JPH0342212A - Method for ageing foamable styrene resin particle - Google Patents
Method for ageing foamable styrene resin particleInfo
- Publication number
- JPH0342212A JPH0342212A JP17778089A JP17778089A JPH0342212A JP H0342212 A JPH0342212 A JP H0342212A JP 17778089 A JP17778089 A JP 17778089A JP 17778089 A JP17778089 A JP 17778089A JP H0342212 A JPH0342212 A JP H0342212A
- Authority
- JP
- Japan
- Prior art keywords
- water
- particles
- resin particles
- ageing
- aging
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000032683 aging Effects 0.000 title claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 30
- 229920005989 resin Polymers 0.000 title abstract description 22
- 239000011347 resin Substances 0.000 title abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001890 Novodur Polymers 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 239000004604 Blowing Agent Substances 0.000 claims description 9
- 230000002431 foraging effect Effects 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 229920006248 expandable polystyrene Polymers 0.000 description 15
- 230000004927 fusion Effects 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010557 suspension polymerization reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000001273 butane Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- -1 α-methylstyrene Chemical compound 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- GCAONVVVMAVFDE-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC GCAONVVVMAVFDE-CLFAGFIQSA-N 0.000 description 1
- IVZSTQJPMCJHFE-ZPHPHTNESA-N (z)-n-hexadecyloctadec-9-enamide Chemical compound CCCCCCCCCCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC IVZSTQJPMCJHFE-ZPHPHTNESA-N 0.000 description 1
- VZGOTNLOZGRSJA-ZZEZOPTASA-N (z)-n-octadecyloctadec-9-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC VZGOTNLOZGRSJA-ZZEZOPTASA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- YCWQBZCTYWZZAX-UHFFFAOYSA-N ditert-butyl 7,8-dioxabicyclo[4.2.0]octane-3,6-dicarboxylate Chemical compound C1C(C(=O)OC(C)(C)C)CCC2(C(=O)OC(C)(C)C)OOC21 YCWQBZCTYWZZAX-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PECBPCUKEFYARY-ZPHPHTNESA-N n-[(z)-octadec-9-enyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC PECBPCUKEFYARY-ZPHPHTNESA-N 0.000 description 1
- HMWYLVAUOZBFGZ-UHFFFAOYSA-N n-docosyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC HMWYLVAUOZBFGZ-UHFFFAOYSA-N 0.000 description 1
- WYZSGZLUHOZOIN-UHFFFAOYSA-N n-dodecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCCCCCCC WYZSGZLUHOZOIN-UHFFFAOYSA-N 0.000 description 1
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MGDIOJPGJAGMGP-UHFFFAOYSA-N pentacosanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCC(N)=O MGDIOJPGJAGMGP-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規にて有用なる発泡性ポリスチレン系樹脂粒
子の熟成法に関するものであり、更に詳細には当該樹脂
粒子を早期にＷ！戒完成するもので発泡性スチレン系樹
脂粒子を工業的に有利に熟成し得ることを特徴とする。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a new and useful method for aging expandable polystyrene resin particles, and more specifically, the present invention relates to a method for aging the resin particles at an early stage. It is characterized by the ability to ripen expandable styrenic resin particles industrially advantageously.
（従来の技術）
スチレン系樹脂にプロパン、ブタン、ペンタン、ヘキサ
ンの如き脂肪族系炭化水素発泡剤等を該樹脂１００重量
部に対して１から１５重量部含浸した発泡性スチレン系
樹脂粒子は、既に良く知られている。(Prior art) Expandable styrenic resin particles are obtained by impregnating 1 to 15 parts by weight of an aliphatic hydrocarbon blowing agent such as propane, butane, pentane, hexane, etc. per 100 parts by weight of the styrene resin. already well known.
一般に発泡性スチレン系樹脂粒子を成形する方法として
、当該樹脂粒子を水蒸気等により予備発泡粒子とし、こ
の予備発泡粒子を小さな孔やスリットが設けられている
金型内で更に加熱して、これらの予備発泡粒子を互いに
融着させて種々の成形体とする方法が知られている。Generally, as a method for molding expandable styrene resin particles, the resin particles are made into pre-expanded particles using water vapor, etc., and the pre-expanded particles are further heated in a mold provided with small holes or slits. Methods of fusing pre-expanded particles together to form various molded bodies are known.
