の1次開裂が過度に発生し、最終的に得られる樹脂粒子中の残存スチレン量は減少しにくいという問題があった。 Further, when an alkyl peroxide having at least 5 carbon atoms in a t-alkyl moiety which is disclosed in Patent Document 4 and is known to generate a radical having a weak hydrogen abstraction force or a derivative thereof is used as a polymerization initiator, It has also been found that as the carbon number of the t-alkyl moiety increases, the 10 hour half-life temperature of the polymerization initiator tends to decrease. When the polymerization temperature is lowered according to this tendency, the problem is that the mobility of the cleaved initiator is lowered, and the fall of the styrene monomer is delayed. Conversely, if the polymerization temperature is not lowered, the primary cleavage of the initiator occurs excessively, and there is a problem that the amount of residual styrene in the finally obtained resin particles is difficult to decrease.
上記問題を解決すべく鋭意検討したところ、重合開始剤として一般式1に示す化合物を選択することによって初めて、生産性を下げることなく、発泡性スチレン系樹脂粒子中の残存スチレン量を大幅に減少させることができることがわかり本発明に至った。 As a result of intensive studies to solve the above problems, the amount of residual styrene in the expandable styrene resin particles is greatly reduced only by selecting the compound represented by the general formula 1 as a polymerization initiator without lowering the productivity. As a result, the present invention has been found.
即ち、本発明はスチレン系単量体100重量部に対し、0.05重量部以上、0.3重量部以下の一般式1に示される化合物を開始剤として併用しスチレン系単量体を重合すると共に、重合中または重合後に発泡剤を含浸することを特徴とする発泡性スチレン系樹脂粒子の製造方法(請求項1)、
That is, the present invention polymerizes a styrene monomer by using together 0.05 to 30 parts by weight of a compound represented by the general formula 1 as an initiator with respect to 100 parts by weight of a styrene monomer. And a method for producing expandable styrenic resin particles characterized by impregnating a foaming agent during or after polymerization (claim 1),
本発明によれば、重合開始剤として一般式1に示す化合物を選択することにより、重合温度を高くする、重合時間を延長するなどの生産性悪化の手段を取ることなく、発泡性スチレン系樹脂粒子中の残存スチレン量を500ppm以下にすることができる。 According to the present invention, by selecting a compound represented by the general formula 1 as a polymerization initiator, a foaming styrene resin can be obtained without taking measures for productivity deterioration such as increasing the polymerization temperature or extending the polymerization time. The amount of residual styrene in the particles can be 500 ppm or less.
以下,本発明の実施の形態をより詳細に説明する。 Hereinafter, embodiments of the present invention will be described in more detail.
本発明に用いるスチレン系単量体とは、スチレン、及びα―メチルスチレン、パラメチルスチレン、t-ブチルスチレン、クロルスチレンなどのスチレン系誘導体や、さらにスチレンと共重合が可能な成分、例えばメチルアクリレート、ブチルアクリレート、メチルメタクリレート、エチルメタクリレート、セチルメタクリレートなどのアクリル酸及びメタクリル酸のエステル、あるいはアクリロニトリル、ジメチルフマレート、エチルフマレートなどの各種単量体を1種又は2種以上、添加しても良い。また、ジビニルベンゼン、アルキレングリコールジメタクリレートなどの2官能性単量体を添加することもできる。 The styrene monomer used in the present invention includes styrene and styrene derivatives such as α-methyl styrene, paramethyl styrene, t-butyl styrene, chlorostyrene, and components that can be copolymerized with styrene, such as methyl Add one or more of various monomers such as acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, cetyl methacrylate and other acrylic acid and methacrylic acid esters, or acrylonitrile, dimethyl fumarate, ethyl fumarate Also good. Bifunctional monomers such as divinylbenzene and alkylene glycol dimethacrylate can also be added.
本発明においては前記スチレン系単量体を後述する分散剤により水中に分散させ、重合開始剤などを加えて、懸濁重合などにより重合し、該重合の途中、あるいは重合後に後述の発泡剤を含浸させて発泡性スチレン系樹脂粒子を得る。 In the present invention, the styrenic monomer is dispersed in water with a dispersant described later, added with a polymerization initiator, and polymerized by suspension polymerization or the like. Impregnated styrene resin particles are obtained by impregnation.
