JPS63193939A - Expandable styrene resin particle and production thereof - Google Patents
Expandable styrene resin particle and production thereofInfo
- Publication number
- JPS63193939A JPS63193939A JP2686687A JP2686687A JPS63193939A JP S63193939 A JPS63193939 A JP S63193939A JP 2686687 A JP2686687 A JP 2686687A JP 2686687 A JP2686687 A JP 2686687A JP S63193939 A JPS63193939 A JP S63193939A
- Authority
- JP
- Japan
- Prior art keywords
- paraffin
- polymerization
- resin particles
- styrene
- styrenic 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 64
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920005989 resin Polymers 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000012188 paraffin wax Substances 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 4
- 229920001890 Novodur Polymers 0.000 claims description 26
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 abstract description 15
- 238000000465 moulding Methods 0.000 abstract description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 4
- 239000001273 butane Substances 0.000 abstract description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000001294 propane Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 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 3
- 235000019731 tricalcium phosphate Nutrition 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- -1 ethylene, propylene, butadiene Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 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
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000203 mixture Substances 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
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、発泡性スチレン系樹脂粒子及びその製造方法
に関する。更に詳しくは、本発明は、発泡性スチレン系
樹脂粒子の成形加工時における、冷却時間を短縮できる
発泡性スチレン系樹脂粒子及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to expandable styrenic resin particles and a method for producing the same. More specifically, the present invention relates to expandable styrenic resin particles that can shorten the cooling time during molding of expandable styrenic resin particles, and a method for producing the same.
（従来の技術）
発泡性スチレン系樹脂粒子の成形加工時には、冷却に長
時間を要する。特に、近年普及している減圧下で冷却す
る成形方法においては、冷却に要する時間は、成形工程
の７０〜８０％を占めるため、生成サイクルが長くなり
、生産性が著しく低下する。この冷却時間を短縮する方
法として、特開昭５５−１２７４４３号公報に開示され
ているように、融点が３７．８〜８０℃のパラフィンロ
ウを樹脂粒子表面に添加する方法がある。(Prior Art) When molding expandable styrenic resin particles, cooling takes a long time. In particular, in the molding method that involves cooling under reduced pressure, which has become popular in recent years, the time required for cooling accounts for 70 to 80% of the molding process, which lengthens the production cycle and significantly reduces productivity. As a method of shortening this cooling time, there is a method of adding paraffin wax having a melting point of 37.8 to 80 DEG C. to the surface of the resin particles, as disclosed in Japanese Patent Application Laid-Open No. 55-127443.
特開昭６０−１９５１３５号公報には、融点が４０〜７
０℃のパラフィンワックスを水性エマルジョンとし、樹
脂粒子表面へ添加する方法が開示されている。JP-A-60-195135 discloses that the melting point is 40 to 7.
A method is disclosed in which paraffin wax at 0° C. is made into an aqueous emulsion and added to the surface of resin particles.
（発明が解決しようとする問題点）
しかしながら、特開昭５５−１２７４４３号公報に開示
されている方法では、常温で固体のパラフィンロウを使
用するため、樹脂粒子表面への均一付着が難しく、予備
発泡時にブロッキングしゃすい、また、成形体の融着性
がばらつく等の問題点がある。また、樹脂粒子表面が若
干粘着性を帯びるため、粒子の流動性を悪くする等の欠
点がある。(Problems to be Solved by the Invention) However, the method disclosed in JP-A-55-127443 uses paraffin wax that is solid at room temperature, which makes it difficult to uniformly adhere to the surface of the resin particles. There are problems such as blocking during foaming and variation in the fusion properties of the molded product. Furthermore, since the surface of the resin particles becomes slightly sticky, there are drawbacks such as poor fluidity of the particles.