このような目的で使用される発泡性スチレン系樹脂粒子
は、製造後の熟成工程を経ずに製品化し、これを成形す
る為の予備発泡した時、多くの場合、均一で安定した予
備発泡粒子、即ち、個々の予備発泡粒子の切断面セルが
互いに均一で、特に中心部と表皮部のセルの比が１前後
（１：０．５〜１：２）で、そのセルの大きさが１５０
μｍ以下（５０〜１５０ ｕｍ）である予備発泡粒子を
得ることが出来なかった。この様な樹脂粒子を得るため
には、通常常温常圧下、大気中で数日から約１ケ月の所
謂熟成期間を必要とするのが一般的である。Expandable styrenic resin particles used for such purposes are made into products without going through a post-manufacturing aging process, and when they are pre-expanded for molding, they often become uniform and stable pre-expanded particles. That is, the cells on the cut surface of each pre-expanded particle are uniform with each other, and in particular, the ratio of the cells in the center to the outer skin is around 1 (1:0.5 to 1:2), and the cell size is 150.
It was not possible to obtain pre-expanded particles having a particle diameter of less than 10 μm (50 to 150 um). In order to obtain such resin particles, a so-called aging period of several days to about one month is generally required in the atmosphere at room temperature and pressure.
その為に、生産管理上は多量の製品在庫を保有する必要
があり、生産効率が悪い。更に生産直後から数日間、即
ち熟成初期段階では発泡剤の飛散量も多く、防炎上の観
点からも好ましくない。Therefore, in terms of production management, it is necessary to hold a large amount of product inventory, which results in poor production efficiency. Furthermore, during several days immediately after production, that is, at the early stage of ripening, a large amount of blowing agent is scattered, which is unfavorable from a flame-proofing point of view.
これらの問題を解決する為の試みとして、■特定の脂肪
酸アミドの存在下にスチレン等のビニル系モノマーを懸
濁重合させ、独立気泡体の均一安定化を図る方法（特開
昭４８−４８５８８号公報、特開昭５９−１６８０３７
号公報）、更には■発泡性スチレン系樹脂粒子を常圧下
火気中で５から一１５℃の温度下に放置することにより
Ｐｔｃを促進する方法（特公昭４３−６５５３号公報）
等がある。As an attempt to solve these problems, we have developed a method in which a vinyl monomer such as styrene is subjected to suspension polymerization in the presence of a specific fatty acid amide, thereby stabilizing the closed cell structure uniformly (Japanese Patent Laid-Open No. 48-48588). Publication, JP 59-168037
(Japanese Patent Publication No. 43-6553), and (1) a method of accelerating Ptc by leaving expandable styrenic resin particles at a temperature of 5 to 15°C in a flame under normal pressure (Japanese Patent Publication No. 43-6553).
etc.
（発明が解決しようとする課題）
しかしながら、上記■の方法で熟威した発泡性スチレン
系樹脂粒子の予備発泡粒子は成形時の融着性が悪くなる
という欠点があり、また■の方法では熟成効果が不十分
で、短時間の熟成では均一で安定した予備発泡粒子が得
にくいという欠点がある。更にこれらの方法では原料費
、設備費、ランニング費等の経費が増大し、コストアッ
プとなるという問題もある。(Problem to be Solved by the Invention) However, the pre-expanded particles of expandable styrenic resin particles aged by the above method (■) have a drawback that the fusion properties during molding become poor, and the aged The disadvantage is that the effect is insufficient and it is difficult to obtain uniform and stable pre-expanded particles with short aging. Furthermore, these methods have the problem of increased expenses such as raw material costs, equipment costs, and running costs, leading to an increase in costs.
