JPH0376338B2 - - Google Patents
Info
- Publication number
- JPH0376338B2 JPH0376338B2 JP59205554A JP20555484A JPH0376338B2 JP H0376338 B2 JPH0376338 B2 JP H0376338B2 JP 59205554 A JP59205554 A JP 59205554A JP 20555484 A JP20555484 A JP 20555484A JP H0376338 B2 JPH0376338 B2 JP H0376338B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- modified polystyrene
- polydimethylsiloxane
- resin composition
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 claims description 38
- 239000004793 Polystyrene Substances 0.000 claims description 28
- 229920002223 polystyrene Polymers 0.000 claims description 28
- -1 polydimethylsiloxane Polymers 0.000 claims description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 21
- 239000011342 resin composition Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 description 14
- 230000007423 decrease Effects 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019646 color tone Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- MZZSDCJQCLYLLL-UHFFFAOYSA-N Secalonsaeure A Natural products COC(=O)C12OC3C(CC1=C(O)CC(C)C2O)C(=CC=C3c4ccc(O)c5C(=O)C6=C(O)CC(C)C(O)C6(Oc45)C(=O)OC)O MZZSDCJQCLYLLL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
（産業上の利用分野）
本発明は、優れた品質総合バランスを有するゴ
ム変性ポリスチレン樹脂組成物に関するものであ
る。
例えばゴム変性ポリスチレンは、家庭電機製品
の部品などに多く用いられているが、従来ABS
樹脂に比して、成形品表面の光沢に劣り、衝撃強
度も低く、着色した際の風合いが及ばないという
欠点を有していた。最近、ABS樹脂の特性に近
づいたゴム変性ポリスチレンの出現の要望がコス
トダウン、薄肉化志向により市場から強まつて来
ている。
本発明の樹脂組成物は光沢、着色性、衝撃強度
の優れた品質総合バランスが、射出成形品、押出
シート、押出真空成形品等にて発現される。高価
なABS樹脂からの代替、製品薄肉化が可能とな
り、コストダウンを計れる経済的な樹脂としての
価値は大である。
（従来の技術）
ゴム変性ポリスチレンは、従来から工業的に多
く用いられているが、その分散ゴム粒子径は一般
に1.0〜5.0μ程度であり、1.0μ以下の小さいゴム粒
子径の場合には、好ましい樹脂が得られていな
い。また、ゴム変性ポリスチレン系樹脂と有機ポ
リシロキサンからなる樹脂組成物はModern
Plastics 1972年11月号114〜116ページ、プラス
チツクス・エージ1974年20巻５月号107ページ、
特開昭55−3494号公報、特開昭53−124561号公
報、特開昭57−187345号公報、特開昭57−187346
号公報などの先行文献に述べられているが、ゴム
粒子径の小さい変性ポリスチレンを用いた場合に
は好ましい樹脂組成物が得られていない。
（発明が解決しようとする問題点）
先に述べた、優れた品質総合バランスを有する
ゴム変性ポリスチレンに対する市場の要望に合致
するには、優れた光沢、着色性、衝撃強度の品質
バランスのゴム変性ポリスチレン樹脂が必要とな
る。上記する光沢、着色性、衝撃強度の品質バラ
ンスの優れた安価なゴム変性ポリスチレン樹脂組
成物を得ることが本発明の目的である。
（問題点を解決するための手段）
本発明は、従来技術では一般的でない特定のミ
クロ構造を有するゴム変性ポリスチレンと特定の
粘度（分子量）を有するポリジメチルシロキサン
よりなる。
即ち、本発明は特定のミクロ構造、特に樹脂相
中に分散したゴム状粒子が従来になく小さいこと
を特徴とするゴム変性ポリスチレンからなる樹脂
組成物である。
有機ポリシロキサンのなかで特定の化合物、す
なわち25℃での粘度が10〜800センチストークス
の範囲にある比較的分子量の小さいポリジメチル
シロキサンと平均粒子径が0.2〜0.5ミクロン、好
ましくは0.3〜0.5ミクロンの範囲にある小さい分
散ゴム粒子径を有するゴム変性ポリスチレンとを
組み合せることによつて驚くべきことに、非常に
品質総合バランスが優れたゴム変性ポリスチレン
樹脂組成物を得ることに成功したものである。
本発明に用いるゴム変性ポリスチレンは、ゴム
状重合体の存在下に芳香族モノビニル単量体を重
合せしめる塊状重合法又は塊状懸濁重合法にて製
造することができる。本発明に特定された特殊な
ミクロ構造を有するゴム変性ポリスチレンは、重
合工程における攪拌の状態、ゴム粒子生成時の混
合状態などをコントロールすることにより製造す
ることができる。芳香族モノビニル単量体として
は、スチレン及びｏ−メチルスチレン、ｐ−メチ
ルスチレン、ｍ−メチルスチレン、２，４−ジメ
チルスチレン、エチルスチレン、ｐ−tert−ブチ
ルスチレン等のアルキル置換スチレン、α−メチ
ルスチレン、α−メチル−ｐ−メチルスチレン等
のα−アルキル置換スチレンなどが用いられる。
また、ゴム状重合体としては、ポリブタジエン、
スチレン−ブタジエン共重合体等であり、ポリブ
タジエンとしてはシス含有量の高いハイシスポリ
ブタジエン、シス含有量の低いローシスポリブタ
ジエンともに用いることができる。製造されたゴ
ム変性ポリスチレンは特定のミクロ構造を有して
いることが必要であり、ゴム状重合体が粒子状に
分散しており、その平均粒子径が0.2〜0.5ミクロ
ン、好ましくは0.3〜0.5ミクロンの範囲にあるこ
とが必要である。平均粒子径が0.2ミクロンより
小さくなると衝撃強度が低下し、また0.5ミクロ
ンより大きくなると光沢が低下して品質総合バラ
ンスが得られた樹脂が得られない。
ここで云う平均粒子径とはゴム変性ポリスチレ
ンの超薄切片法による透過型電子顕微鏡写真を撮
影し、写真中のゴム状重合体粒子1000個の粒子径
を測定して次式により算出したものである。
平均粒子径＝ΣniDi2／ΣniDi
（ここにniは粒子径Diのゴム状重合体粒子の個数
である。）
ゴム状重合体粒子の平均粒子径は、重合時の攪
拌強度、用いるゴム状重合体の溶液粘度などによ
り左右され、これらを変更することにより調節す
ることができる。
更に好ましくは、ゴム変性ポリスチレンのゴム
粒子の粒子径分布が1.1〜2.5、好ましくは1.1〜
2.0の範囲にあることである。粒子径分布が上記
の範囲にある時に特に外観が良好である。粒子径
分布は重量平均粒子径を数平均粒子径で割つた値
で表現される。
本発明で用いるポリジメチルシロキサンは、
(Industrial Application Field) The present invention relates to a rubber-modified polystyrene resin composition having an excellent overall quality balance. For example, rubber-modified polystyrene is often used in parts of home appliances, but conventionally ABS