また、特開昭６０−１９５１３５号公報に開示されてい
る方法は、パラフィンワックスを水性エマルジョンとし
ているので、粒子表面への均一付着ができ、上述の欠点
は改善されるが、水性であるため、粒子の流動性を悪く
する欠点を有する。Furthermore, since the method disclosed in JP-A-60-195135 uses paraffin wax as an aqueous emulsion, it can be uniformly adhered to the particle surface and the above-mentioned drawbacks are improved, but since it is aqueous, It has the disadvantage of worsening the fluidity of particles.
従って、本発明は、上記の問題点を解決し、成形加工時
の冷却時間を短縮でき、粒子表面へのブリードがなく、
粒子の流動性を損なわず、また、予備発泡時の耐ブロツ
キング性において優れた、新しい発泡性スチレン系樹脂
粒子及びその製造方法を提供することを目的とする。Therefore, the present invention solves the above problems, shortens the cooling time during molding, eliminates bleeding to the particle surface,
The object of the present invention is to provide new expandable styrenic resin particles that do not impair the fluidity of the particles and have excellent blocking resistance during pre-foaming, and a method for producing the same.
（問題点を解決するための手段）
第一の発明は、常温で液状又は気体状の発泡剤を含有す
る発泡性スチレン系樹脂粒子において、該粒子が、融点
４０〜７０℃のパラフィンを該粒子に対して０．０１〜
０．５重量％含有して成る発泡性スチレン系樹脂粒子に
関する。(Means for Solving the Problems) The first invention provides expandable styrenic resin particles containing a blowing agent that is liquid or gaseous at room temperature, wherein the particles contain paraffin having a melting point of 40 to 70°C. 0.01~
It relates to expandable styrenic resin particles containing 0.5% by weight.
本発明における発泡性スチレン系樹脂粒子に含まれるス
チレン系樹脂は、スチレン又はα−メチルスチレン、ビ
ニルトルエン、ｐ−クロロスチレンなどのスチレン系誘
導体の単独又は共重合体、アクリロニトリル、アクリル
酸エチル、アクリル酸ブチル等のアクリル酸エステル、
メタクリル酸メチル、メタクリル酸ブチル、メタクリル
酸セチル等のメタクリル酸エステル、ビニルピリジン、
ビニルカルバゾール、エチレン、プロピレン、ブタジェ
ン等の千ツマ−（以下、これらを「他のモノマー」とい
う）とスチレン又はスチレン系誘導体との共重合体であ
る。これらのモノマーのうち、スチレン又はスチレン系
誘導体を５０重量％以上使用するのが好ましい。The styrenic resin contained in the expandable styrenic resin particles in the present invention is styrene or a styrene derivative such as α-methylstyrene, vinyltoluene, p-chlorostyrene, acrylonitrile, ethyl acrylate, acrylic Acrylic acid esters such as butyl acid,
Methacrylic acid esters such as methyl methacrylate, butyl methacrylate, cetyl methacrylate, vinylpyridine,
It is a copolymer of monomers such as vinylcarbazole, ethylene, propylene, butadiene (hereinafter referred to as "other monomers") and styrene or styrene derivatives. Among these monomers, it is preferable to use styrene or styrene derivatives in an amount of 50% by weight or more.
第一の発明に使用するパラフィンの融点は、４０〜７０
℃である。融点が４０℃未満では、粒子中に含浸させた
パラフィンが粒子表面ヘブリードしやすくなるため、粒
子表面が粘着性を帯び、流動性を悪（する。また、融点
が７０ ’ｃを越えると、樹脂粒子中への含浸性が悪く
なり、成形体の融着を悪化させる。パラフィンは、スチ
レン系樹脂粒子中に０．０１〜０．５重量％、好ましく
は０．０３〜０．２重量％含有させる。パラフィンが０
．０１重量％未満であると、冷却時間の短縮効果はなく
、０、５重量％を越えると、粒子表面へのブリードによ
り、粒子の流動性が悪くなり、成形体の融着性が悪化す
る。The paraffin used in the first invention has a melting point of 40 to 70.