（課題を解決するための手段）
上記に鑑み、本発明者らは掛かる従来の欠点を解決する
ため鋭意検討した結果、発泡性スチレン系樹脂粒子を３
０℃以上の水中に攪拌等により浸漬させることにより短
時間で熟成を完了させることができ、この直後に取り出
し、直ちに予備発泡させ、成形に供した場合でも良好な
る成形体を安定して得る事が出来ること、およびこの成
形体は成形時の融着性および成形品表面の平滑性が向上
することを見い出し、本発明を完成するに至った。(Means for Solving the Problems) In view of the above, the present inventors have made intensive studies to solve the conventional drawbacks, and have found that expandable styrene resin particles
Aging can be completed in a short time by immersing it in water at 0°C or higher with stirring, etc., and even if it is taken out immediately after and pre-foamed immediately and used for molding, a good molded product can be stably obtained. The present inventors have discovered that this molded product has improved fusion adhesion during molding and improved surface smoothness of the molded product, and has completed the present invention.
すなわち、本発明は、発泡性スチレン系樹脂粒子を常圧
下、３０℃以上の水中で熟成することを特徴とする発泡
性スチレン系樹脂粒子の熟成方法を提供するものである
。That is, the present invention provides a method for aging expandable styrenic resin particles, which is characterized by aging expandable styrenic resin particles in water at 30° C. or higher under normal pressure.
本発明で用いるスチレン系樹脂としてはスチレンの単独
重合体、スチレンと共重合可能な他の七ツマ−１例えば
α−メチルスチレン、核ハロゲン化スチレン、核アルキ
ル化スチレン等の他のスチレン系モノマー：アクリロニ
トリル；アクリル酸、メタクリル酸；アクリル酸又はメ
タクリル酸と１〜８個の炭素原子を有するアルコールと
のエステル；ビニルカルバゾールなどのＮ−ビニル化合
物：無水マレイン酸；ブタジェン、ブタンジオールジア
クリレートなどの二個の重合可能な二重接合を有する化
合物等との共重合体、更にスチレン４０〜９０ｗｔ％及
び１０〜６０％のエチレン又はプロピレンとのブロック
共重合体又はグラフト共重合体等が挙げられる。Examples of the styrenic resin used in the present invention include styrene homopolymers, other styrene monomers copolymerizable with styrene, such as α-methylstyrene, nuclear halogenated styrene, nuclear alkylated styrene, etc. Acrylonitrile; acrylic acid, methacrylic acid; esters of acrylic acid or methacrylic acid with alcohols having 1 to 8 carbon atoms; N-vinyl compounds such as vinyl carbazole; maleic anhydride; Examples include copolymers with a compound having a polymerizable double junction, and block copolymers or graft copolymers with 40 to 90 wt% styrene and 10 to 60% ethylene or propylene.
本発明で用いる発泡性スチレン系樹脂粒子の製造法は、
特に限定されない。例えば、−船釣な発泡性スチレン系
樹脂粒子の製造法、即ち重合、発泡剤封入、篩分けを経
て製品化する所謂−段法又は重合、篩分けした後、発泡
剤封入を経て製品化する所謂二段法のどちらでも発泡剤
封入後の樹脂粒子に本発明の熟成方法を施す事が出来る
。なかでも、前記■の方法の様に脂肪酸アミドの存在下
で製造した樹脂粒子は、本発明の熟成方法で熟威し、予
備発泡させることによりセルが比較的小さく、均一であ
って、しかも成形時の融着性および成形品表面の平滑性
に優れる予備発泡粒子が得られる点で好ましい。The method for producing expandable styrenic resin particles used in the present invention is as follows:
Not particularly limited. For example, - A method for manufacturing expandable styrene resin particles, i.e., a so-called step method in which the particles are manufactured through polymerization, encapsulation of a blowing agent, and sieving; In either of the so-called two-stage methods, the aging method of the present invention can be applied to the resin particles after encapsulating the blowing agent. In particular, the resin particles produced in the presence of a fatty acid amide as in the method (2) above are matured by the aging method of the present invention and pre-foamed to have relatively small and uniform cells, and are moldable. This is preferable in that pre-expanded particles with excellent fusion properties and surface smoothness of the molded product can be obtained.
ここで用いる脂肪酸アミドとしては、例えば下記一般式
（１）および（ＩＩ）で表わされるものが挙げられる。Examples of fatty acid amides used here include those represented by the following general formulas (1) and (II).