Compared to resins, they have the disadvantages of inferior gloss on the surface of molded products, low impact strength, and poor texture when colored. Recently, there has been a growing demand in the market for rubber-modified polystyrene that has properties close to those of ABS resin due to the desire for cost reduction and thinner walls. The resin composition of the present invention exhibits an excellent overall quality balance of gloss, colorability, and impact strength in injection molded products, extrusion sheets, extrusion vacuum molded products, and the like. It has great value as an economical resin that can replace expensive ABS resin, make products thinner, and reduce costs. (Prior art) Rubber-modified polystyrene has been widely used industrially, but its dispersed rubber particle size is generally about 1.0 to 5.0μ, and in the case of small rubber particle sizes of 1.0μ or less, A desirable resin has not been obtained. In addition, a resin composition consisting of a rubber-modified polystyrene resin and an organic polysiloxane is a Modern
Plastics November 1972 issue pages 114-116, Plastics Age Vol. 20, 1974 May issue page 107,
JP-A-55-3494, JP-A-53-124561, JP-A-57-187345, JP-A-57-187346
Although it is stated in prior literature such as Japanese Patent Publication No. 2003-111033, a preferable resin composition has not been obtained when modified polystyrene having a small rubber particle size is used. (Problems to be Solved by the Invention) In order to meet the market demand for rubber-modified polystyrene with an excellent overall quality balance as described above, it is necessary to use rubber-modified polystyrene with an excellent quality balance of gloss, coloring property, and impact strength. Polystyrene resin is required. It is an object of the present invention to obtain an inexpensive rubber-modified polystyrene resin composition that has an excellent quality balance among the above-mentioned gloss, colorability, and impact strength. (Means for Solving the Problems) The present invention consists of rubber-modified polystyrene having a specific microstructure not common in the prior art and polydimethylsiloxane having a specific viscosity (molecular weight). That is, the present invention is a resin composition made of rubber-modified polystyrene characterized by a specific microstructure, in particular, the rubber particles dispersed in the resin phase are smaller than ever before. Among organopolysiloxanes, certain compounds are used, namely polydimethylsiloxane, which has a relatively low molecular weight with a viscosity in the range of 10 to 800 centistokes at 25°C, and an average particle size of 0.2 to 0.5 microns, preferably 0.3 to 0.5 microns. By combining rubber-modified polystyrene with a small dispersed rubber particle size in the range of . The rubber-modified polystyrene used in the present invention can be produced by a bulk polymerization method or a bulk suspension polymerization method in which an aromatic monovinyl monomer is polymerized in the presence of a rubbery polymer. The rubber-modified polystyrene having the special microstructure specified in the present invention can be produced by controlling the stirring state during the polymerization process, the mixing state during rubber particle production, and the like. Examples of aromatic monovinyl monomers include styrene and alkyl-substituted styrenes such as o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, and α- α-alkyl substituted styrenes such as methylstyrene and α-methyl-p-methylstyrene are used.