分散剤としては一般的に懸濁重合に用いられている分散剤、例えば、燐酸カルシウム、ハイドロキシアパタイト、ピロリン酸マグネシウムなどの難水溶性無機塩が上げられる。これら、難水溶性無機塩を用いる場合には、α-オレフィンスルフォン酸ソーダ、ドデシルベンゼンスルフォン酸ソーダなどのアニオン性界面活性剤を併用すると、分散安定性が増すので効果的である。また、難溶性無機塩は得られる発泡性スチレン系樹脂粒子の粒子径を調節するために、重合中に1回以上追加することもある。 Examples of the dispersant include dispersants generally used for suspension polymerization, such as poorly water-soluble inorganic salts such as calcium phosphate, hydroxyapatite, and magnesium pyrophosphate. In the case of using these poorly water-soluble inorganic salts, it is effective to use an anionic surfactant such as sodium α-olefin sulfonate and sodium dodecylbenzene sulfonate because the dispersion stability is increased. Further, the hardly soluble inorganic salt may be added one or more times during the polymerization in order to adjust the particle diameter of the resulting expandable styrene resin particles.
本発明は重合開始剤として下記一般式1に示される化合物を含むことを内容とする。 The present invention includes a compound represented by the following general formula 1 as a polymerization initiator.
発泡性スチレン系樹脂粒子の製造において、一般的には、樹脂を形成するための開始剤と残存スチレン量を低下させるための開始剤を併用させることが行われている。そして、これらの開始剤の選定は重合温度、重合時間、および必要とする樹脂の分子量を勘案して適宜決められる。本発明においては、一般式1に示される化合物を単独で使用することも可能であるが、他の重合開始剤を併用することにより、重合温度、重合時間、樹脂の分子量等の選択幅をより広げた上で、残存スチレン量を少なくした良好な製品を得ることができるので、併用することは好ましい実施態様である。 In the production of expandable styrene resin particles, generally, an initiator for forming a resin and an initiator for reducing the amount of residual styrene are used in combination. The selection of these initiators is appropriately determined in consideration of the polymerization temperature, the polymerization time, and the required molecular weight of the resin. In the present invention, the compound represented by the general formula 1 can be used alone, but by using other polymerization initiators in combination, the selection range such as the polymerization temperature, the polymerization time, and the molecular weight of the resin can be further increased. Since it is possible to obtain a good product with a small amount of residual styrene after spreading, it is a preferred embodiment to use in combination.
前記一般式1に示す化合物の使用量は求める発泡性スチレン系樹脂粒子の分子量により異なるが、スチレン100重量部に対して0.05重量部以上、0.3重量部以下、好ましくは0.1〜0.2重量部である。0.05重量部未満でも残存スチレン量を低下させることはできるが、長時間の重合時間を必要とし、工業生産上好ましくない。また、0.3重量部を越えても、残存スチレン量を低下させる能力は顕著に変わらないため、工業生産を鑑みた場合、コストアップの観点から好ましくない。 The amount of the compound represented by the general formula 1 varies depending on the molecular weight of the foamable styrene resin particles to be obtained. -0.2 parts by weight. Even if the amount is less than 0.05 parts by weight, the amount of residual styrene can be reduced, but it requires a long polymerization time, which is not preferable for industrial production. Moreover, even if it exceeds 0.3 weight part, since the capability to reduce the amount of residual styrene does not change remarkably, when considering industrial production, it is not preferable from a viewpoint of cost increase.