υ
（式中、ＲおよびＲ′は炭素原子数６〜２４の炭化水素
基、ｎは１〜６を示す。）
具体例としては、メチレンビスラウリン酸アミド、エチ
レンビスステアリン酸アξド、ヘキサメチレンビスパル
逅チン酸アミド、エチレンビスオレイン酸アもド、Ｎ−
ラウリルステアリン酸アミド、Ｎ−パル旦チルステアリ
ン酸ア旦ド、Ｎ−オレイルステプリン酸アくド、Ｎ−ス
テアリルステアミン酸アミド、Ｎ−ベヘニルステアミン
酸アミド、Ｎ〜エルカイルステアリル酸アξド、Ｎ−ラ
ウリルオレイン酸アミド、Ｎ−パルミチルオレイン酸ア
ミド、Ｎ−オレイルオレイン酸アミド、Ｎ−ステアリル
オレイン酸アごド、Ｎ−へヘニルオレイン酸ア旦ド、Ｎ
−エルカイルオレイン酸ア旦ド等及びこれらと同様のラ
ウリン酸アξド、パルミチン酸アくド、ベヘニン酸アミ
ド、エルカ酸アミド等がある。υ (In the formula, R and R' are hydrocarbon groups having 6 to 24 carbon atoms, and n is 1 to 6.) Specific examples include methylene bislauric acid amide, ethylene bisstearic acid amide, hexa Methylene bispartanamide, ethylene bisoleic acid amide, N-
Lauryl stearic acid amide, N-paltanyl stearic acid amide, N-oleyl stearic acid amide, N-stearyl stearic acid amide, N-behenyl stearic acid amide, N~erkyyl stearic acid amide N-lauryl oleic acid amide, N-palmityl oleic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-hhenyl oleic acid amide, N
- erucyl oleic acid amide, etc., and similar lauric acid ξ-do, palmitic acid amide, behenic acid amide, erucic acid amide, etc.
その使用量は、スチレン系樹脂１００部に対して０．０
Ｏ５重量部以上、好ましくは０．０１〜３．０重量部
である。The amount used is 0.0 parts per 100 parts of styrene resin.
The amount of O is 5 parts by weight or more, preferably 0.01 to 3.0 parts by weight.
また、トルエン、エチルベンゼンの如き有機溶剤の他、
水素添加植物性硬化油及びエポキシ化不飽和脂肪酸エス
テル、ジオクチルアジペート、ジブチルマレート等の所
謂可塑化成分等を含有していても良い。In addition to organic solvents such as toluene and ethylbenzene,
It may contain so-called plasticizing components such as hydrogenated vegetable hydrogenated oil, epoxidized unsaturated fatty acid ester, dioctyl adipate, dibutyl maleate, and the like.
さらに、発泡性スチレン系樹脂粒子の形状に関しては、
特別に限定されるものでないが、成形特の金型への充填
効率やスチームの加熱効率の良い球形状である事が好ま
しい。Furthermore, regarding the shape of the expandable styrenic resin particles,
Although not particularly limited, it is preferable to have a spherical shape that has good filling efficiency into a mold and high steam heating efficiency.
発泡剤としてはプロパン、ブタン、ペンタン等、公知の
脂肪族系飽和炭化水素を単独又は任意に混合して使用す
ることが出来る。この場合使用する発泡剤の種類、混合
比に依り水の温度および時間が若干異なるが、概ね発泡
剤単独の沸点が高い程、水の温度は高い方が好ましい。As the blowing agent, known aliphatic saturated hydrocarbons such as propane, butane, pentane, etc. can be used alone or in any combination. In this case, the temperature of the water and the time will vary slightly depending on the type of blowing agent used and the mixing ratio, but in general, the higher the boiling point of the blowing agent alone, the higher the temperature of the water is preferable.