It is ℃. If the melting point is less than 40°C, the paraffin impregnated into the particles tends to bleed onto the particle surface, making the particle surface sticky and impairing fluidity. Impregnating into the particles becomes poor, which worsens the fusion of the molded object.Paraffin is contained in the styrenic resin particles in an amount of 0.01 to 0.5% by weight, preferably 0.03 to 0.2% by weight. Paraffin is 0.
．． If it is less than 0.01% by weight, there will be no effect of shortening the cooling time, and if it exceeds 0.5% by weight, the fluidity of the particles will deteriorate due to bleeding to the particle surface, and the fusion properties of the molded product will deteriorate.
第二の発明は、第一の発明の発泡性スチレン系樹脂粒子
の製造方法に関する。The second invention relates to a method for producing the expandable styrenic resin particles of the first invention.
すなわち、第二の発明は、スチレン系モノマーを水性媒
体中で懸濁重合するに当たり、融点４０〜７０℃のパラ
フィンを重合系に存在させ、重合後半又は重合完了後に
発泡剤を含浸させることを特徴とする発泡性スチレン系
樹脂粒子の製造方法に関する。That is, the second invention is characterized in that when a styrenic monomer is suspension-polymerized in an aqueous medium, paraffin having a melting point of 40 to 70°C is present in the polymerization system, and a blowing agent is impregnated in the latter half of the polymerization or after the completion of the polymerization. The present invention relates to a method for producing expandable styrenic resin particles.
発泡性スチレン系樹脂粒子中に、融点が４０〜７０℃の
パラフィンを０．０１〜０．５重量％含有させるには、
スチレン系モノマーに予めパラフィンを溶解させて（重
合初期から重合系に脂肪族パラフィンを存在させて）重
合するか又はスチレン系モノマーの重合率が９０重景％
までの間にパラフィンを重合系に添加すればよく、この
場合、パラフィンは少量の溶剤又はスチレン系モノマー
に溶解して重合系に添加するのが好ましい。その際使用
する溶剤は、例えばベンゼン、トルエン、シクロヘキサ
ン等の有機溶剤である。パラフィンは、重合率が５０重
量％以上の時点で添加するのが好ましい。重合率が５０
％未満の時に、パラフィンを添加すると、分散系に影響
し、過大粒子を多く発生させる傾向があるためである。In order to contain 0.01 to 0.5% by weight of paraffin having a melting point of 40 to 70°C in the expandable styrenic resin particles,
Polymerization is carried out by dissolving paraffin in the styrene monomer in advance (with aliphatic paraffin present in the polymerization system from the initial stage of polymerization), or the polymerization rate of the styrene monomer is 90%.
Paraffin may be added to the polymerization system during this time. In this case, paraffin is preferably dissolved in a small amount of a solvent or a styrene monomer and then added to the polymerization system. The solvent used in this case is, for example, an organic solvent such as benzene, toluene, or cyclohexane. Paraffin is preferably added when the polymerization rate is 50% by weight or more. Polymerization rate is 50
This is because if paraffin is added when the amount is less than %, it will affect the dispersion system and tend to generate many oversized particles.
また、パラフィンの添加が、重合率９０重量％を越えて
からでは、樹脂粒子中への含浸が困難となる。Furthermore, if paraffin is added after the polymerization rate exceeds 90% by weight, it becomes difficult to impregnate the paraffin into the resin particles.
第二の発明においては、重合後半又は重合完了後に発泡
剤を添加するが、スチレン系樹脂粒子中にパラフィンを
添加した後に発泡剤の含浸を行うことが重要である。パ
ラフィンは、得られた発泡性スチレン系樹脂粒子中に、
０．０１〜０．５重量％含まれるように使用されるが、
このためには、七ツマー総量に対して約０．０１〜０．
８重量％使用すればよい。In the second invention, the blowing agent is added in the latter half of the polymerization or after the completion of the polymerization, but it is important to impregnate the blowing agent after adding the paraffin into the styrene resin particles. Paraffin is contained in the resulting expandable styrenic resin particles.