本発明にて使用される難燃剤は、粒子に難燃性を付与する目的で用いられる。少量で良好な難燃性を発揮させ、かつ成形性を悪化させない難燃剤として、一般的にはハロゲン系難燃剤が多用される。本発明におけるハロゲン系難燃剤としては、市販の一般的なものが使用されるが、その例としては、テトラブロモシクロオクタン、テトラブロモブタン、ヘキサブロモベンゼン、ヘキサブロモシクロドデカン、ポリグリセリンジブロモプロピルエーテル、テトラブロモビスフェノールA、モノクロロペンタブロモシクロヘキサン等をはじめとして多くの難燃剤が挙げられる。これらの中でもヘキサブロモシクロドデカンが最も好ましい。難燃剤の使用量については特に制限はなく、所望の難燃性を付与するに必要な量を添加する事ができる。 The flame retardant used in the present invention is used for the purpose of imparting flame retardancy to the particles. In general, halogen-based flame retardants are frequently used as flame retardants that exhibit good flame retardancy in a small amount and do not deteriorate moldability. As the halogen flame retardant in the present invention, commercially available general ones are used. Examples thereof include tetrabromocyclooctane, tetrabromobutane, hexabromobenzene, hexabromocyclododecane, polyglycerin dibromopropyl ether. And many flame retardants such as tetrabromobisphenol A, monochloropentabromocyclohexane and the like. Of these, hexabromocyclododecane is most preferred. There is no restriction | limiting in particular about the usage-amount of a flame retardant, The quantity required in order to provide desired flame retardance can be added.
本発明にて使用される発泡剤としては、C3からC5の炭化水素であるプロパン、イソブタン、ノルマルブタン、イソペンタン、ノルマルペンタン、ネオペンタンなどの脂肪族炭化水素類、およびジフルオロエタン、テトラフルオロエタンなどのオゾン破壊係数がゼロであるハイドロフルオロカーボン類などの揮発性発泡剤が使用できる。また、これらの発泡剤を併用することもできる。使用量としてはスチレン系樹脂粒子100重量部に対して、3〜12重量部、好ましくは5〜9重量部である。 Examples of the blowing agent used in the present invention include aliphatic hydrocarbons such as propane, isobutane, normal butane, isopentane, normal pentane, and neopentane, which are C 3 to C 5 hydrocarbons, and difluoroethane and tetrafluoroethane. Volatile blowing agents such as hydrofluorocarbons having an ozone depletion coefficient of zero can be used. Moreover, these foaming agents can also be used together. The amount used is 3 to 12 parts by weight, preferably 5 to 9 parts by weight, based on 100 parts by weight of the styrene resin particles.
このようにして得られた発泡性スチレン系樹脂粒子は残存スチレン量が500ppm以下と少なくなっている。 The foamable styrene resin particles thus obtained have a residual styrene content of 500 ppm or less.
以下に実施例、及び比較例を挙げるが、本発明はこれによって限定されるものではない。なお、実施例、及び比較例中の残存スチレン量については以下の方法で測定した。 Examples and Comparative Examples are given below, but the present invention is not limited thereby. In addition, about the amount of residual styrene in an Example and a comparative example, it measured with the following method.
(残存スチレン測定法)
発泡性スチレン系樹脂粒子を塩化メチレンに溶解し、(株)島津製作所製ガスクロマトグラフィーGC−14B(カラム充填剤:PEG20M Chromosorb WAW、カラム温度:110℃、キャリアガス:ヘリウム)を用いて、内部標準法(内部標準:シクロペンタノール)にて発泡性スチレン系樹脂粒子中に含まれる残存スチレン量(ppm)を定量した。
(Residual styrene measurement method)
Dissolve the expandable styrene resin particles in methylene chloride and use the gas chromatography GC-14B (column filler: PEG20M Chromosorb WAW, column temperature: 110 ° C., carrier gas: helium) manufactured by Shimadzu Corporation. The amount of residual styrene (ppm) contained in the expandable styrene resin particles was determined by a standard method (internal standard: cyclopentanol).
(実施例1)
6Lオートクレーブに水96重量部、第3リン酸カルシウム0.14重量部、α-オレインスルフォン酸ソーダ0.003重量部、過酸化ベンゾイル0.11部、1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサン0.19部を仕込んだ後、最後にスチレン100重量部を仕込み、98℃で4時間重合を行った。 その後ノルマルリッチブタン(ノルマル/イソ=70/30)を8部仕込み、114℃で2時間重合を行った。
(Example 1)
In a 6 L autoclave, 96 parts by weight of water, 0.14 part by weight of tricalcium phosphate, 0.003 part by weight of sodium α-olein sulfonate, 0.11 part of benzoyl peroxide, 1,1-bis (t-amylperoxy)- After charging 0.19 part of 3,3,5-trimethylcyclohexane, finally, 100 parts by weight of styrene was added and polymerization was carried out at 98 ° C. for 4 hours. Thereafter, 8 parts of normal rich butane (normal / iso = 70/30) was charged, and polymerization was carried out at 114 ° C. for 2 hours.