本発明の熟成方法は、製造された発泡性スチレン系樹脂
粒子を常圧下で３０’Ｃ以上の水中に浸漬させておけば
よく、例えば該粒子の上に重しとなるものを置いて水中
に浸漬させる方法等でもよいが、なかでも製造された発
泡性スチレン系樹脂粒子を系から分離後、３０℃以上の
水中に加え、ゆるやかに攪拌しながら熟成させる方法、
あるいは懸濁液中で発泡剤をスチレン系樹脂粒子中に含
浸させた後、該粒子を分離せずに系の感圧と冷却を行い
、必要に応じて水を加えて希釈した懸濁液又はその水希
釈液中でゆるやかに攪拌しながら熟成させる方法等が好
ましい。また、水の温度、熟成時間としては、なかでも
３５〜６０’Ｃの水中に１〜４８時間が好ましく、４０
〜５５゛ｃの水中に２〜ｌＯ時間が特に好ましい。In the aging method of the present invention, the produced expandable styrenic resin particles may be immersed in water at 30'C or higher under normal pressure. For example, a weight may be placed on top of the particles and immersed in water. Methods such as immersion may be used, but among these methods, the produced expandable styrenic resin particles are separated from the system and then added to water at 30° C. or higher, and aged with gentle stirring.
Alternatively, after impregnating the blowing agent into styrene resin particles in a suspension, the system is pressure sensitive and cooled without separating the particles, and if necessary, water is added to dilute the suspension or Preferred is a method in which the product is aged in a water diluted solution while being gently stirred. In addition, the water temperature and aging time are preferably 1 to 48 hours in water at 35 to 60'C, and 40 to 48 hours.
Particularly preferred is 2-10 hours in ~55°C water.
（実施例）
以下に実施例および比較例を示して本発明の方法を具体
的に説明する。尚、例中の％は融着率を除きいずれも重
量％である。(Example) The method of the present invention will be specifically explained below with reference to Examples and Comparative Examples. Note that all percentages in the examples are percentages by weight except for the fusion rate.
実施例１
タービン型攪拌翼を備えた５１ステンレス製反応機に蒸
留水２０００ｇを仕込み、懸濁安定剤としてリン酸カル
シウム８．４ｇ及びドデシルベンゼンスルホン酸ナトリ
ウム０．０５ｇを溶解させ、次いでスチレン２０００
ｇ、ペルオキシへキサヒドロテレフタル酸ジ第３級ブチ
ル８ｇ及び過安息香酸第３ブチル２ｇを順次仕込んだ。Example 1 2,000 g of distilled water was charged into a 51 stainless steel reactor equipped with a turbine-type stirring blade, and 8.4 g of calcium phosphate and 0.05 g of sodium dodecylbenzenesulfonate were dissolved as suspension stabilizers, followed by 2,000 g of styrene.
g, 8 g of di-tert-butyl peroxyhexahydroterephthalate, and 2 g of tert-butyl perbenzoate were sequentially charged.
器内を窒素ガスで置換後、５００ｒｐ＋ｓの撹拌下で昇
温しで９０℃で１０時間懸濁重合させ、重合率が９０％
に達した時点で反応器を密閉状態にし、トルエン４０ｇ
およびブタン１６０ｇを窒素加圧により反応器に圧入し
た後、１２０ ’Ｃに昇温しで３時間維持した。しかる
後、３０℃以下に冷却し、過剰の発泡剤を大気下に抜き
、発泡性ポリスチレン粒子を製造した。この発泡性ポリ
スチレン粒子は製造直後にブタン７％を含有していた。After purging the inside of the vessel with nitrogen gas, the temperature was raised under stirring at 500 rpm + s, and suspension polymerization was carried out at 90°C for 10 hours, resulting in a polymerization rate of 90%.
When the temperature is reached, the reactor is sealed and 40g of toluene is added.
After injecting 160 g of butane into the reactor under nitrogen pressure, the temperature was raised to 120'C and maintained for 3 hours. Thereafter, the mixture was cooled to 30° C. or lower, and excess foaming agent was removed to the atmosphere to produce expandable polystyrene particles. The expandable polystyrene particles contained 7% butane immediately after production.