It is used to contain 0.01 to 0.5% by weight,
For this purpose, approximately 0.01 to 0.
It is sufficient to use 8% by weight.
第二の発明において、スチレン系モノマーとしては、ス
チレン及び第一の発明におけるスチレン誘導体があり、
これは一種又は二種以上使用される。また、他のモノマ
ーとして、第一の発明におけるスチレン又はスチレン誘
導体と共重合体を形成しうる他のモノマーをスチレン又
はスチレン誘導体と併用できる。他の七ツマ−は、モノ
マーの総量に対して５０重量％以下で使用される。In the second invention, the styrenic monomer includes styrene and the styrene derivative in the first invention,
One or more types of these may be used. Further, as other monomers, other monomers capable of forming a copolymer with styrene or the styrene derivative in the first invention can be used in combination with the styrene or the styrene derivative. Other hexamers are used in amounts up to 50% by weight based on the total amount of monomers.
発泡剤としては、常温で液状又は気体状の易揮発性の有
機化合物で、その沸点が上記スチレン系樹脂粒子の軟化
点以下のものを、単独又は混合物として使用する。この
ような発泡剤は、例えば、プロパン、ブタン、イソブタ
ン、ペンタン、イソペンタン、ヘキサン、シクロヘキサ
ン、塩化メチル、フロンガス等である。発泡剤の使用量
は、スチレン系樹脂粒子に対して１〜２０重量％とする
。As the blowing agent, easily volatile organic compounds that are liquid or gaseous at room temperature and whose boiling point is equal to or lower than the softening point of the styrene resin particles are used alone or as a mixture. Such blowing agents include, for example, propane, butane, isobutane, pentane, isopentane, hexane, cyclohexane, methyl chloride, chlorofluorocarbon gas, and the like. The amount of the blowing agent used is 1 to 20% by weight based on the styrene resin particles.
発泡剤の含浸は、前記のように重合途中又は重合完了後
に、水性媒体中に重合物粒子を懸濁させた状態で発泡剤
を添加することにより行われる。重合途中で発泡剤を添
加する場合には、重合系の安定性、得られる発泡性スチ
レン系樹脂粒子の品質から、９５％以上の重合率で添加
するのが好ましい。The impregnation of the foaming agent is carried out by adding the foaming agent during the polymerization or after the completion of the polymerization, with the polymer particles suspended in the aqueous medium, as described above. When a blowing agent is added during polymerization, it is preferably added at a polymerization rate of 95% or more in view of the stability of the polymerization system and the quality of the resulting expandable styrenic resin particles.
懸濁重合する際に、分散剤として、難溶性リン酸塩、水
溶性高分子保護コロイド等を用いる。難溶性リン酸塩は
、スチレン系モノマーに対して０．０１重量％以上、水
溶性高分子保護コロイドは１〜０．００１重量％の範囲
で使用するのが好ましい。その他、陰イオン界面活性剤
、水溶性無機塩等を重合系に添加することもできる。During suspension polymerization, sparingly soluble phosphates, water-soluble polymeric protective colloids, and the like are used as dispersants. The sparingly soluble phosphate is preferably used in an amount of 0.01% by weight or more based on the styrene monomer, and the water-soluble polymer protective colloid is preferably used in a range of 1 to 0.001% by weight. In addition, anionic surfactants, water-soluble inorganic salts, etc. can also be added to the polymerization system.