得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると200ppmであった。 The residual styrene content of the obtained expandable styrene resin particles was 200 ppm as measured by gas chromatography.
(実施例2)
6Lオートクレーブに水96重量部、第3リン酸カルシウム0.14重量部、α-オレインスルフォン酸ソーダ0.003重量部、過酸化ベンゾイル0.11部、ヘキサブロモシクロドデカン1.0部、1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサン0.19部を仕込んだ後、最後にスチレン100重量部を仕込み、98℃で4時間重合を行った。その後ノルマルリッチブタン(ノルマル/イソ=70/30)を8部仕込み、114℃で5時間重合を行った。
(Example 2)
In a 6 L autoclave, 96 parts by weight of water, 0.14 part by weight of tribasic calcium phosphate, 0.003 part by weight of α-olein sulfonate, 0.11 part of benzoyl peroxide, 1.0 part of hexabromocyclododecane, 1,1-bis ( After adding 0.19 part of (t-amylperoxy) -3,3,5-trimethylcyclohexane, 100 parts by weight of styrene was finally added and polymerization was carried out at 98 ° C. for 4 hours. Thereafter, 8 parts of normal rich butane (normal / iso = 70/30) was charged, and polymerization was carried out at 114 ° C. for 5 hours.
得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると300ppmであった。 The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography and found to be 300 ppm.
(実施例3)
1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサン0.07部仕込んだ以外は実施例1と同様に行った。得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると350ppmであった。
(Example 3)
The same procedure as in Example 1 was conducted except that 0.07 part of 1,1-bis (t-amylperoxy) -3,3,5-trimethylcyclohexane was charged. The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography and found to be 350 ppm.
(実施例4)
1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサン0.07部仕込んだ以外は実施例2と同様に行った。得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると450ppmであった。
Example 4
The same operation as in Example 2 was conducted except that 0.07 part of 1,1-bis (t-amylperoxy) -3,3,5-trimethylcyclohexane was charged. The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography and found to be 450 ppm.
(比較例1)
1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサンのかわりに1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサンを0.22部仕込んだ以外は実施例1と同様に行った。得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると750ppmであった。
(Comparative Example 1)
0.21 part of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane instead of 1,1-bis (t-amylperoxy) -3,3,5-trimethylcyclohexane The same procedure as in Example 1 was performed except that the preparation was performed. The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography to be 750 ppm.
(比較例2)
1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサンのかわりに1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサンを0.22部仕込んだ以外は実施例1と同様に行った。得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると950ppmであった。
(Comparative Example 2)
0.21 part of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane instead of 1,1-bis (t-amylperoxy) -3,3,5-trimethylcyclohexane The same procedure as in Example 1 was performed except that the preparation was performed. The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography and found to be 950 ppm.
(比較例3)
1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサン0.04部仕込んだ以外は実施例1と同様に行った。得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると600ppmであった。
(Comparative Example 3)
The same procedure as in Example 1 was conducted except that 0.04 part of 1,1-bis (t-amylperoxy) -3,3,5-trimethylcyclohexane was charged. The residual styrene content of the obtained expandable styrene resin particles was 600 ppm as measured by gas chromatography.
(比較例4)
1,1−ビス(t−アミルパーオキシ)−3,3,5−トリメチルシクロヘキサン0.04部仕込んだ以外は実施例2と同様に行った。得られた発泡性スチレン系樹脂粒子の残存スチレン量をガスクロマトグラフィーにて測定すると700ppmであった。
(Comparative Example 4)
The same operation as in Example 2 was conducted except that 0.04 part of 1,1-bis (t-amylperoxy) -3,3,5-trimethylcyclohexane was charged. The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography to be 700 ppm.
(比較例5)
114℃での重合時間を5時間にした以外は比較例1と同様に行った。得られた発泡性スチレン系樹脂粒子中の残存スチレン量をガスクロマトグラフィーにて測定すると500ppmであった。
(Comparative Example 5)
The same procedure as in Comparative Example 1 was conducted except that the polymerization time at 114 ° C. was changed to 5 hours. The amount of residual styrene in the obtained expandable styrene resin particles was measured by gas chromatography and found to be 500 ppm.
