JPS60206844A - Expandable thermoplastic copolymer particle - Google Patents
Expandable thermoplastic copolymer particleInfo
- Publication number
- JPS60206844A JPS60206844A JP6306884A JP6306884A JPS60206844A JP S60206844 A JPS60206844 A JP S60206844A JP 6306884 A JP6306884 A JP 6306884A JP 6306884 A JP6306884 A JP 6306884A JP S60206844 A JPS60206844 A JP S60206844A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- oil
- particles
- expandable thermoplastic
- thermoplastic copolymer
- 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.)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、耐熱性・耐溶剤性に優れ、かつ発泡性・成形
性の良好な発泡性熱可塑性共重合体粒子に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to expandable thermoplastic copolymer particles that have excellent heat resistance and solvent resistance, as well as good foamability and moldability.
発泡性重合体粒子としては、発泡性ポリスチレン樹脂粒
子がよく知られており、該粒子を用いることによって安
価で容易に型発泡成形体を得ることが出来る。しかしな
がら、該発泡成形体は、重合物を構成する単量体がスチ
レンであるので比較的温度の高い配管の保温材、屋根用
断熱材、自動車部材、ソーラーシステム用保温材等の耐
熱性を要求される用途には使用できない欠点がある。ま
た、特に自動車部材等において、他素材と貼り合わせて
用いる場合、耐溶剤性が劣るため、接着材の選択が困難
であるという欠点も有している。As expandable polymer particles, expandable polystyrene resin particles are well known, and by using these particles, a molded foamed article can be easily obtained at low cost. However, since the monomer constituting the polymer is styrene, this foamed molded product requires heat resistance for use in relatively high-temperature pipe insulation materials, roof insulation materials, automobile parts, insulation materials for solar systems, etc. There are drawbacks that prevent it from being used for certain purposes. Furthermore, when used in combination with other materials, particularly in automobile parts, etc., it also has the disadvantage that it is difficult to select an adhesive material because of poor solvent resistance.
この為、本発明者らは、実用性に於て充分な耐熱性と耐
溶剤性を有する発泡性熱可塑性重合体粒子を得るには、
重合体を構成する単量体組成として、アルファメチルス
チレン１０重量％以上、かつ、アクリロニトリルを５％
以上含有してなる共重合体粒子を得、この樹脂粒子に易
揮発性発泡剤を含有せしめる必要があると考えた。しか
るに、かかる発泡性熱可塑性共重合体粒子を予備発泡し
た後、型成形を行ない、発泡成形体を得、該発泡成形体
を高温下に放置しておいた場合、その発泡成形体の寸法
変化はほとんど無いにも拘らず、成形体表面層部分を形
成する発泡粒子が夫々膨張することによって、成形体表
面にみにくい凹凸（以下、三次発泡と云う）が発生し、
美観が著しく損なわれてしまうという問題が明らかにな
ってきた。Therefore, in order to obtain expandable thermoplastic polymer particles having sufficient heat resistance and solvent resistance for practical use, the present inventors
The monomer composition constituting the polymer is 10% by weight or more of alpha methylstyrene and 5% of acrylonitrile.
It was thought that it was necessary to obtain copolymer particles containing the above-mentioned resin particles and to incorporate an easily volatile blowing agent into the resin particles. However, after pre-foaming such expandable thermoplastic copolymer particles, molding is performed to obtain a foamed molded product, and when the foamed molded product is left under high temperature, dimensional changes in the foamed molded product occur. Although there is almost no foaming, unsightly irregularities (hereinafter referred to as tertiary foaming) occur on the surface of the molded product due to the expansion of the foamed particles forming the surface layer of the molded product.
It has become clear that the aesthetic appearance has been severely damaged.
本発明者らは、かかる欠点に鑑み鋭意研究を重ねた結果
、上記方法にて得られた発泡性熱可塑性共重合体粒子の
表面に、特定の食用油を塗布することによって高温条件
下でも三次発泡がなく、寸法変化もほとんどない耐熱性
の優れた発泡成形体を与える発泡性熱可塑性共重合体粒
子を見出し、本発明を完成するに到った。As a result of extensive research in view of these drawbacks, the present inventors have found that by applying a specific edible oil to the surface of the expandable thermoplastic copolymer particles obtained by the above method, the tertiary state can be maintained even under high temperature conditions. The present inventors have discovered expandable thermoplastic copolymer particles that provide a foamed molded article with excellent heat resistance that does not cause foaming and has almost no dimensional change, and has completed the present invention.