この粒子を懸濁重合液から分離後、常圧下、■３５℃の
水中で１２時間、■４５℃の水中で７時間、■５０℃の
水中で３時間、それぞれ６０ｒｐｍの攪拌下に熟成を行
った。その後脱水、洗滌、乾燥し、さらにブロッキング
防止剤（ステアリン酸亜鉛）を表面に付着させて目的と
する熟成された発泡性ポリスチレン粒子を得た。この粒
子を１００℃のスチームに依り９０秒間発泡させたとこ
ろ、各々断面セルの均一な予備発泡粒子を得た。またこ
の予備発泡粒子を２４時間放置した後、金型内に充填し
、０．８ ｋｇ／ｃ＋ｓ” （ゲージ圧）のスチーム
で３０Ｘ４０Ｘ３ｍｍＯ魚箱のフタを成形したところ、
融着性と表面平滑性の優れた成形棒を得るに到った。After separating the particles from the suspension polymerization solution, they were aged under normal pressure for 12 hours in 35°C water, 7 hours in 45°C water, and 3 hours in 50°C water with stirring at 60 rpm. Ta. Thereafter, the particles were dehydrated, washed, and dried, and an antiblocking agent (zinc stearate) was attached to the surface to obtain the target aged expandable polystyrene particles. When these particles were foamed for 90 seconds using steam at 100° C., pre-expanded particles with uniform cross-sectional cells were obtained. After leaving the pre-expanded particles for 24 hours, they were filled into a mold and molded into a 30x40x3mmO fish box lid using steam at 0.8 kg/c+s" (gauge pressure).
A molded rod with excellent fusion properties and surface smoothness was obtained.
比較例１
発泡性ポリスチレン系樹脂粒子を懸濁重合液から分離後
、２０℃の水中で６Ｏｒｐｍの攪拌下に４８時間熟成さ
せた以外は全て実施例１と同様にして、発泡性ポリスチ
レン粒子を得た。この粒子を実施例１と同様にスチーム
に依り発泡させたところ、断面セルは不均一で、かつ中
心部は粗大化し、商品として使用に耐えないものであっ
た。Comparative Example 1 Expandable polystyrene particles were obtained in the same manner as in Example 1, except that the expandable polystyrene resin particles were separated from the suspension polymerization liquid and then aged in water at 20° C. for 48 hours with stirring at 6 Orpm. Ta. When these particles were foamed with steam in the same manner as in Example 1, the cross-sectional cells were non-uniform and the center became coarse, making them unsuitable for commercial use.
比較例２
発泡性ポリスチレン粒子を懸濁重合液から分離後、２５
℃の大気中に１週間放置して熟成させた以外は全て実施
例１と同様にして、発泡性ポリスチレン粒子を得た。こ
の粒子を実施例１と同様にスチームに依り発泡させたと
ころ、断面セルは不均一で、かつ中心部は粗大化し、商
品として使用に耐えないものであった。Comparative Example 2 After separating expandable polystyrene particles from suspension polymerization liquid, 25
Expandable polystyrene particles were obtained in the same manner as in Example 1, except that the particles were left in the atmosphere at ℃ for one week to ripen. When these particles were foamed with steam in the same manner as in Example 1, the cross-sectional cells were non-uniform and the center became coarse, making them unsuitable for commercial use.
比較例３
発泡性ポリスチレン粒子を懸濁重合液から分離後、−５
℃の大気中に４８時間放置して熟成させた以外は全て実
施例１と同様にして、発泡性ポリスチレン粒子を得た。Comparative Example 3 -5 after separating expandable polystyrene particles from suspension polymerization solution
Expandable polystyrene particles were obtained in the same manner as in Example 1, except that the particles were left to mature in the atmosphere at .degree. C. for 48 hours.
この粒子を実施例１と同様にスチームに依り発泡させた
ところ、断面セルは不均一で、かつ中心部は粗大化し、
商品として使用に耐えないものであった。When these particles were foamed with steam in the same manner as in Example 1, the cross-sectional cells were non-uniform and the center became coarse.
It was not suitable for use as a product.
実施例２
ブタンの代わりにペンタンを用い、さらに水の温度と熟
成時間をそれぞれ３５℃の水中で２０時間、４５℃の水
中で１２時間及び５０℃の水中で６時間に変えた外は全
て実施例１と同様にして製造した。この樹脂粒子をスチ
ームに依り発泡させたところ、各々断面セルの均一な予
備発泡粒子を得た。またこの予備発泡粒子を２４時間放
置した後、成形したところ、融着性と表面平滑性の優れ
た成形体を得るに到った。Example 2 All experiments were carried out except that pentane was used instead of butane, and the water temperature and aging time were changed to 20 hours in 35°C water, 12 hours in 45°C water, and 6 hours in 50°C water, respectively. Produced in the same manner as in Example 1. When these resin particles were foamed with steam, pre-expanded particles with uniform cross-sectional cells were obtained. Furthermore, when the pre-expanded particles were left to stand for 24 hours and then molded, a molded article with excellent fusion properties and surface smoothness was obtained.