本発明に使用する重合開始剤は、通常、スチレン系モノ
マーの重合に使用される開始剤であってよく、例えば、
過酸化ベンゾイル、ジクミルペルオキシド、過酢酸ｔｅ
ｒｔ−ブチル、過安息香酸ｔｅｒｔ−ブチル、メチルエ
チルケトンペルオキシド等であり、単独又は２種以上使
用できる。その使用量は、得られる重合体の目的とする
分子量により決められるものであるが、好ましくは０．
１〜０．４重量％である。重合開始剤は、スチレン系モ
ノマーに溶解して使用する。The polymerization initiator used in the present invention may be an initiator normally used for polymerizing styrenic monomers, for example,
benzoyl peroxide, dicumyl peroxide, peracetic acid te
These include rt-butyl, tert-butyl perbenzoate, methyl ethyl ketone peroxide, etc., and they can be used alone or in combination of two or more. The amount used is determined by the desired molecular weight of the resulting polymer, but is preferably 0.
It is 1 to 0.4% by weight. The polymerization initiator is used after being dissolved in a styrene monomer.
（実施例）
次に、実施例に基づいて本発明を詳述するが、本発明は
これに限定されるものではない。例中、「部」は、特に
断らない限り、「重量部」を意味する。(Example) Next, the present invention will be described in detail based on Examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight" unless otherwise specified.
実施例１
攪拌機付きオートクレーブ中で第三リン酸カルシウム０
．１部及び１％ドデシルベンゼンスルホン酸ナトリウム
水溶液０．５部を蒸留水１００部に分散又は溶解させる
。これに過酸化ベンゾイル０．２５部、融点６０℃のパ
ラフィン０．２部及び過安息香酸ｔｅｒ ｔ−ブチル０
．０５部を溶解させたスチレン１００部を攪拌しながら
添加し、窒素ガス雰囲気下で９０℃で重合を開始させた
。２時間３０分後に、第三リン酸カルシウム０．３部を
加え、更に７時間目に第三リン酸カルシウム０．３部を
加えた後、シクロヘキサン２部及びブタン８部を窒素で
圧入した。その後、１２０℃に５時間保持した後、室温
に冷却し、発泡性スチレン系樹脂粒子を得た。Example 1 Tricalcium phosphate 0 in an autoclave with a stirrer
．． 1 part and 0.5 part of a 1% aqueous solution of sodium dodecylbenzenesulfonate are dispersed or dissolved in 100 parts of distilled water. To this, 0.25 parts of benzoyl peroxide, 0.2 parts of paraffin with a melting point of 60°C, and 0 tert-butyl perbenzoate.
．． 100 parts of styrene in which 05 parts of styrene was dissolved was added with stirring, and polymerization was started at 90° C. under a nitrogen gas atmosphere. After 2 hours and 30 minutes, 0.3 part of tribasic calcium phosphate was added, and after 7 hours, 0.3 part of tribasic calcium phosphate was further added, and then 2 parts of cyclohexane and 8 parts of butane were pressurized with nitrogen. Thereafter, the temperature was maintained at 120° C. for 5 hours, and then cooled to room temperature to obtain expandable styrenic resin particles.
この粒子には、パラフィンが約０．１４重貴簡含まれて
いた。The particles contained about 0.14 paraffins.
実施例２
８点６０℃のパラフィンをシクロヘキサン２部に溶解し
、９０℃で２時間３０分重合後に添加した以外は実施例
１と同様に重合及び発泡剤の添加を行い、発泡性スチレ
ン系樹脂粒子を得た。この粒子には、パラフィンが約０
．１４重量％含まれていた。Example 2 Polymerization and blowing agent addition were carried out in the same manner as in Example 1, except that 8 points of paraffin at 60°C were dissolved in 2 parts of cyclohexane and added after polymerization at 90°C for 2 hours and 30 minutes. Particles were obtained. The particles contain approximately 0 paraffin.
．． It contained 14% by weight.
比較例１
融点６０℃のパラフィンワックスを使用しない以外は実
施例１と同様に操作し、発泡性スチレン系樹脂粒子を得
た。Comparative Example 1 Expandable styrenic resin particles were obtained in the same manner as in Example 1 except that paraffin wax with a melting point of 60° C. was not used.