すなわち本発明は、重合体を構成する単量体が、アルフ
ァメチルスチレン１０〜８０重量％、アクリロニトリル
５〜５０重量％、更にスチレン、クロルスチレン、パラ
メチルスチレン、［−ブチルスチレン、アクリル酸エス
テル、メタクリル酸エステルから選ばれた少なくとも１
種の化合物０〜７０重量％であり、易揮発性発泡剤２〜
１５重量％を含有し、表面が常温で液状の食用油で被覆
された発泡性熱可塑性共重合体粒子を内容とするもので
ある。That is, in the present invention, the monomers constituting the polymer include 10 to 80% by weight of alpha methylstyrene, 5 to 50% by weight of acrylonitrile, and further styrene, chlorostyrene, paramethylstyrene, [-butylstyrene, acrylic ester, At least one selected from methacrylic acid esters
0 to 70% by weight of the seed compound and 2 to 70% of the easily volatile blowing agent.
It contains expandable thermoplastic copolymer particles containing 15% by weight, the surface of which is coated with an edible oil that is liquid at room temperature.
本発明に使用されるアルファメチルスチレンの量は、１
０〜８０重量％の範囲で、所望する耐熱゛ 性と発泡倍
率によって決められるが、１０重量％未満であると耐熱
性向上の効果が見られなくなり、また８０重量％を越え
る量のアルファメチルスチレンを含む共重合体を高い重
合転化率で製造することは非常に困難である。The amount of alpha methylstyrene used in the present invention is 1
The amount is determined in the range of 0 to 80% by weight, depending on the desired heat resistance and expansion ratio, but if it is less than 10% by weight, the effect of improving heat resistance will not be seen, and if the amount exceeds 80% by weight, alpha methylstyrene It is very difficult to produce a copolymer containing this at a high polymerization conversion rate.
５０倍発発泡形体で１００°Ｃの耐熱性を得る為には、
アルファメチルスチレン２０〜５０重量％を用いる必要
があり、５〜１５倍発泡成形体で１１０°Ｃの耐熱性を
得る為には５０〜８０重量％のアルファメチルスチレン
を用いる必要がある。In order to obtain heat resistance of 100°C with a 50 times expanded foam,
It is necessary to use 20 to 50% by weight of alpha methylstyrene, and in order to obtain a heat resistance of 110°C with a 5 to 15 times foamed product, it is necessary to use 50 to 80% by weight of alpha methylstyrene.
又、本発明に使用されるアクリロニトリルは、発泡体に
耐油性を発揮させる為に必要であり、また従来、アルフ
ァメチルスチレンを多量用いて、懸濁重合で高い重合転
化率を得ることは困難であったが、このアクリロニトリ
ルを併用することによって可能ならしめているのである
。用いるアクリロニ） ＩＪル量が５重量％未満では組
成物の重合転化率が低くなり、かつ耐油性において効果
が発揮できなくなり好ましくない。又、５０重量％をこ
えて用いても重合転化率は変らず、樹脂が黄褐色に着色
するので好ましくない。In addition, acrylonitrile used in the present invention is necessary to make the foam exhibit oil resistance, and conventionally, it has been difficult to obtain a high polymerization conversion rate in suspension polymerization using a large amount of alpha methylstyrene. However, it has been made possible by using acrylonitrile in combination. If the amount of acrylonitrile used is less than 5% by weight, the polymerization conversion rate of the composition will be low and the oil resistance will not be effective, which is not preferable. Further, even if it is used in an amount exceeding 50% by weight, the polymerization conversion rate does not change and the resin is colored yellowish brown, which is not preferable.
アルファメチルスチレン及びアクリロニトリル以外の単
量体としては、スチレン、クロルスチレン、パラメチル
スチレン、ｔ−ブチルスチレン等の各種置換スチレン；
メチルアクリレート、エチルアクリレート、ブチルアク
リレート等のアクリル酸エステル；メチルメタクリレー
ト、エチルメタクリレート、ブチルメタクリレート等の
メタクリル酸エステルの中の１種又は２種以上を適宜用
いることができる。Monomers other than alpha-methylstyrene and acrylonitrile include various substituted styrenes such as styrene, chlorostyrene, para-methylstyrene, and t-butylstyrene;
One or more of acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate can be used as appropriate.
本発明に用いられる易揮発性発泡剤としては、プロパン
、ブタン、ペンタン等の脂肪族炭化水素ｉシクロブタン
、シクロペンタン、シクロヘキサン等の環式脂肪族炭化
水素及びトリクロルフルオルメタン、ジクロルフルオル
メタン、ジクロルフルオルメタン、メチルクロライド、
ジクロルテトラフルオルメタン、エチルクロライド等の
ハロゲン化炭化水素があげられる。これら発泡剤の用い
られるべき量は、所望する発泡成形体の発泡倍率によっ
て異なるが、２重量％から１５重量％を含有せしむるこ
とにより２倍から１００倍の発泡成形体を得ることが可
能である。Easily volatile blowing agents used in the present invention include aliphatic hydrocarbons such as propane, butane, and pentane, cycloaliphatic hydrocarbons such as cyclobutane, cyclopentane, and cyclohexane, and trichlorofluoromethane and dichlorofluoromethane. , dichlorofluoromethane, methyl chloride,
Examples include halogenated hydrocarbons such as dichlorotetrafluoromethane and ethyl chloride. The amount of these blowing agents to be used varies depending on the desired expansion ratio of the foamed molded product, but by containing 2 to 15% by weight, it is possible to obtain a foamed molded product that is 2 times to 100 times larger. It is.
本発明は、上記組成物に加えて常温で液状の食用油で粒
子表面が被覆されていることを特徴としている。従来、
発泡性熱可塑性樹脂粒子表面を塗布剤で被覆して表面を
改質する技術としては、発泡性ポリスチレン系樹脂粒子
を各種滑剤を被覆することによって該粒子の予備発泡時
のブロンキング防止、型成形を行なう際の融着性改良、
及び成形冷却時間の短縮などの技術が知られているが、
これらの技術の中で用いられている各種滑剤を、本発明
の共重合体組成物に用いても、成形加工及び得られる発
泡体に何ら顕著な効果を与えない。The present invention is characterized in that, in addition to the above composition, the particle surfaces are coated with an edible oil that is liquid at room temperature. Conventionally,
The technology to modify the surface of expandable thermoplastic resin particles by coating them with a coating agent includes coating expandable polystyrene resin particles with various lubricants to prevent bronking during pre-foaming of the particles, and to prevent mold forming. Improved fusion properties when performing
Although technologies such as shortening molding and cooling time are known,
Even if the various lubricants used in these techniques are used in the copolymer composition of the present invention, they do not have any significant effect on the molding process or the resulting foam.
これは、本発明に於る共重合体が、用いる単量体に起因
して耐油性を有している為である。しかして、従来、発
泡性スチレン系樹脂粒子に常温で液状の食用油を被覆す
るときは粒子表面にひび割れが生じたり、粒子中の発泡
剤がすみやかに逸散してしまったり、また予備発泡時の
ブロッキングが多量発生して使用上、問題があった。し
かるに、本発明において、常温で液状の食用油で、上記
組成物を被覆したところ、粒子表面にひび割れが生じた
り粒子中の発泡剤がすみやかに逸散してしまう等の問題
点もなく、かつ該粒子を用いて得られた発泡成形体の三
次発泡抑制に顕著な効果が得られたのである。This is because the copolymer of the present invention has oil resistance due to the monomer used. Conventionally, when coating expandable styrene resin particles with edible oil that is liquid at room temperature, cracks occur on the particle surface, the blowing agent in the particles quickly evaporates, or during pre-foaming. There was a problem in usage as a large amount of blocking occurred. However, in the present invention, when the above composition is coated with an edible oil that is liquid at room temperature, there are no problems such as cracking on the particle surface or rapid dissipation of the blowing agent in the particle. A remarkable effect was obtained in suppressing tertiary foaming of the foamed molded article obtained using the particles.
かかる目的で使用される食用油としては、ヤシ油、パー
ム核油、パーム油、アマニ油、大豆油、キリ油、トウモ
ロコシ油、ゴマ油、ナタネ油、綿実油、オリーブ油、落
花生油など常温で液状の食用油があげられる。その中で
も特に、ヤシ油、パーム核油等の、食用油を構成する脂
肪酸組成が炭素数１２個の脂肪酸を４０重量％以上含む
低級酸型油脂を用いることにより上記効果が顕著で、か
つ予備発泡時にブロッキングが増加することもないので
ある。このような食用油の使用量は、発泡性熱可塑性共
重合体粒子に対して００１〜１．０重量％が好ましい。Edible oils used for this purpose include coconut oil, palm kernel oil, palm oil, linseed oil, soybean oil, tung oil, corn oil, sesame oil, rapeseed oil, cottonseed oil, olive oil, peanut oil, and other edible oils that are liquid at room temperature. I can give you oil. Among these, the above effects are particularly noticeable by using lower acid type fats and oils such as coconut oil and palm kernel oil, which have a fatty acid composition of 12 carbon atoms or more and contain 40% by weight or more of the fatty acid composition constituting the edible oil. Sometimes there is no increase in blocking. The amount of such edible oil used is preferably 0.01 to 1.0% by weight based on the expandable thermoplastic copolymer particles.
００１重量％未満では三次発泡抑制の効果が小さく、１
．０重量％をこえて用いると該粒子を予備発泡した後、
型成形するときの成形性が悪化し、型どうりの形状を有
し、かつ表面平滑な成形体を得る条件中が非常に狭いか
、あるいは全くなくなり好ましくない。If it is less than 0.001% by weight, the effect of suppressing tertiary foaming is small;
．． If more than 0% by weight is used, after pre-foaming the particles,
This is undesirable because the moldability during molding deteriorates, and the range of conditions for obtaining a molded product having the shape of the mold and a smooth surface is very narrow or completely eliminated.
本発明の発泡性熱可塑性共重合体粒子を得る方法として
は、■乳化重合法で上記組成物の共重合体を得た後、ペ
レット化し、オートクレーブ中で易揮発性発泡剤を含浸
し、得られた発泡性熱可塑性共重合体粒子を食用油で被
覆する方法、■塊状重合法で上記組成物の共重合体を得
た後、ペレット化し、オートクレーブ中で易揮発性発泡
剤を含浸し、得られた発泡性熱可塑性共重合体粒子を食
用油で被覆する方法、■懸濁重合にて上記組成物゛ の
共重合体粒子を得、次いで易揮発性発泡剤を含浸し、得
られた発泡性熱可塑性共重合体粒子を食用油で被覆する
方法が掲げられる。しかしながら、。The method for obtaining the expandable thermoplastic copolymer particles of the present invention is as follows: (1) After obtaining the copolymer of the above composition by an emulsion polymerization method, it is pelletized and impregnated with an easily volatile blowing agent in an autoclave. A method of coating the foamable thermoplastic copolymer particles obtained with edible oil; A method of coating the obtained expandable thermoplastic copolymer particles with an edible oil, (2) obtaining copolymer particles of the above composition by suspension polymerization, and then impregnating them with an easily volatile blowing agent; A method of coating expandable thermoplastic copolymer particles with edible oil is mentioned. however,.
■の乳化重合法に於ては、プロセスの煩雑さによるコス
トアンプと乳化剤、凝固剤の混入による品質の低下があ
り、■の塊状重合法に於ては、重合後ペレット化を行な
った後、発泡剤含浸を行なわなければならないというプ
ロセスの煩雑さの点で、懸濁重合法■に劣っている。In the emulsion polymerization method (2), there is a cost increase due to the complexity of the process and a decrease in quality due to the contamination of emulsifiers and coagulants.In the bulk polymerization method (2), after pelletizing after polymerization, It is inferior to suspension polymerization method (2) in terms of the complexity of the process, which requires impregnation with a blowing agent.
しかしながら、従来、アルファメチルスチレンを上記の
如く多量使用し、懸濁重合又は塊状重合で、実用に供し
得る程に高分子量の共重合体を得ることは非常に困難と
されていた。本発明に於て、この懸濁重合及び塊状重合
によって実用に供し得る程に高分子量のアルファメチル
スチレン−アクリロニトリル系共重合体の重合を可能な
らしめたものは、特定の開始剤の使用と、重合温度条件
の選択である。However, in the past, it has been considered very difficult to obtain a copolymer with a high molecular weight that can be put to practical use by using a large amount of alpha methylstyrene as described above and carrying out suspension polymerization or bulk polymerization. In the present invention, what makes it possible to polymerize an alpha methylstyrene-acrylonitrile copolymer with a high molecular weight that can be used practically by suspension polymerization and bulk polymerization is the use of a specific initiator, This is the selection of polymerization temperature conditions.
かかる観点から、使用されるべき開始剤としては、ｔ−
ブトキシラジカルを発生させる二官能性有機過酸化物が
用いられるが、特に１０時間半減期温度が６０〜１２０
°Ｃであるものが好適である。From this point of view, the initiator to be used is t-
Difunctional organic peroxides that generate butoxy radicals are used, especially those with a 10-hour half-life temperature of 60 to 120
°C is preferred.
これらの条件を満たし、実際に使用に供せられる開始剤
としては、ジ−ｔ−ブチルパーオキシヘキサハイドロテ
レフタレート １．１−ジ−ｔ−ブチルパーオキシ−８
，８，５−）リメチルシクロヘキサン、ジ−ｔ−ブチル
パーオキシアゼレート２．５−ジメチル−２，５−ジー
（ｔ−ブチルパーオキシ）ヘキサン、１．１−ジー［−
ブチルパーオキシシクロヘキサン、ｌ、３−ビス−（１
−ブチルパーオキシイソプロピル）ベンゼン、２，２−
ジー（ｔ−ブチルパーオキシ）ブタン、４，４−ジーｔ
−プチルパーオキシバレリツク酸ｎ−ブチルエステル、
ジ−ｔ−ブチルパーオキシトリメチルアジペート等があ
げられる。これらの開始剤の使用量は、単量体総量のＯ
１〜２．０重量％てあり、０．１重量％未満では工業的
に実用性のある重合転化率が全く得られないか、もしく
は長時間を要し、著しく生産性の悪いものとなる。２，
０重量％をこえると分子量が著しく低下し、満足すべき
発泡成形が行なえないか、もしくはかろうじて発泡成形
が行なえても強度が大巾に劣った発泡成形体しか得られ
ない。Initiators that meet these conditions and can be used in practice include di-t-butylperoxyhexahydroterephthalate 1.1-di-t-butylperoxy-8
,8,5-)limethylcyclohexane, di-t-butylperoxyazelate 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di[-
Butylperoxycyclohexane, l,3-bis-(1
-butylperoxyisopropyl)benzene, 2,2-
Di(t-butylperoxy)butane, 4,4-dit
-butyl peroxyvaleric acid n-butyl ester,
Examples include di-t-butylperoxytrimethyl adipate. The amount of these initiators used is based on the total amount of monomers.
If the amount is less than 0.1% by weight, an industrially practical polymerization conversion rate may not be obtained at all, or it may take a long time, resulting in extremely poor productivity. 2,
If it exceeds 0% by weight, the molecular weight will drop significantly and satisfactory foam molding will not be possible, or even if foam molding can be carried out, only a foam molded product with significantly inferior strength will be obtained.
又、これらの開始剤を用いる場合の重合温度は８０〜１
３５°Ｃが好ましく、８０°Ｃ未満では重合転化率が極
めて低くなり、また１３０°Ｃをこえると分子量が低下
して、満足な発泡成形体が得難い。In addition, when using these initiators, the polymerization temperature is 80 to 1
The temperature is preferably 35°C, and if it is less than 80°C, the polymerization conversion rate will be extremely low, and if it exceeds 130°C, the molecular weight will decrease, making it difficult to obtain a satisfactory foam molded product.
かくして得られた本発明の発泡性熱可塑性共重合体粒子
は、水蒸気、熱風等の加熱媒体により所望する倍率まで
予備発泡せしめた後、閉塞し得るが密閉し得ない型中に
充填され、水蒸気等の加熱媒体によって再び加熱するこ
とによって所望の形状を有する耐熱性発泡体となし得る
。The thus obtained expandable thermoplastic copolymer particles of the present invention are pre-expanded to a desired magnification using a heating medium such as steam or hot air, and then filled into a mold that can be closed but cannot be sealed. By heating again with a heating medium such as, a heat-resistant foam having a desired shape can be obtained.
以下、本発明を実施例にて説明する。The present invention will be explained below with reference to Examples.
実施例１
撹拌機付きオートクレーブ中に純水１１０重量部、第三
リン酸カルシウム０．０８重量部、ドデシルベンゼンス
ルフオン酸ソーダｏ、ｏｏａ重量部を仕込んだ後、撹拌
下、アルファメチルスチレン３０重量部、アクリロニト
リル２０重量部、スチレン５０重量部からなる単量体と
、トルエン１０重量部、ジ−ｔ−ブチルパーオキシヘキ
サハイドロテレフタレート０．５重量部を混合して、オ
ートクレーブ中に加え、９５°Ｃに昇温した後、３時間
後に第三リン酸カルシウム０３部を加え更に５時間の重
合を行なった。得られた組成物の重合転化率は９９．４
％であった。次いでブタン１０重量部を加え、１００°
Ｃで８時間の発泡剤含浸を行なった。得られた発泡性熱
可塑性共重合体粒子を樹脂（Ａ）とし、この樹脂（Ａ）
を用いて以下の実験を行なった。Example 1 After charging 110 parts by weight of pure water, 0.08 parts by weight of tribasic calcium phosphate, and parts by weight of sodium dodecylbenzenesulfonate o and ooa into an autoclave equipped with a stirrer, 30 parts by weight of alpha methylstyrene was added under stirring. A monomer consisting of 20 parts by weight of acrylonitrile and 50 parts by weight of styrene, 10 parts by weight of toluene, and 0.5 parts by weight of di-t-butylperoxyhexahydroterephthalate was mixed, added to an autoclave, and heated to 95°C. After raising the temperature, 03 parts of tribasic calcium phosphate was added 3 hours later, and polymerization was further carried out for 5 hours. The polymerization conversion rate of the obtained composition was 99.4
%Met. Next, add 10 parts by weight of butane and heat to 100°.
Blowing agent impregnation was carried out at C for 8 hours. The obtained expandable thermoplastic copolymer particles are referred to as resin (A), and this resin (A)
The following experiment was conducted using
実施例２
実施例１で得た樹脂（Ａ）に、撹拌機付きのブレングー
中で、ヤシ油０１重量部と、ブロッキング防止剤として
ステアリン酸カルシウム粉末０．１重量部を被覆した。Example 2 The resin (A) obtained in Example 1 was coated with 0.1 part by weight of coconut oil and 0.1 part by weight of calcium stearate powder as an antiblocking agent in a blender equipped with a stirrer.
次いで、該樹脂を水蒸気で加熱することにより見掛倍率
５０倍に予備発泡した後、閉塞し得るが密閉し得ない金
型に充填し、水蒸気で加熱することにより４５α×３０
αＸ２ｆｆｉの板状発泡成形体を得た。Next, the resin is heated with steam to pre-foam to an apparent magnification of 50 times, and then filled into a mold that can be closed but cannot be sealed, and heated with steam to form a foam of 45α×30
A plate-shaped foam molded product of αX2ffi was obtained.
上記の発泡成形体を１００°Ｃの熱風式均熱乾燥機内に
１週間放置した後の、初期寸法に対する寸法変化率及靜
、成形体表面の三次発泡状態を調べ、結果を表−１に示
した。After the above foamed molded product was left in a hot air soaking dryer at 100°C for one week, the dimensional change rate with respect to the initial dimension, the tertiary foaming state on the surface of the molded product were investigated, and the results are shown in Table 1. Ta.
実施例３〜５
実施例２において、ヤシ油をオリーブ油、大豆油、パー
ム核油に変えた以外は同様にして実施した。結果を表−
１に示した。Examples 3 to 5 Examples were carried out in the same manner as in Example 2 except that coconut oil was changed to olive oil, soybean oil, or palm kernel oil. Display the results -
Shown in 1.
比較例１〜３
実施例２において、ヤシ油を用いないブランク（比較例
１）、硬化大豆油（比較例２）、硬化ひまし油（比較例
３）を用いて実施例２と同様にした。結果を表−１に示
した。Comparative Examples 1 to 3 The same procedure as in Example 2 was carried out using a blank without coconut oil (Comparative Example 1), hydrogenated soybean oil (Comparative Example 2), and hydrogenated castor oil (Comparative Example 3). The results are shown in Table-1.
実施例６，７
実施例２において、ヤシ油の量を、夫々０．０５重量部
、０５重量部とした以外は同様にした。結果を表−２に
示す。Examples 6 and 7 The same procedure as in Example 2 was carried out except that the amounts of coconut oil were changed to 0.05 parts by weight and 0.05 parts by weight, respectively. The results are shown in Table-2.
表−１ × ◎：三次発泡 全くなし ○： ／ｌ はとんとなし △：／／ かなり有り 表−２ × ◎：三次発泡 全くなし ○：ｌ／ はとんどなし △：ｌｌ かなり有り 特許出願人 鐘淵化学工業株式会社 代理人 弁理士 浅 野 真 −Table-1 × ◎：No tertiary foaming at all ○: /l is ridiculous △：／／ Quite a lot Table-2 × ◎：No tertiary foaming at all ○:l/ is almost impossible △:ll Quite a bit Patent applicant Kanebuchi Chemical Industry Co., Ltd. Agent: Patent Attorney Makoto Asano -
Claims (3)
レン１０〜８０重量％、アクリロニトリル５〜５０重量
％、更にスチレン、クロルスチレン、パラメチルスチレ
ン、ｔ−ブチルスチレン、アクリル酸エステル、メタク
リル酸エステルから選ばれた少なくとも１種の化合物０
〜７０重量％であり、易揮発性発泡剤２〜１５重量％を
含有し、表面が常温で液状の食用油で被覆された発泡性
熱可塑性共重合体の粒子。(1) The monomers constituting the polymer are 10 to 80% by weight of alpha methylstyrene, 5 to 50% by weight of acrylonitrile, and further styrene, chlorostyrene, paramethylstyrene, t-butylstyrene, acrylic ester, and methacrylic acid. At least one compound selected from esters 0
-70% by weight, containing 2-15% by weight of a readily volatile blowing agent, and whose surface is coated with an edible oil that is liquid at room temperature.
肪酸を４０重量％以上含む低級酸型油脂である特許請求
の範囲第１項記載の発泡性熱可塑性共重合体の粒子。(2) The particles of the expandable thermoplastic copolymer according to claim 1, wherein the fatty acid composition constituting the edible oil is a lower acid type oil containing 40% by weight or more of fatty acids having 12 carbon atoms.
範囲第１項記載の発泡性熱可塑性共重合体の粒子。(3) The expandable thermoplastic copolymer particles according to claim 1, wherein the edible oil is coconut oil or palm kernel oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6306884A JPS60206844A (en) | 1984-03-29 | 1984-03-29 | Expandable thermoplastic copolymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6306884A JPS60206844A (en) | 1984-03-29 | 1984-03-29 | Expandable thermoplastic copolymer particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60206844A true JPS60206844A (en) | 1985-10-18 |
Family
ID=13218654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6306884A Pending JPS60206844A (en) | 1984-03-29 | 1984-03-29 | Expandable thermoplastic copolymer particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60206844A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2565225A1 (en) | 2011-08-31 | 2013-03-06 | Basf Se | Coated expandable polymer particle |
| DE102012217659A1 (en) | 2012-09-27 | 2014-03-27 | Basf Se | Expandable polymer particle useful for producing foam molded part or block of foam which is useful in e.g. furniture, construction and stand construction automotive industry, comprises polymerized styrene and/or alpha-methyl styrene |
| WO2022030230A1 (en) * | 2020-08-07 | 2022-02-10 | 株式会社カネカ | Foamable polystyrene resin particles, polystyrene pre-foamed particles, and foamed molded product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52142764A (en) * | 1976-05-24 | 1977-11-28 | Arco Polymers Inc | Antioxidant for |
| JPS5765735A (en) * | 1980-09-13 | 1982-04-21 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant expandable synthetic resin particle and molded article thereof |
| JPS57185328A (en) * | 1982-04-07 | 1982-11-15 | Dow Chemical Co | Foam-linked body with foamable synthetic resin particles |
-
1984
- 1984-03-29 JP JP6306884A patent/JPS60206844A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52142764A (en) * | 1976-05-24 | 1977-11-28 | Arco Polymers Inc | Antioxidant for |
| JPS5765735A (en) * | 1980-09-13 | 1982-04-21 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant expandable synthetic resin particle and molded article thereof |
| JPS57185328A (en) * | 1982-04-07 | 1982-11-15 | Dow Chemical Co | Foam-linked body with foamable synthetic resin particles |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2565225A1 (en) | 2011-08-31 | 2013-03-06 | Basf Se | Coated expandable polymer particle |
| DE102012217659A1 (en) | 2012-09-27 | 2014-03-27 | Basf Se | Expandable polymer particle useful for producing foam molded part or block of foam which is useful in e.g. furniture, construction and stand construction automotive industry, comprises polymerized styrene and/or alpha-methyl styrene |
| WO2022030230A1 (en) * | 2020-08-07 | 2022-02-10 | 株式会社カネカ | Foamable polystyrene resin particles, polystyrene pre-foamed particles, and foamed molded product |
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