実施例３
懸濁重合反応に用いた重合液を発泡性ポリスチレン粒子
から分離せずに、そのまま加温し、実施例１と同様の３
条件で熟成を行った。この発泡性ポリスチレン粒子を実
施例１と同様にスチームに依り発泡させたところ、各々
断面セルの均一な予備発泡粒子を得た。またこの予備発
泡粒子を２４時間放置した後、成形したところ、融着性
と表面平滑性の優れた成形体を得るに到った。Example 3 The polymerization solution used in the suspension polymerization reaction was heated as it was without separating it from the expandable polystyrene particles, and the same procedure as in Example 1 was carried out.
Aging was performed under these conditions. When these expandable polystyrene particles were foamed with steam in the same manner as in Example 1, pre-expanded particles with uniform cross-sectional cells were obtained. Furthermore, when the pre-expanded particles were left to stand for 24 hours and then molded, a molded article with excellent fusion properties and surface smoothness was obtained.
比較例４
エチレンビスステアリン酸アξド２ｇの存在下に重合さ
せた以外は実施例１と同様にして発泡性ポリスチレン粒
子を得た。この粒子を実施例１と同様にスチームに依り
発泡させたところ、断面セルが８０μｍ前後と比較的小
さく、しかも均一な予備発泡粒子を得た。しかし、この
予備発泡粒子を２４時間放置した後、成形したところ、
融着性が悪く、商品として使用に耐えないものであった
。Comparative Example 4 Expandable polystyrene particles were obtained in the same manner as in Example 1, except that the polymerization was carried out in the presence of 2 g of ethylene bisstearate ξ. When these particles were foamed with steam in the same manner as in Example 1, pre-expanded particles with relatively small cross-sectional cells of around 80 μm and uniformity were obtained. However, when these pre-expanded particles were molded after being left for 24 hours,
It had poor fusion properties and could not be used as a commercial product.
実施例４
比較例４で得た発泡性ポリスチレン粒子を実施例１と同
様にして３条件で熟成を行った。この発泡性ポリスチレ
ン粒子を実施例１と同様にスチームに依り発泡させたと
ころ、各々断面セルが８０μｍ前後と比較的小さく、し
かも均一な予備発泡粒子を得た。この予備発泡粒子を２
４時間放置した後、成形したところ、融着性と表面平滑
性の優れた成形体を得るに至った。Example 4 The expandable polystyrene particles obtained in Comparative Example 4 were aged in the same manner as in Example 1 under three conditions. When these expandable polystyrene particles were foamed with steam in the same manner as in Example 1, pre-expanded particles were obtained which had relatively small cross-sectional cells of around 80 μm and were uniform. These pre-expanded particles
After leaving it for 4 hours, it was molded, and a molded product with excellent fusion properties and surface smoothness was obtained.
実施例５
ポリスチレン粒子の代わりにメタクリル酸含有率１０％
のスチレン−メタクリル酸共重合樹脂粒子を用いた以外
は実施例１と同様にして３条件で熟成を行った。この発
泡性スチレン−メタクリル酸共重合樹脂粒子を実施例１
と同様にスチームに依り発泡させた゛ところ、各々断面
セルの均一な予備発泡粒子を得た。この予備発泡粒子を
２４時間放置した後、成形したところ、融着性と表面平
滑性の優れた成形体を得るに至った。Example 5 Methacrylic acid content 10% instead of polystyrene particles
Aging was carried out under three conditions in the same manner as in Example 1, except that styrene-methacrylic acid copolymer resin particles were used. Example 1 This expandable styrene-methacrylic acid copolymer resin particles
When foaming was carried out using steam in the same manner as above, pre-foamed particles with uniform cross-sectional cells were obtained. When the pre-expanded particles were left to stand for 24 hours and then molded, a molded article with excellent fusion properties and surface smoothness was obtained.
以下の第１表に実施例１〜４および比較例１〜４の試験
結果をまとめて示す。Table 1 below summarizes the test results of Examples 1 to 4 and Comparative Examples 1 to 4.
／′
／
（発明の効果）
本発明の熟成方法によれば、短時間で熟成を完了させる
ことができ、均一で安定した予備発泡粒子を容易に得る
ことができる。しかも成形時の融着率が高く、成形品の
表面平滑性も良好である。/'/ (Effects of the Invention) According to the aging method of the present invention, aging can be completed in a short time, and uniform and stable pre-expanded particles can be easily obtained. Moreover, the fusion rate during molding is high, and the surface smoothness of the molded product is also good.
Claims (1)
水中で熟成することを特徴とする発泡性スチレン系樹脂
粒子の熟成方法。 ２、３５〜６０℃の水中で１〜４８時間熟成する請求項
１記載の熟成方法。 ３、４０〜５５℃の水中で２〜１０時間熟成する請求項
１記載の熟成方法。 ４、スチレン系樹脂粒子に発泡剤を含浸するに要した懸
濁液又はその水希釈液中で熟成させる請求項１記載の熟
成方法。 ５、発泡性スチレン系樹脂粒子を分離した後、熟成する
請求項１記載の熟成方法。[Claims] 1. A method for aging expandable styrenic resin particles, which comprises aging expandable styrenic resin particles in water at 30° C. or higher under normal pressure. 2. The aging method according to claim 1, wherein the aging is carried out in water at 35 to 60°C for 1 to 48 hours. 3. The aging method according to claim 1, wherein aging is carried out in water at 40 to 55°C for 2 to 10 hours. 4. The aging method according to claim 1, wherein the styrenic resin particles are aged in a suspension required for impregnating the blowing agent or a diluted solution thereof in water. 5. The aging method according to claim 1, wherein the expandable styrenic resin particles are separated and then aged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1177780A JP2893731B2 (en) | 1989-07-10 | 1989-07-10 | Aging method for expandable styrene resin particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1177780A JP2893731B2 (en) | 1989-07-10 | 1989-07-10 | Aging method for expandable styrene resin particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0342212A true JPH0342212A (en) | 1991-02-22 |
| JP2893731B2 JP2893731B2 (en) | 1999-05-24 |
Family
ID=16036981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1177780A Expired - Lifetime JP2893731B2 (en) | 1989-07-10 | 1989-07-10 | Aging method for expandable styrene resin particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2893731B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156599A (en) * | 2006-11-30 | 2008-07-10 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particle, foamed molded article, their production methods, pre-foamed particle |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787435A (en) * | 1980-11-20 | 1982-05-31 | Kanegafuchi Chem Ind Co Ltd | Expandable thermoplastic polymer particle |
| JPS58126128A (en) * | 1982-01-25 | 1983-07-27 | Asahi Chem Ind Co Ltd | Rigid thermoplastic resin foamed body and its manufacture |
| JPS58222122A (en) * | 1982-06-18 | 1983-12-23 | Kanegafuchi Chem Ind Co Ltd | Production of expandable styrene polymer particle |
| JPS61116526A (en) * | 1984-11-12 | 1986-06-04 | Sekisui Plastics Co Ltd | Molding process of foaming resin |
-
1989
- 1989-07-10 JP JP1177780A patent/JP2893731B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787435A (en) * | 1980-11-20 | 1982-05-31 | Kanegafuchi Chem Ind Co Ltd | Expandable thermoplastic polymer particle |
| JPS58126128A (en) * | 1982-01-25 | 1983-07-27 | Asahi Chem Ind Co Ltd | Rigid thermoplastic resin foamed body and its manufacture |
| JPS58222122A (en) * | 1982-06-18 | 1983-12-23 | Kanegafuchi Chem Ind Co Ltd | Production of expandable styrene polymer particle |
| JPS61116526A (en) * | 1984-11-12 | 1986-06-04 | Sekisui Plastics Co Ltd | Molding process of foaming resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156599A (en) * | 2006-11-30 | 2008-07-10 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particle, foamed molded article, their production methods, pre-foamed particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2893731B2 (en) | 1999-05-24 |
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