比較例２
常温で液状の流動パラフィンを使用した以外は実施例１
と同様に操作し、発泡性スチレン系樹脂粒子を得た。Comparative Example 2 Example 1 except that liquid paraffin, which is liquid at room temperature, was used.
Expandable styrenic resin particles were obtained in the same manner as above.
上記実施例１及び２において、発泡性スチレン系樹脂粒
子が含むパラフィン量は、該粒子をｎ −ヘキサン中で
還流した後、ビーズを分離して得られたｎ−ヘキサン溶
液を乾固して残存したパラフィン量を測定することによ
り求めた。In Examples 1 and 2 above, the amount of paraffin contained in the expandable styrenic resin particles is determined by refluxing the particles in n-hexane, separating the beads, drying the resulting n-hexane solution, and determining the amount of paraffin remaining. It was determined by measuring the amount of paraffin.
以上のようにして得た実施例１及び２並びに比較例１及
び２の発泡性スチレン系樹脂粒子を脱水乾燥し、０．８
〜１．２ｎに分級した後、粒子表面にステアリン酸亜鉛
を０．０５部混合し、５０倍に予備発泡させ、東洋機械
金属社性のＴＨ−５成形機を用いて１００ Ｘ １００
Ｘ ４５ ｎの成形体を製造し、成形試験を行った。The expandable styrenic resin particles of Examples 1 and 2 and Comparative Examples 1 and 2 obtained as described above were dehydrated and dried.
After classifying to ~1.2n, 0.05 part of zinc stearate was mixed on the particle surface, pre-foamed to 50 times, and 100 x 100 using a TH-5 molding machine manufactured by Toyo Machinery & Metals.
A molded body of X 45 n was manufactured and a molding test was conducted.
その結果を下記の表１に示す。The results are shown in Table 1 below.
なお、冷却時間の評価は、予備発泡粒子を２４時間室温
で熟成した後、スチーム圧力１．０ｋｇ／ｒｒｒを３０
秒与えた後、冷却水を１０１流し、放冷時間を種々に変
え、成形体の厚さ変化率が２％となる放冷時間を求め、
冷却時間の指標とした。The cooling time was evaluated by aging the pre-expanded particles at room temperature for 24 hours, then applying a steam pressure of 1.0 kg/rrr to 30
After cooling for 10 seconds, the cooling water was poured for 101 seconds, the cooling time was varied, and the cooling time at which the thickness change rate of the molded body was 2% was determined.
This was used as an index of cooling time.
融着性の評価は、成形体を割ったときの破断面の粒子の
破断している割合を求めて行った。The fusion property was evaluated by determining the percentage of broken particles on the fracture surface when the molded body was broken.
その他、発泡性スチレン系樹脂粒子の予備発泡粒子の流
動性及び予備発泡時のブロッキングについて表１に示す
。In addition, Table 1 shows the fluidity of the pre-expanded particles of the expandable styrene resin particles and the blocking during pre-expanding.
表１ 試験結果
表から明らかなとおり、本発明の発泡性スチレン系樹脂
粒子は、作業上の問題もなく、冷却時間の短縮に有効で
ある。Table 1 As is clear from the test results table, the expandable styrenic resin particles of the present invention cause no operational problems and are effective in shortening the cooling time.
（発明の効果）
第一の発明に係る、又は第二の発明により得られる発泡
性スチレン系樹脂粒子は、成形加工時の冷却時間を短縮
できる。また、本発明においては、常温で固体状のパラ
フィンを使用するので、粒子表面へのブリードがなく、
予備発泡粒子の流動性を損なわず、更に、予備発泡時の
耐ブロッキング性において優れた発泡性スチレン系樹脂
粒子が得られる。(Effects of the Invention) The expandable styrenic resin particles according to the first invention or obtained by the second invention can shorten the cooling time during molding. In addition, since the present invention uses paraffin that is solid at room temperature, there is no bleeding to the particle surface.
It is possible to obtain expandable styrenic resin particles that do not impair the fluidity of the pre-expanded particles and further have excellent anti-blocking properties during pre-expanding.
代理人 弁理士 若 林 邦 彦。Agent: Patent attorney Kunihiko Wakabayashi.
Claims (1)
チレン系樹脂粒子において、該粒子が、融点４０〜７０
℃のパラフィンを該粒子に対して０．０１〜０．５重量
％含有して成る発泡性スチレン系樹脂粒子。 ２、スチレン系モノマーを水性媒体中で懸濁重合するに
当たり、融点４０〜７０℃のパラフィンを重合系に存在
させ、重合後半又は重合完了後に発泡剤を含浸させるこ
とを特徴とする発泡性スチレン系樹脂粒子の製造方法。 ３、スチレン系モノマーを水性媒体中で懸濁重合するに
当たり、スチレン系モノマーの重合率が５０〜９０重量
％の時に融点４０〜７０℃のパラフィンを少量の溶剤又
はスチレン系モノマーに溶解させて重合系に添加する特
許請求の範囲第２項記載の発泡性スチレン系樹脂粒子の
製造方法。[Claims] 1. Expandable styrenic resin particles containing a blowing agent that is liquid or gaseous at room temperature, the particles have a melting point of 40 to 70
Expandable styrenic resin particles containing 0.01 to 0.5% by weight of paraffin at ℃. 2. Expandable styrenic monomers are suspension-polymerized in an aqueous medium, and paraffin with a melting point of 40 to 70°C is present in the polymerization system, and a blowing agent is impregnated in the latter half of the polymerization or after the completion of the polymerization. Method for producing resin particles. 3. When carrying out suspension polymerization of styrene monomer in an aqueous medium, when the polymerization rate of styrene monomer is 50 to 90% by weight, paraffin with a melting point of 40 to 70°C is dissolved in a small amount of solvent or styrene monomer and polymerized. A method for producing expandable styrenic resin particles according to claim 2, which is added to a system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2686687A JPS63193939A (en) | 1987-02-06 | 1987-02-06 | Expandable styrene resin particle and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2686687A JPS63193939A (en) | 1987-02-06 | 1987-02-06 | Expandable styrene resin particle and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63193939A true JPS63193939A (en) | 1988-08-11 |
Family
ID=12205211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2686687A Pending JPS63193939A (en) | 1987-02-06 | 1987-02-06 | Expandable styrene resin particle and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63193939A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04300927A (en) * | 1991-03-29 | 1992-10-23 | Hitachi Chem Co Ltd | Production of fomable styrenic resin particles |
| JP2001220458A (en) * | 2000-02-08 | 2001-08-14 | Mitsubishi Kagaku Form Plastic Kk | Foamable styrenic resin particle |
| KR100478436B1 (en) * | 2001-07-20 | 2005-03-23 | 제일모직주식회사 | Method of Preparing Expandable Polystyrene Having Good Expandability and Mechanical Strength |
| JP2009275270A (en) * | 2008-05-16 | 2009-11-26 | Nippon Steel Corp | Pelletization-processing method for sintering raw material for iron making |
-
1987
- 1987-02-06 JP JP2686687A patent/JPS63193939A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04300927A (en) * | 1991-03-29 | 1992-10-23 | Hitachi Chem Co Ltd | Production of fomable styrenic resin particles |
| JP2001220458A (en) * | 2000-02-08 | 2001-08-14 | Mitsubishi Kagaku Form Plastic Kk | Foamable styrenic resin particle |
| KR100478436B1 (en) * | 2001-07-20 | 2005-03-23 | 제일모직주식회사 | Method of Preparing Expandable Polystyrene Having Good Expandability and Mechanical Strength |
| JP2009275270A (en) * | 2008-05-16 | 2009-11-26 | Nippon Steel Corp | Pelletization-processing method for sintering raw material for iron making |
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