(比較例6)
114℃での重合時間を8時間にした以外は比較例2と同様に行った。得られた発泡性スチレン系樹脂粒子中の残存スチレン量をガスクロマトグラフィーにて測定すると600ppmであった。
The same procedure as in Comparative Example 2 was performed except that the polymerization time at 114 ° C. was changed to 8 hours. The amount of residual styrene in the obtained expandable styrene resin particles was 600 ppm as measured by gas chromatography.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003298408A JP4729841B2 (en) | 2003-08-22 | 2003-08-22 | Expandable styrenic resin particles and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003298408A JP4729841B2 (en) | 2003-08-22 | 2003-08-22 | Expandable styrenic resin particles and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005068266A JP2005068266A (en) | 2005-03-17 |
JP4729841B2 true JP4729841B2 (en) | 2011-07-20 |
Family
ID=34403912
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003298408A Expired - Fee Related JP4729841B2 (en) | 2003-08-22 | 2003-08-22 | Expandable styrenic resin particles and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4729841B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4494074B2 (en) * | 2004-04-09 | 2010-06-30 | 株式会社カネカ | Expandable polystyrene resin particles |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2915134B2 (en) * | 1990-11-19 | 1999-07-05 | 三菱化学ビーエーエスエフ株式会社 | Method for producing styrene-modified polyethylene resin particles |
JP2003064212A (en) * | 2001-08-27 | 2003-03-05 | Kanegafuchi Chem Ind Co Ltd | Foamable polystyrene-based resin particle and foam molding of polystyrene-based resin |
-
2003
- 2003-08-22 JP JP2003298408A patent/JP4729841B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2005068266A (en) | 2005-03-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101299384B1 (en) | Flame-retardant expandable styrene resin particles and method for producing same | |
JP5109227B2 (en) | Process for producing expandable styrene resin particles and expandable styrene resin particles obtained from the process | |
JP2007009018A (en) | Process for producing expandable styrenic resin particle, expandable styrenic resin particle and molded product of styrenic resin expanded particle | |
JPH11106548A (en) | Styrene-based foaming resin particulate | |
JP6205278B2 (en) | Expandable styrene resin particles and method for producing the same | |
US4281067A (en) | Method of polymerizing styrene | |
JP6542623B2 (en) | Method for producing expandable polystyrene resin particles | |
JP6220663B2 (en) | Expandable styrene resin particles imparted with flame retardancy and process for producing the same | |
JP4729841B2 (en) | Expandable styrenic resin particles and method for producing the same | |
JP4035979B2 (en) | Expandable polystyrene resin particles and method for producing the same | |
JP2004211042A (en) | Self fire-extinguishing type foaming styrenic resin particle, reserve foaming particle and foamed molded material | |
JP2007246566A (en) | Foamable thermoplastic resin particle and foamed molded article obtained from the same | |
JP2002356575A (en) | Foamable polystyrene resin particles and foamed molded material | |
JPH07179647A (en) | Resin particle for production of flame retardant foam of good dimensional stability and its production | |
JP2005126537A (en) | Foamable styrene-based resin particle, styrene-based resin foaming particle and molding of styrene-based resin foaming particle | |
JP2004155870A (en) | Expandable styrenic resin particle for building material and its expanded molded product | |
JP2003335891A (en) | Expandable polystyrene resin particle, polystyrene expansion molded product and its preparation process | |
KR100622807B1 (en) | Process for the production of expandable polystyrene | |
JP2011026506A (en) | Low volatile expandable polystyrene-based resin particle, manufacturing method therefor, low volatile polystyrene-based resin pre-expanded particle, and low volatile polystyrene-based resin expansion molded article | |
JP2018053181A (en) | Method for producing foamable styrene resin particle | |
JP4494074B2 (en) | Expandable polystyrene resin particles | |
JP6539436B2 (en) | Expandable polystyrene resin particles | |
JP3935849B2 (en) | Self-extinguishing styrene resin foam particles and self-extinguishing foam | |
JPH0461896B2 (en) | ||
JP2019059843A (en) | Manufacturing method of foamable styrene resin particle |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060626 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090115 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090120 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090323 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100302 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20100409 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100427 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110322 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110404 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140428 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4729841 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140428 Year of fee payment: 3 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |