JPH11106548A - Styrene-based foaming resin particulate - Google Patents
Styrene-based foaming resin particulateInfo
- Publication number
- JPH11106548A JPH11106548A JP28304797A JP28304797A JPH11106548A JP H11106548 A JPH11106548 A JP H11106548A JP 28304797 A JP28304797 A JP 28304797A JP 28304797 A JP28304797 A JP 28304797A JP H11106548 A JPH11106548 A JP H11106548A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- resin particles
- plasticizer
- weight
- expandable resin
- 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)
Abstract
Description
【０００１】[0001]
【技術分野】本発明は，残存モノマーやベンゼン等の発
泡剤以外の揮発性物質の含有量が極めて少ない，発泡成
形体を製造することができるスチレン系発泡性樹脂粒子
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to styrene-based expandable resin particles having a very low content of volatile substances other than a foaming agent such as residual monomer and benzene and capable of producing an expanded molded article.
【０００２】[0002]
【従来技術】スチレン系発泡性樹脂粒子は比較的安価
で，特殊な方法を用いずに低圧の蒸気等で発泡成形がで
き，高い緩衝・断熱の効果が得られる社会的に有用な材
料である。2. Description of the Related Art Styrene-based expandable resin particles are relatively inexpensive, can be foam-formed with low-pressure steam, etc. without using a special method, and are socially useful materials capable of obtaining high buffering and heat insulating effects. .
【０００３】近年，医療分野あるいは直接食品に接触す
る包装材料分野向けに，残存するスチレンモノマー及び
ベンゼン類を低減する試みがなされている。例えば，特
開平４−２６８３４７号には残存スチレンモノマーが２
０００ｐｐｍ未満，ベンゼン含有量が１ｐｐｍ未満のス
チレン系発泡性樹脂粒子及びその製造方法が開示されて
いる。In recent years, attempts have been made to reduce residual styrene monomer and benzene for the medical field or the packaging material field which comes into direct contact with food. For example, Japanese Unexamined Patent Publication No. 4-268347 discloses that the residual styrene monomer is 2%.
Styrene-based expandable resin particles having a benzene content of less than 000 ppm and a benzene content of less than 1 ppm and a method for producing the same are disclosed.
【０００４】また，特開平６−８０７０８号には，スチ
レンモノマーが４００ｐｐｍ未満，ベンゼン含有量が５
ｐｐｍ未満のスチレン系発泡性樹脂粒子の製造方法が開
示されている。JP-A-6-80708 discloses that a styrene monomer is less than 400 ppm and a benzene content is less than 5 ppm.
A method for producing styrene-based expandable resin particles of less than ppm is disclosed.
【０００５】[0005]
【解決しようとする課題】しかしながら，上記のスチレ
ン系発泡性樹脂粒子には次の問題点がある。即ち，スチ
レンモノマーやベンゼン成分はスチレン系樹脂に対して
優れた可塑効果を持つことが知られている。よって，こ
れらの成分の含有量を低下させると，スチレン系発泡性
樹脂粒子の発泡性が悪くなり高倍化するのが困難になっ
たり，成形時における予備発泡粒子同士の融着が低下す
る。また，スチレン系発泡性樹脂粒子の発泡性を補うた
めにスチレン系発泡性樹脂粒子の基材樹脂の分子量を低
下させると，機械的強度が低下するという欠点がある。However, the styrene-based expandable resin particles have the following problems. That is, it is known that a styrene monomer or a benzene component has an excellent plasticizing effect on a styrene resin. Therefore, when the contents of these components are reduced, the expandability of the styrene-based expandable resin particles deteriorates, making it difficult to increase the doubling, and the fusion of the pre-expanded particles during molding decreases. Further, when the molecular weight of the base resin of the styrene-based expandable resin particles is reduced in order to supplement the expandability of the styrene-based expandable resin particles, there is a disadvantage that the mechanical strength is reduced.
【０００６】本発明は，優れた発泡性をもち，成形品に
したときに高い機械的強度を発揮でき，かつ残存スチレ
ンモノマー及びベンゼン含有量が極めて少ない，スチレ
ン系発泡性樹脂粒子を提供しようとするものである。An object of the present invention is to provide styrene-based expandable resin particles having excellent expandability, exhibiting high mechanical strength when molded, and having extremely low residual styrene monomer and benzene contents. Is what you do.
【０００７】[0007]
【課題の解決手段】請求項１記載の発明は，スチレン系
発泡性樹脂粒子の中に，残留スチレンモノマーが１〜３
００ｐｐｍと，ベンゼン１ｐｐｍ以下と，スチレンと相
溶性を有するＳＰ値が７〜１０の可塑剤０．１〜２重量
％と，発泡剤とを含有してなることを特徴とするスチレ
ン系発泡性樹脂粒子である。According to the first aspect of the present invention, the styrene-based expandable resin particles contain 1 to 3 residual styrene monomers.
A styrene-based foamable resin comprising: 00 ppm, 1 ppm or less of benzene, 0.1 to 2% by weight of a plasticizer having an SP value of 7 to 10, which is compatible with styrene, and a foaming agent. Particles.
【０００８】本発明において最も注目すべきことは，上
記特定範囲で残存スチレンモノマーとベンゼンとを含有
し，かつスチレンと相溶性のある特定の可塑剤を上記特
定範囲で含有させたことである。The most remarkable point in the present invention is that the specific range contains the residual styrene monomer and benzene and the specific plasticizer compatible with styrene within the specific range.
【０００９】本発明のスチレン系発泡性樹脂粒子は，残
留スチレンモノマー量が１〜３００ｐｐｍ，ベンゼン含
有量が１ｐｐｍ以下である必要がある。残留スチレンモ
ノマー量が３００ｐｐｍを超え，かつやベンゼン含有量
が１ｐｐｍを超えると，そのスチレン系発泡性樹脂粒子
を発泡させて得られた発泡成形体からスチレンモノマー
やベンゼンが揮発する。そのため，その発泡成形体を，
包装材として用いた場合，内容物等がこれらの有機物質
で汚染されるため好ましくない。The styrene-based expandable resin particles of the present invention must have a residual styrene monomer content of 1 to 300 ppm and a benzene content of 1 ppm or less. If the residual styrene monomer amount exceeds 300 ppm and the benzene content exceeds 1 ppm, the styrene monomer and benzene volatilize from the foamed molded product obtained by foaming the styrene-based expandable resin particles. Therefore, the foam molding
When used as a packaging material, the contents are undesirably contaminated with these organic substances.
【００１０】一方，残留スチレンモノマー量を１ｐｐｍ
より少なくすると，スチレン系発泡性樹脂粒子の製造時
における重合時間が長くなりすぎ，製造コストが高くな
る。また，ベンゼン含有量は少ない程良く，０ｐｐｍで
あってもよい。On the other hand, the residual styrene monomer content is 1 ppm
If the amount is smaller, the polymerization time during the production of the styrene-based expandable resin particles becomes too long, and the production cost increases. The lower the benzene content, the better, and may be 0 ppm.
【００１１】残留スチレンモノマー量，ベンゼン含有量
を上記範囲内にする方法については，特に限定はされな
いが，例えば懸濁重合時において開始剤として脂肪族パ
ーオキシエステルを使用することが有効である。通常，
スチレン系発泡性樹脂粒子の重合は８０℃〜１００℃で
重合の第１段階を行い，１００℃〜１３０℃で重合の第
２段階を行っており，高温部の開始剤と低温部の開始剤
を使用する。The method for keeping the residual styrene monomer content and benzene content within the above ranges is not particularly limited, but, for example, it is effective to use an aliphatic peroxyester as an initiator during suspension polymerization. Normal,
The polymerization of the styrene-based expandable resin particles is performed at 80 ° C. to 100 ° C. in the first stage of polymerization and at 100 ° C. to 130 ° C. in the second stage of polymerization. Use
【００１２】本発明のスチレン系発泡性樹脂粒子を得る
方法としては，例えば低温部の開始剤として１０時間半
減期を得るための温度が７２〜７４℃であるパーオキシ
エステル系脂肪族過酸化物と，高温部の開始剤として１
０時間半減期を得るための温度が９０〜１２０℃である
パーオキシエステル系脂肪族過酸化物とを組み合わせて
使用する方法が挙げられる。これらの物質は，残留モノ
マー量を上記範囲になるように組み合わせる。As a method for obtaining the styrene foamable resin particles of the present invention, for example, a peroxyester-based aliphatic peroxide having a temperature of 72 to 74 ° C. for obtaining a 10-hour half-life as an initiator in a low-temperature part is used. And 1
A method in which a temperature for obtaining a half-life of 0 hour is used in combination with a peroxyester-based aliphatic peroxide having a temperature of 90 to 120 ° C. These materials are combined so that the amount of residual monomer is within the above range.
【００１３】また，本発明のスチレン系発泡性樹脂粒子
を得るために，可塑剤を重合反応系中に添加することが
必要である。ここでいう可塑剤とは，スチレンと相溶性
を持つ物質であり，溶解度パラメーター（ＳＰ値）が７
〜１０の有機化合物を用いる。Further, in order to obtain the styrene foamable resin particles of the present invention, it is necessary to add a plasticizer to the polymerization reaction system. The plasticizer referred to here is a substance that is compatible with styrene and has a solubility parameter (SP value) of 7 or less.
10 to 10 organic compounds are used.
【００１４】ここに，ポリスチレンのＳＰ値は９．１で
あることから，可塑剤としてＳＰ値が７〜１０のものを
使用することが，ポリスチレンとの相溶性が高いため好
ましい。ＳＰ値が７未満もしくは１０を超える場合に
は，ポリスチレンとの相溶性が低く，可塑効果が低下す
る。Here, since the SP value of polystyrene is 9.1, it is preferable to use a plasticizer having an SP value of 7 to 10 because of its high compatibility with polystyrene. If the SP value is less than 7 or more than 10, the compatibility with polystyrene is low, and the plastic effect is reduced.
【００１５】上記可塑剤は，スチレン系発泡性樹脂粒子
中に０．１〜２重量％含有させる。０．１重量％未満の
場合は可塑化効果が少なく，スチレン系発泡性樹脂粒子
より得られる発泡成形体における融着性や外観性が悪
い。また，２重量％を超えると，強度低下への影響が大
きく，また，製造コストが高くなる。The plasticizer is contained in the styrene foamable resin particles in an amount of 0.1 to 2% by weight. When the amount is less than 0.1% by weight, the plasticizing effect is small, and the foamed article obtained from the styrene-based foamable resin particles has poor fusion-bonding properties and appearance. On the other hand, if it exceeds 2% by weight, the effect on the strength reduction is large and the production cost is increased.
【００１６】本発明のスチレン系発泡性樹脂粒子を得る
一つの具体的な方法としては，スチレン系単量体を重合
開始剤及び懸濁剤の存在下で水性媒体中に分散させた後
に重合反応を開始し，懸濁重合中に発泡剤を添加する
か，又は重合後に発泡剤を含浸させる方法が挙げられ
る。One specific method for obtaining the styrene-based expandable resin particles of the present invention is to disperse a styrene-based monomer in an aqueous medium in the presence of a polymerization initiator and a suspending agent and then carry out a polymerization reaction. And a method of adding a blowing agent during suspension polymerization or impregnating the blowing agent after polymerization.
【００１７】本発明のスチレン系発泡性樹脂粒子を得る
ために使用できるスチレン系単量体としては，スチレ
ン，α−メチルスチレン，ｏ−メチルスチレン，ｍ−メ
チルスチレン，ｐ−メチルスチレン，ビニルトルエン，
ｐ−エチルスチレン，２，４−ジメチルスチレン，ｐ−
メトキシスチレン，ｐ−フェニルスチレン，ｏ−クロロ
スチレン，ｍ−クロロスチレン，ｐ−クロロスチレン，
２，４−ジクロロスチレン，ｐ−ｎ−ブチルスチレン，
ｐ−ｔ−ブチルスチレン，ｐ−ｎ−ヘキシルスチレン，
ｐ−オクチルスチレン，スチレンスルホン酸，スチレン
スルホン酸ナトリウム等が挙げられる。The styrene monomers usable for obtaining the styrene foamable resin particles of the present invention include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and vinyltoluene. ,
p-ethylstyrene, 2,4-dimethylstyrene, p-
Methoxystyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene,
2,4-dichlorostyrene, pn-butylstyrene,
pt-butylstyrene, pn-hexylstyrene,
p-octylstyrene, styrenesulfonic acid, sodium styrenesulfonate and the like.
【００１８】また，アクリル酸メチル，アクリル酸エチ
ル，アクリル酸プロピル，アクリル酸ブチル，アクリル
酸−２−エチルヘキシル等のアクリル酸の炭素数１〜１
０のアルキルエステル；メタクリル酸メチル，メタクリ
ル酸エチル，メタクリル酸プロピル，メタクリル酸ブチ
ル，メタクリル酸−２−エチルヘキシル等のメタクリル
酸の炭素数１〜１０のアルキルエステル；ヒドロキシエ
チルアクリレート，ヒドロキシエチルメタクリレート，
ヒドロキシプロピルアクリレート，ヒドロキシプロピル
メタクリレート，ヒドロキシブチルアクリレート，ヒド
ロキシブチルメタクリレート等の水酸基を有する不飽和
化合物；アクリロニトリル，メタクリロニトリル等のニ
トリル基含有不飽和化合物；酢酸ビニル，プロピオン酸
ビニル等の有機酸ビニル化合物；エチレン，プロピレ
ン，１−ブテン，２−ブテン，イソブテン等の不飽和モ
ノオレフィン類；ブタジエン，イソプレン，クロロプレ
ン等のジエン化合物；塩化ビニル，塩化ビニリデン，臭
化ビニル，フッ化ビニル等のハロゲン化ビニル；ビニル
メチルケトン，ビニルエチルケトン，ビニルヘキシルケ
トン等のビニルケトン類；ビニルメチルエーテル，ビニ
ルエチルエーテル，ビニルイソブチルエーテル等のビニ
ルエーテル類；Ｎ−ビニルピロリドン，Ｎ−ビニルイン
ドール，Ｎ−ビニルカルバゾール，Ｎ−ビニルピロール
等のＮ−ビニル化合物；アクリルアミド，メタクリルア
ミド，Ｎ−メチロールアクリルアミド，Ｎ−メチロール
メタクリルアミド等のアミド基を有する不飽和化合物；
アクリル酸，メタクリル酸，イタコン酸等の不飽和カル
ボン酸；Ｎ−フェニルマレイミド，Ｎ−（メチル）フェ
ニルマレイミド，Ｎ−（ヒドロキシ）フェニルマレイミ
ド，Ｎ−（メトキシ）フェニルマレイミド，Ｎ−安息香
酸マレイミド，Ｎ−メチルマレイミド，Ｎ−エチルマレ
イミド，Ｎ−ｎ−プロピルマレイミド，Ｎ−イソプロピ
ルマレイミド，Ｎ−ｎ−ブチルマレイミド，Ｎ−イソブ
チルマレイミド，Ｎ−ｔ−ブチルマレイミド等のマレイ
ミド系化合物；ジビニルベンゼン，エチレングリコール
ジメタクリレート等の架橋性多官能ビニル化合物；グリ
シジルアクリレート，グリシジルメタクリレート等のエ
ポキシ基を有する不飽和化合物，などの各種のビニル系
化合物を併用しても良い。Also, acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. has 1 to 1 carbon atoms.
Alkyl esters of 0; alkyl methacrylates having 1 to 10 carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; hydroxyethyl acrylate, hydroxyethyl methacrylate,
Unsaturated compounds having a hydroxyl group such as hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate; unsaturated compounds containing a nitrile group such as acrylonitrile and methacrylonitrile; vinyl organic compounds such as vinyl acetate and vinyl propionate Unsaturated monoolefins such as ethylene, propylene, 1-butene, 2-butene and isobutene; diene compounds such as butadiene, isoprene and chloroprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Nirupiroridon, N- vinyl indole, N- vinylcarbazole, N- vinyl compounds such as N- vinyl pyrrole; acrylamide, methacrylamide, N- methylol acrylamide, the unsaturated compound having an amide group such as N- methylol methacrylamide;
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid and itaconic acid; N-phenylmaleimide, N- (methyl) phenylmaleimide, N- (hydroxy) phenylmaleimide, N- (methoxy) phenylmaleimide, N-benzoic maleimide; Maleimide compounds such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide; divinylbenzene, ethylene Various vinyl compounds such as a crosslinkable polyfunctional vinyl compound such as glycol dimethacrylate; an unsaturated compound having an epoxy group such as glycidyl acrylate and glycidyl methacrylate may be used in combination.
【００１９】また，上記の重合開始剤としては，たとえ
ばアゾビスイソブチロニトリル等のアゾ系化合物，クメ
ンヒドロパーオキサイド，ジクミルパーオキサイド，ｔ
−ブチルパーオキシ−２−エチルヘキサノエート，ｔ−
ブチルパーオキシイソプロピルカーボネート，ｔ−ブチ
ルパーオキシ２−エチルヘキシルモノカーボネート，ラ
ウロイルパーオキサイド等の単量体に可溶な開始剤が挙
げられる。Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile, cumene hydroperoxide, dicumyl peroxide, t
-Butylperoxy-2-ethylhexanoate, t-
Examples of the initiator include those soluble in monomers such as butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, and lauroyl peroxide.
【００２０】重合開始剤の使用量は，仕込み単量体の全
重量１００重量部に対して０．０１〜３重量部が好まし
い。０．０１重量部未満では重合速度が遅くなり過ぎ，
逆に３重量部を超えると製造コストが高くなる。The amount of the polymerization initiator to be used is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the total weight of the charged monomers. If the amount is less than 0.01 part by weight, the polymerization rate becomes too slow.
Conversely, if the amount exceeds 3 parts by weight, the production cost increases.
【００２１】スチレン系発泡性樹脂粒子を得るために使
用される懸濁剤としては，例えばポリビニルアルコー
ル，メチルセルロース，ポリビニルピロリドン等の水溶
性高分子，ピロリン酸マグネシウム，第３燐酸カルシウ
ム等の難溶性無機塩等を用いることができ，これらは界
面活性剤を併用してもよい。なお，難溶性無機塩を用い
る場合は，アルキルスルホン酸ソーダ，ドデシルベンゼ
ンスルホン酸ソーダ等のアニオン性界面活性剤を併用す
るのが好ましい。Examples of the suspending agent used to obtain the styrene-based expandable resin particles include water-soluble polymers such as polyvinyl alcohol, methylcellulose and polyvinylpyrrolidone, and poorly soluble inorganics such as magnesium pyrophosphate and tertiary calcium phosphate. Salts and the like can be used, and these may be used in combination with a surfactant. When a poorly soluble inorganic salt is used, it is preferable to use an anionic surfactant such as sodium alkylsulfonate and sodium dodecylbenzenesulfonate together.
【００２２】懸濁剤の使用量は，仕込み単量体の全重量
１００重量部に対し０．０１〜５．０重量部が好まし
い。前記した難溶性無機塩とアニオン性界面活性剤との
併用系では，それぞれ仕込み単量体の全重量１００重量
部に対し，難溶性無機塩を０．０５〜３．０重量部，ア
ニオン性界面活性剤を０．０００１〜０．５重量部用い
ることが好ましい。The amount of the suspending agent to be used is preferably 0.01 to 5.0 parts by weight based on 100 parts by weight of the total weight of the charged monomers. In the above-mentioned combination system of the hardly soluble inorganic salt and the anionic surfactant, 0.05 to 3.0 parts by weight of the hardly soluble inorganic salt and 100 parts by weight of the total weight of the charged monomers are used. It is preferable to use 0.0001 to 0.5 parts by weight of the activator.
【００２３】尚，単量体の水性媒体への添加方法は，予
め一括に仕込んでもよいし，徐々に添加しながら行って
も良い。（特公昭４６−２９８７号，特公昭４９−２９
９４号参照）Incidentally, the method of adding the monomer to the aqueous medium may be preliminarily charged in a lump or may be performed while gradually adding the monomer. (JP-B-46-2987, JP-B-49-29)
(See No. 94)
【００２４】本発明のスチレン系発泡性樹脂粒子を得る
ために使用される発泡剤としては，たとえばプロパン，
ノルマルブタン，イソブタン，ノルマルペンタン，イソ
ペンタン，ネオペンタン，ヘキサン等の脂肪族炭化水
素；シクロブタン，シクロペンタン等の脂環族炭化水
素；塩化メチル，ジクロルフルオロメタン等のハロゲン
化炭化水素等の物理発泡剤；さらには炭酸ガス，窒素，
アンモニア等の無機ガスが挙げられる。これらの発泡剤
は１種類を単独で，又は２種以上を併用して使用でき
る。The foaming agent used to obtain the styrene-based foamable resin particles of the present invention includes, for example, propane,
Aliphatic hydrocarbons such as normal butane, isobutane, normal pentane, isopentane, neopentane and hexane; alicyclic hydrocarbons such as cyclobutane and cyclopentane; physical blowing agents such as halogenated hydrocarbons such as methyl chloride and dichlorofluoromethane Also carbon dioxide, nitrogen,
An inorganic gas such as ammonia can be used. These foaming agents can be used alone or in combination of two or more.
【００２５】発泡剤は，通常，スチレン系発泡性樹脂粒
子の発泡剤含有量が１〜２０重量％になる程度の量が供
給される。ただし，環境に及ぼす影響を考慮した場合，
発泡剤含有量は少なければ少ない方が良い。The foaming agent is usually supplied in such an amount that the foaming agent content of the styrene-based foamable resin particles becomes 1 to 20% by weight. However, considering the effect on the environment,
The smaller the content of the blowing agent, the better.
【００２６】次に，請求項２記載の発明のように，上記
可塑剤は，脂肪族または芳香族のカルボン酸と炭素数が
１〜２２のアルコールとのエステルであることが好まし
い。上記のエステルは，ポリスチレンに対する相溶性が
高く，可塑化効果も高いため，成形時において，予備発
泡粒子同士の融着の度合いが高くなるという効果が得ら
れる。一方，炭素数が２２を超えるものについては，工
業的に入手しにくいだけでなく，スチレンモノマーに対
する溶解性が悪化する。そのため，均一分散化に時間が
かかるため好ましくない。Next, as in the second aspect of the present invention, the plasticizer is preferably an ester of an aliphatic or aromatic carboxylic acid and an alcohol having 1 to 22 carbon atoms. Since the above-mentioned ester has high compatibility with polystyrene and a high plasticizing effect, the effect of increasing the degree of fusion between the pre-expanded particles during molding can be obtained. On the other hand, those having more than 22 carbon atoms are not only industrially difficult to obtain, but also have poor solubility in styrene monomers. Therefore, it takes time for uniform dispersion, which is not preferable.
【００２７】次に，請求項３記載の発明のように，ＧＰ
Ｃ法により測定したスチレン系発泡性樹脂粒子の重量平
均分子量（Ｍｗ）の値は，２２万〜３５万の間にあるこ
とが好ましい。この場合には，予備発泡粒子同士がよく
融着し，かつ高い機械的強度をもつ発泡成形耐が得られ
る。また，Ｍｗが２２万未満では，発泡成形体の強度が
低下するおそれがある。一方，３５万を超えると，予備
発泡及び発泡成型時において基材樹脂の伸びが不足し，
発泡成形体の融着や外観に悪影響を及ぼすため好ましく
ない。Next, according to the third aspect of the present invention, the GP
The value of the weight average molecular weight (Mw) of the styrene-based expandable resin particles measured by the method C is preferably between 220,000 and 350,000. In this case, the pre-expanded particles are well fused to each other, and foam molding resistance having high mechanical strength can be obtained. When Mw is less than 220,000, the strength of the foamed molded article may be reduced. On the other hand, if it exceeds 350,000, the elongation of the base resin becomes insufficient during pre-foaming and foam molding,
It is not preferable because it has a bad influence on the fusion bonding and appearance of the foam molded article.
【００２８】次に，請求項４記載の発明のように，上記
エステルは，炭素数が６〜２２の脂肪酸とグリセリンの
トリエステルまたはモノエステルのアセチル化物である
ことが好ましい。上記の物質は，ポリスチレンに対する
可塑化効果が特に高く，予備発泡粒子同士が特によく融
着した発泡成形体が得られる。また，これらの可塑剤は
揮発性がないか，もしくは低く，発泡成形体より溶出し
ないため好ましい。また，炭素数が６未満では，可塑剤
が揮発するため好ましくない。一方，炭素数が２２を超
えるものについては，工業的に入手しにくいだけでな
く，スチレンモノマーに対する溶解性が悪化する。その
ため，均一分散化に時間がかかるため好ましくない。Next, as in the invention of claim 4, the ester is preferably an acetylated product of a triester or monoester of glycerin with a fatty acid having 6 to 22 carbon atoms. The above-mentioned substances have a particularly high plasticizing effect on polystyrene, and a foam molded article in which pre-expanded particles are fused particularly well can be obtained. Further, these plasticizers are preferable because they have no or low volatility and do not elute from the foamed molded product. On the other hand, if the number of carbon atoms is less than 6, the plasticizer volatilizes, which is not preferable. On the other hand, those having more than 22 carbon atoms are not only industrially difficult to obtain, but also have poor solubility in styrene monomers. Therefore, it takes time for uniform dispersion, which is not preferable.
【００２９】次に，請求項５記載の発明のように，上記
エステルは，フタル酸もしくはアジピン酸と炭素数６〜
２２の脂肪族アルコールとのモノエステルまたはジエス
テルであることが好ましい。上記の物質は，ポリスチレ
ンに対する可塑化効果が特に高く，予備発泡粒子同士の
特によく融着した発泡成形体が得られる。また，これら
の可塑剤は揮発性がないか，もしくは，低く発泡成形体
より溶出しないため好ましい。また，炭素数が６未満で
は，可塑剤が揮発するため好ましくない。一方，炭素数
が２２を超えるものについては，工業的に入手しにくい
だけでなく，スチレンモノマーに対する溶解性が悪化す
る。そのため，均一分散化に時間がかかるため好ましく
ない。Next, as in the fifth aspect of the present invention, the ester comprises phthalic acid or adipic acid and C6-C6.
It is preferably a monoester or diester with an aliphatic alcohol of No. 22. The above-mentioned substances have a particularly high plasticizing effect on polystyrene, so that a foam molded article in which the pre-expanded particles are fused particularly well can be obtained. In addition, these plasticizers are preferable because they have no volatility or are low and do not elute from the molded foam. On the other hand, if the number of carbon atoms is less than 6, the plasticizer volatilizes, which is not preferable. On the other hand, those having more than 22 carbon atoms are not only industrially difficult to obtain, but also have poor solubility in styrene monomers. Therefore, it takes time for uniform dispersion, which is not preferable.
【００３０】次に，請求項６記載の発明のように，上記
発泡剤は，沸点が１００℃以下の脂肪族炭化水素または
脂環族炭化水素を，１〜５重量％含有されていることが
好ましい。この場合には，発泡成形体に残存する発泡剤
が殆どなくなることから，発泡成形体からの揮発成分が
少なくなるので好ましい。また，含有されている量が１
重量％未満では，発泡力が不足するため，発泡しなかっ
たり，成形時において予備発泡粒子同士の融着が不足す
るなどの問題が起こるので好ましくない。一方，５重量
％を超えると，発泡成形体中に発泡剤が多量に存在し，
徐々に揮発するため好ましくない。Next, as in the sixth aspect of the present invention, the foaming agent may contain 1 to 5% by weight of an aliphatic hydrocarbon or an alicyclic hydrocarbon having a boiling point of 100 ° C. or less. preferable. In this case, since there is almost no foaming agent remaining in the foamed molded article, the volatile component from the foamed molded article is reduced, which is preferable. In addition, the amount contained is 1
If the amount is less than the percentage by weight, the foaming power is insufficient, and problems such as insufficient foaming and insufficient fusion of the pre-expanded particles during molding occur. On the other hand, if it exceeds 5% by weight, a large amount of the foaming agent is present in the foamed molded article,
It is not preferable because it evaporates gradually.
【００３１】また，スチレン系単量体には，気泡形成剤
としてのメタクリル酸メチル系共重合体，ポリエチレン
ワックス，タルク，エチレンビスステアリルアミド，メ
チレンビスステアリルアミド，エチレン−酢酸ビニル共
重合体樹脂等を添加しておくことができる。The styrene-based monomer includes a methyl methacrylate-based copolymer as a foam-forming agent, polyethylene wax, talc, ethylenebisstearylamide, methylenebisstearylamide, ethylene-vinyl acetate copolymer resin and the like. Can be added.
【００３２】さらに，難燃剤，難燃助剤，帯電防止剤，
導電化剤，セル核剤，粒度分布調整剤等の一般的にスチ
レン系発泡性樹脂粒子の製造に使用されている添加剤を
適宜添加したり，ブタジエンゴム，スチレン・ブタジエ
ンゴム等のゴム成分を混合することもできる。Further, a flame retardant, a flame retardant auxiliary, an antistatic agent,
Additives commonly used in the production of styrene-based expandable resin particles, such as a conductive agent, a cell nucleating agent, and a particle size distribution modifier, may be appropriately added, or rubber components such as butadiene rubber and styrene / butadiene rubber may be added. They can also be mixed.
【００３３】また，得られたスチレン系発泡性樹脂粒子
に熱処理を施して，更にそれら粒子を用いて成形された
発泡成形体の表面外観を向上させてもよい。本発明のス
チレン系発泡性樹脂粒子は，これを予備発泡させ，その
後それを加熱発泡させ，発泡成形体とする。予備発泡方
法としては，例えば円筒形の予備発泡機を用いて，スチ
ーム等で加熱し発泡させる等の方法がある。Further, the obtained styrene-based foamable resin particles may be subjected to a heat treatment to further improve the surface appearance of a foam molded article molded using the particles. The styrenic foamable resin particles of the present invention are prefoamed and then heat-foamed to obtain a foamed molded article. As a pre-foaming method, for example, there is a method of foaming by heating with steam or the like using a cylindrical pre-foaming machine.
【００３４】また，予備発泡樹脂粒子を発泡成形させる
方法としては例えば，金型内に予備発泡粒子を充填し，
スチーム等を吹き込んで加熱する，通常の所謂型内成形
法で発泡成形体を得る等の方法が挙げられる。この様に
して，得られた発泡成形体の密度は，低過ぎると強度が
不足し，逆に高過ぎると経済的に不適当であることか
ら，１０〜５０ｇ／Ｌであるのが好ましい。As a method of foaming the pre-expanded resin particles, for example, a pre-expanded particle is filled in a mold,
Heating by blowing steam or the like, and a method of obtaining a foamed molded article by a usual so-called in-mold molding method can be used. The density of the foamed article obtained in this way is preferably 10 to 50 g / L, because if the density is too low, the strength is insufficient, and if it is too high, it is economically unsuitable.
【００３５】[0035]
【発明の実施の形態】以下に，本発明に関する実施例及
び比較例につき説明する。 実施例１ 攪拌器付き５０リットルオートクレーブに，イオン交換
水１８リットル，懸濁剤としての第３燐酸カルシウム
（太平化学社製）４０ｇ，界面活性剤としてのドデシル
ベンゼンスルホン酸ナトリウム０．５ｇを投入した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples relating to the present invention will be described below. Example 1 Into a 50 liter autoclave equipped with a stirrer, 18 liters of ion-exchanged water, 40 g of tertiary calcium phosphate (manufactured by Taihei Chemical Co., Ltd.) as a suspending agent, and 0.5 g of sodium dodecylbenzenesulfonate as a surfactant were charged. .
【００３６】次いで攪拌下に，開始剤としてのｔ−ブチ
ルパーオキシ−２−エチルヘキサノエート５４ｇ，及び
ｔ−ブチルパーオキシイソプロピルモノカーボネート４
５ｇ，可塑化剤としてのグリセリントリステアレート
（ＧＴＳ）９０ｇを，スチレンモノマー１８ｋｇに溶解
させたものを投入した。Then, under stirring, 54 g of t-butylperoxy-2-ethylhexanoate as initiator and t-butylperoxyisopropyl monocarbonate 4
A solution prepared by dissolving 5 g of glycerin tristearate (GTS) 90 g as a plasticizer in 18 kg of styrene monomer was charged.
【００３７】攪拌下で３０分間室温のまま放置した後，
１時間半かけて９０℃まで昇温し，６０℃で懸濁助剤と
しての過硫酸カリウムの０．１％水溶液を９０ｇ加え，
そのまま７時間かけて１２０℃まで昇温した。途中，９
０℃到達から４時間３０分経過したところで，発泡剤と
してのブタン４００ｇとペンタン８００ｇとをオートク
レーブ内に圧入した。その後，１２０℃で６時間保持し
た後，６時間かけて３０℃まで冷却した。After leaving at room temperature for 30 minutes under stirring,
The temperature was raised to 90 ° C. over one and a half hours, and at 60 ° C., 90 g of a 0.1% aqueous solution of potassium persulfate as a suspending aid was added.
The temperature was raised to 120 ° C. over 7 hours. On the way, 9
When 4 hours and 30 minutes had passed since the temperature reached 0 ° C., 400 g of butane as a blowing agent and 800 g of pentane were pressed into the autoclave. Thereafter, the temperature was maintained at 120 ° C. for 6 hours, and then cooled to 30 ° C. over 6 hours.
【００３８】次いで，遠心分離器にて脱水し，酸洗浄し
てスチレン系発泡性樹脂粒子の表面の第３リン酸カルシ
ウムを除去した。その後，流動乾燥装置で上面付着水分
を除去し，スチレン系発泡性樹脂粒子を得た。Next, dehydration was performed by a centrifugal separator, and acid washing was performed to remove tribasic calcium phosphate on the surface of the styrene-based expandable resin particles. Thereafter, the water adhering to the upper surface was removed by a fluidized drying apparatus to obtain styrene-based foamable resin particles.
【００３９】得られたスチレン系発泡性樹脂粒子を予備
発泡機（株式会社ダイセン工業製ＤＹＨ−８５０）で，
常法により嵩密度２０ｇ／Ｌに発泡させた。こうして得
られた予備発泡粒子を，１日室温で放置（熟成）した
後，これを２８×３５×１５ｃｍの大きさの箱型の金型
内に充填し，０．７ｋｇｆ／ｃｍ2 ・Ｇの水蒸気を２０
秒間吹き込んで加熱成形し，発泡成形体を得た。The obtained styrene-based expandable resin particles were subjected to a pre-expansion machine (DYH-850 manufactured by Daisen Industries Co., Ltd.)
The foam was foamed to a bulk density of 20 g / L by a conventional method. After the thus obtained pre-expanded particles are left (aged) at room temperature for one day, they are filled in a box-shaped mold having a size of 28 × 35 × 15 cm, and are filled with 0.7 kgf / cm 2 · G. 20 steam
The mixture was blown for 2 seconds and heated to obtain a foamed molded product.
【００４０】上記のようにして得られるスチレン系発泡
性樹脂粒子の重量平均分子量，スチレン系発泡性樹脂粒
子に含まれる残存スチレンモノマー量，ベンゼン量，発
泡成形体の表面外観，融着度，曲げ強度，圧縮強度およ
び落球衝撃強度高さを下記の方法で評価した。The weight average molecular weight of the styrene foamable resin particles obtained as described above, the amount of residual styrene monomer contained in the styrene foamable resin particles, the amount of benzene, the surface appearance of the foamed molded product, the degree of fusion, the bending. The strength, compressive strength and falling ball impact strength were evaluated by the following methods.
【００４１】評価方法 重量平均分子量；スチレン系発泡性樹脂粒子をクロロホ
ルムの０．２５％溶液にして，ＧＰＣ法にて測定し，標
準ポリスチレンで換算した。 残留スチレンモノマー量；スチレン系発泡性樹脂粒子を
ジメチルホルムアミドの溶液にして，ポリエチレングリ
コールを充填したカラムを用いたガスクロマトグラフィ
ー法を用いて測定した。Evaluation method Weight average molecular weight: Styrene-based expandable resin particles were made into a 0.25% solution of chloroform, measured by GPC method, and converted to standard polystyrene. Residual styrene monomer content: The styrene-based expandable resin particles were converted into a solution of dimethylformamide and measured by gas chromatography using a column filled with polyethylene glycol.
【００４２】ベンゼン含有量；スチレン系発泡性樹脂粒
子をジメチルホルムアセトアミドの溶液にして，ポリエ
チレングリコールを充填したカラムを用いたガスクロマ
トグラフィー法により測定した。 表面外観；発泡成形体の表面外観を目視により下記基準
にて評価した。 ○；溶融した粒子はなく，粒子間の間隙もなく，見栄え
がよい。 △；溶融した粒子が表面にあるか又は粒子間に間隙があ
り見栄えが悪い。 ×；溶融した粒子があるか又は粒子間に間隙があり見栄
えが著しく悪い。もしくは発泡成形体が得られない。Benzene content: The styrene-based expandable resin particles were converted into a solution of dimethylformacetamide and measured by gas chromatography using a column filled with polyethylene glycol. Surface appearance: The surface appearance of the foamed molded article was visually evaluated according to the following criteria. ；: No melted particles, no gaps between particles, good appearance. Δ: The melted particles are on the surface or there are gaps between the particles, and the appearance is poor. X: There are molten particles or there are gaps between the particles, and the appearance is extremely poor. Or a foamed molded article cannot be obtained.
【００４３】融着度；発泡成形体において予備発泡粒子
同士が完全に接着（融着）している割合であり，発泡成
形体を割った断面において，予備発泡粒子の界面以外で
裂けている割合を目視で測定した。Degree of fusion: the ratio of the pre-expanded particles being completely bonded (fused) to each other in the expanded molded article, and the percentage of the cross-section of the expanded molded article torn apart from the interface of the pre-expanded particles. Was measured visually.
【００４４】曲げ強度；発泡成形体を縦３００ｍｍ，横
７５ｍｍ，厚さ２５ｍｍに切断して試験片とし，ＪＩＳ
Ａ ９５１１に準拠して曲げ強度を測定した。 圧縮強度；発泡成形体を縦５０ｍｍ，厚さ２５ｍｍに切
断して試験片とし，ＪＩＳ Ｚ ０２３４に準拠して圧
縮強度を測定した。Flexural strength: A foamed product was cut into a test piece by cutting it into a piece having a length of 300 mm, a width of 75 mm and a thickness of 25 mm.
The bending strength was measured according to A 9511. Compressive strength: The foamed molded product was cut into a test piece by cutting it into a piece having a length of 50 mm and a thickness of 25 mm, and the compressive strength was measured in accordance with JIS Z 0234.
【００４５】落球衝撃強度高さ；発泡成形体を縦２００
ｍｍ，横４０ｍｍ，厚さ２５ｍｍに切断して試験片と
し，重量２５５ｇの剛球を垂直に落下させ発泡成形体の
５０％が破壊したところの落下高さとする。（ＪＩＳ
Ｋ７２１１に準拠）Height of falling ball impact strength;
mm, 40 mm in width, and 25 mm in thickness are cut into a test piece, and a hard sphere having a weight of 255 g is dropped vertically to obtain a drop height at which 50% of the foam molded body is broken. (JIS
(Based on K7211)
【００４６】実施例２ 発泡剤として使用するブタンとペンタンの量を，それぞ
れブタン５００ｇとペンタン１Ｋｇを加える他は，全て
上記実施例１と同様に行った。Example 2 The same procedure as in Example 1 was carried out except that butane and pentane used as a foaming agent were added in the amounts of 500 g of butane and 1 kg of pentane, respectively.
【００４７】実施例３ ｔ−ブチルパーオキシイソプロピルモノカーボネートの
代わりに，開始剤としてｔ−ブチルパーオキシ−２−エ
チルヘキシルモノカーボネート４５ｇを加える他は，全
て上記実施例１と同様に行った。Example 3 In the same manner as in Example 1 except that 45 g of t-butylperoxy-2-ethylhexyl monocarbonate was added as an initiator instead of t-butylperoxyisopropyl monocarbonate.
【００４８】実施例４ グリセリントリステアレートの代わりに可塑剤としてジ
（２−エチルヘキシル）フタレート（ＤＯＰ）を９０ｇ
添加する以外は，全て上記実施例１と同様に行った。Example 4 90 g of di (2-ethylhexyl) phthalate (DOP) as a plasticizer instead of glycerin tristearate
Except for the addition, the procedure was the same as in Example 1 above.
【００４９】実施例５ グリセリントリステアレートの代わりに可塑剤としてグ
リセリンジアセトモノラウレート（ＧＡＬ）（理研ビタ
ミン社製，商品名リケマールＰＬ−０１２）を９０ｇ添
加する以外は，全て上記実施例１と同様に行った。Example 5 The procedure of Example 1 was repeated except that 90 g of glycerin diacetmonolaurate (GAL) (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemar PL-012) was added as a plasticizer instead of glycerin tristearate. Performed similarly.
【００５０】実施例６ グリセリントリステアレートの代わりに可塑剤としてコ
コナッツオイル（ＣＣＯ）を９０ｇ添加する以外は全て
上記実施例１と同様に行った。Example 6 The same procedure as in Example 1 was carried out except that 90 g of coconut oil (CCO) was added as a plasticizer instead of glycerin tristearate.
【００５１】実施例７ 開始剤としてのｔ−ブチルパーオキシ−２−エチルヘキ
サノエートの添加量を９０ｇとする以外は，全て上記実
施例１と同様に行った。Example 7 The procedure of Example 1 was repeated, except that the amount of t-butylperoxy-2-ethylhexanoate used as an initiator was changed to 90 g.
【００５２】実施例８ 同じく上記ｔ−ブチルパーオキシ−２−エチルヘキサノ
エートの添加量を２７ｇとする以外は，全て上記実施例
１と同様に行った。Example 8 The same procedure was performed as in Example 1 except that the amount of t-butylperoxy-2-ethylhexanoate was changed to 27 g.
【００５３】比較例１ 可塑剤としてのグリセリントリステアレートの添加量を
０とする他は，全て上記実施例１と同様に行った。Comparative Example 1 The procedure of Example 1 was repeated except that the amount of glycerin tristearate as a plasticizer was changed to 0.
【００５４】以上の各実施例及び各比較例における，ス
チレン系発泡性樹脂粒子の重量平均分子量，スチレン系
発泡性樹脂粒子に含まれる残存スチレンモノマー量，ベ
ンゼン量，発泡成形体の表面外観，融着度，曲げ強度，
圧縮強度及び落球衝撃強度高さについて，表１に示し
た。In each of the above Examples and Comparative Examples, the weight average molecular weight of the styrene foamable resin particles, the amount of residual styrene monomer and benzene contained in the styrene foamable resin particles, the surface appearance of the foamed molded article, Degree of attachment, bending strength,
Table 1 shows the compressive strength and the falling ball impact strength.
【００５５】[0055]
【表１】 [Table 1]
【００５６】表１より，本発明のスチレン系発泡性樹脂
粒子は，表面外観，融着度，曲げ強度，圧縮強度及び衝
撃強度がいずれも優れていることが分かる。From Table 1, it can be seen that the styrenic foamable resin particles of the present invention have excellent surface appearance, degree of fusion, bending strength, compression strength and impact strength.
【００５７】[0057]
【発明の効果】以上により，優れた発泡性をもち，成形
品にしたときに高い機械的強度を発揮でき，かつ残存ス
チレンモノマー及びベンゼン含有量が極めて少ない，ス
チレン系発泡性樹脂粒子を提供することができる。As described above, the present invention provides styrene-based expandable resin particles having excellent expandability, exhibiting high mechanical strength when molded, and having extremely low residual styrene monomer and benzene contents. be able to.
Claims (6)
スチレンモノマーが１〜３００ｐｐｍと，ベンゼン１ｐ
ｐｍ以下と，スチレンと相溶性を有するＳＰ値が７〜１
０の可塑剤０．１〜２重量％と，発泡剤とを含有してな
ることを特徴とするスチレン系発泡性樹脂粒子。1. A styrene-based expandable resin particle containing 1 to 300 ppm of a residual styrene monomer and 1 p
pm or less and SP value compatible with styrene of 7-1
Styrene-based foamable resin particles, comprising 0.1 to 2% by weight of a plasticizer and a foaming agent.
族または芳香族のカルボン酸と炭素数が１〜２２のアル
コールとのエステルであることを特徴とするスチレン系
発泡性樹脂粒子。2. The styrenic foamable resin particles according to claim 1, wherein the plasticizer is an ester of an aliphatic or aromatic carboxylic acid and an alcohol having 1 to 22 carbon atoms.
より測定したスチレン系発泡性樹脂粒子の重量平均分子
量（Ｍｗ）の値は，２２万〜３５万の間にあることを特
徴とするスチレン系発泡性樹脂粒子。3. The styrene-based expandable resin particle according to claim 1, wherein the weight average molecular weight (Mw) of the styrene-based expandable resin particle is between 220,000 and 350,000. Expandable resin particles.
素数が６〜２２の脂肪酸とグリセリンのトリエステルま
たはモノエステルのアセチル化物であることを特徴とす
るスチレン系発泡性樹脂粒子。4. The styrene-based expandable resin particles according to claim 2, wherein the ester is an acetylated product of a triester or a monoester of a fatty acid having 6 to 22 carbon atoms and glycerin.
タル酸もしくはアジピン酸と炭素数６〜２２の脂肪族ア
ルコールとのモノエステルまたはジエステルであること
を特徴とするスチレン系発泡性樹脂粒子。5. The styrene foamable resin particles according to claim 2, wherein the ester is a monoester or a diester of phthalic acid or adipic acid and an aliphatic alcohol having 6 to 22 carbon atoms.
が１００℃以下の脂肪族炭化水素または脂環族炭化水素
を，１〜５重量％含有されていることを特徴とするスチ
レン系発泡性樹脂粒子。6. The styrenic foam according to claim 1, wherein the foaming agent contains 1 to 5% by weight of an aliphatic hydrocarbon or an alicyclic hydrocarbon having a boiling point of 100 ° C. or less. Resin particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28304797A JP4326034B2 (en) | 1997-09-30 | 1997-09-30 | Styrenic expandable resin particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28304797A JP4326034B2 (en) | 1997-09-30 | 1997-09-30 | Styrenic expandable resin particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11106548A true JPH11106548A (en) | 1999-04-20 |
| JP4326034B2 JP4326034B2 (en) | 2009-09-02 |
Family
ID=17660532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28304797A Expired - Fee Related JP4326034B2 (en) | 1997-09-30 | 1997-09-30 | Styrenic expandable resin particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4326034B2 (en) |
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|---|---|---|---|---|
| JP2002356575A (en) * | 2001-03-30 | 2002-12-13 | Mitsubishi Kagaku Form Plastic Kk | Foamable polystyrene resin particles and foamed molded material |
| JP2003055493A (en) * | 2001-08-10 | 2003-02-26 | Kanegafuchi Chem Ind Co Ltd | Expanded sheet comprising polypropylene-based resin composition and molded product |
| 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 |
| JP2007009018A (en) * | 2005-06-29 | 2007-01-18 | Jsp Corp | Process for producing expandable styrenic resin particle, expandable styrenic resin particle and molded product of styrenic resin expanded particle |
| JP2010222490A (en) * | 2009-03-24 | 2010-10-07 | Kaneka Corp | Foamable styrenic resin particle |
| WO2010113874A1 (en) | 2009-03-30 | 2010-10-07 | 積水化成品工業株式会社 | Expandable polystyrene resin particles and process for producing same |
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1997
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| JP2003055493A (en) * | 2001-08-10 | 2003-02-26 | Kanegafuchi Chem Ind Co Ltd | Expanded sheet comprising polypropylene-based resin composition and molded product |
| 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 |
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