In addition, as the rubbery polymer, polybutadiene,
Styrene-butadiene copolymer, etc., and as the polybutadiene, both high-cis polybutadiene with a high cis content and low-cis polybutadiene with a low cis content can be used. The produced rubber-modified polystyrene must have a specific microstructure, in which the rubber-like polymer is dispersed in particles with an average particle size of 0.2 to 0.5 microns, preferably 0.3 to 0.5 microns. It needs to be in the micron range. If the average particle diameter is smaller than 0.2 microns, the impact strength will be reduced, and if it is larger than 0.5 microns, the gloss will be reduced, making it impossible to obtain a resin with an overall quality balance. The average particle diameter referred to here is calculated by taking a transmission electron micrograph of rubber-modified polystyrene using an ultra-thin section method, measuring the particle diameter of 1000 rubber-like polymer particles in the photograph, and using the following formula. be. Average particle size = ΣniDi 2 /ΣniDi (where ni is the number of rubbery polymer particles with particle size Di.) The average particle size of rubbery polymer particles is determined by the stirring intensity during polymerization, the rubbery polymer used, It depends on the viscosity of the solution, etc., and can be adjusted by changing these. More preferably, the particle size distribution of the rubber particles of the rubber-modified polystyrene is 1.1 to 2.5, preferably 1.1 to 2.5.
It should be in the range of 2.0. The appearance is particularly good when the particle size distribution is within the above range. Particle size distribution is expressed as a value obtained by dividing the weight average particle size by the number average particle size. The polydimethylsiloxane used in the present invention is
【式】で表わされる構造単位を有して
いることが必要である。本発明のような小さなゴ
ム粒子径を有するゴム変性ポリスチレンの場合に
は、ポリジメチルシロキサン以外の先行技術文献
に述べられているような有機ポリシロキサンでは
好ましい樹脂組成物が得られない。また、ポリジ
メチルシロキサンの粘度も25℃で10〜800センチ
ストークスと比較的分子量の低いものが必要とな
る。粘度が10センチストークス以下になると衝撃
強度の低下がみられ、また800センチストークス
以上になると衝撃強度の低下と着色性の低下がみ
られて好ましくない。更に樹脂組成物中のポリジ
メチルシロキサンの含有量も50〜500ppmと微量
であることが必要である。含有量が50ppm以下と
なると衝撃強度の低下がみられ、500ppm以上と
なると着色性の低下が好ましくない。ポリジメチ
ルシロキサンの粘度が大になつた場合、また含有
量が多くなつた場合に着色性が低下する理由は、
定かではないが、ゴム変性ポリスチレン中へのポ
リジメチルシロキサンの相溶性が低下する為では
ないかと考えられる。このような点からも、ポリ
ジメチルシロキサンの粘度及び含有量が好ましい
樹脂組成物を得る為に重要である。
本発明の樹脂組成物を製造する方法は、特に限
定されることはなく、例えばスチレンモノマーに
ポリジメチルシロキサンを添加して重合を行つて
もよいし、ゴム変性ポリスチレンとポリジメチル
シロキサンを押出機等を用いて溶融混合を行つて
もよい。更にはポリジメチルシロキサンとポリス
チレンからポリジメチルシロキサン濃度の高いマ
スターペレツトを製造し、そのマスターペレツト
とゴム変性ポリスチレンを混合し成形物を得ても
よい。
更に本発明の樹脂組成物に染顔料、滑剤、充填
剤、離型剤、可塑剤、帯電防止剤等の添加剤を必
要に応じて添加することができる。
（効果）
本発明の樹脂組成物は、光沢、着色性、衝撃強
度の物性面での品質総合バランスに優れる。着色
性が良好であることは、着色時に使用する染顔料
コストが大巾に安くなり工業的に非常に大きな意
味を持つのである。
本発明の樹脂は、弱電気器、雑貨等の分野にお
いて形成品として使用できる。特に鮮やかな色調
が要求される成形品において好ましい結果を得る
ことができる。
（実施例）
以下に実施例を示す。実施例に示されたデータ
ーは次の方法に基いて測定されたものである。
アイゾツト衝撃強度；ASTM D256によつた。
引張強度；ASTM D638
光沢；ASTM D638のダンベルの試験片のゲ
ート部とエンドゲート部の光沢度（入射角60°）
を測定し平均した。
着色性；樹脂100重量部に黒系の染顔料計
0.0193重量部の一定量を添加して、黒着色品とし
て、成形片（たて89mm、よこ50mm、厚み2.5mm）
をつくる。対照サンプルとして、９重量％のポリ
ブタジエンゴムを含有するハイインパクトポリス
チレンに染顔料を添加してつくつた黒色成形片を
つくつておき、色調、風合いを比較してランク付
する。
自然色のハイインパクトポリスチレンに１Kgあ
たり、25円、20円、15円相当の染顔料を添加して
作成した黒着色成形片をそれぞれ対照サンプル
Ａ、Ｂ、Ｃとする。It is necessary to have a structural unit represented by the formula: In the case of rubber-modified polystyrene having a small rubber particle size as in the present invention, preferred resin compositions cannot be obtained with organopolysiloxanes such as those described in prior art documents other than polydimethylsiloxane. Furthermore, the polydimethylsiloxane must have a relatively low molecular weight, with a viscosity of 10 to 800 centistokes at 25°C. If the viscosity is less than 10 centistokes, the impact strength will decrease, and if the viscosity is more than 800 centistokes, the impact strength will decrease and the colorability will decrease, which is not preferable. Furthermore, it is necessary that the content of polydimethylsiloxane in the resin composition is as small as 50 to 500 ppm. When the content is 50 ppm or less, a decrease in impact strength is observed, and when the content is 500 ppm or more, a decrease in colorability is undesirable. The reason why the colorability decreases when the viscosity of polydimethylsiloxane increases or when the content increases is as follows.
Although it is not certain, it is thought that this is because the compatibility of polydimethylsiloxane in rubber-modified polystyrene decreases. From this point of view as well, the viscosity and content of polydimethylsiloxane are important in order to obtain a preferable resin composition. The method for producing the resin composition of the present invention is not particularly limited, and for example, polydimethylsiloxane may be added to styrene monomer and polymerized, or rubber-modified polystyrene and polydimethylsiloxane may be mixed using an extruder, etc. Melt mixing may be performed using a . Furthermore, master pellets with a high polydimethylsiloxane concentration may be produced from polydimethylsiloxane and polystyrene, and the master pellets may be mixed with rubber-modified polystyrene to obtain a molded product. Furthermore, additives such as dyes and pigments, lubricants, fillers, mold release agents, plasticizers, and antistatic agents can be added to the resin composition of the present invention, if necessary. (Effects) The resin composition of the present invention has an excellent overall quality balance in terms of physical properties such as gloss, colorability, and impact strength. Good coloring properties are of great industrial significance, as the cost of dyes and pigments used for coloring can be significantly reduced. The resin of the present invention can be used as a molded article in fields such as light electrical appliances and miscellaneous goods. Particularly favorable results can be obtained in molded products that require vivid color tones. (Example) Examples are shown below. The data shown in the examples were measured based on the following method. Izot impact strength: Based on ASTM D256. Tensile strength: ASTM D638 Gloss: Glossiness of gate and end gate of ASTM D638 dumbbell test piece (incidence angle 60°)
were measured and averaged. Colorability: 100 parts by weight of resin plus black dye and pigment
A fixed amount of 0.0193 parts by weight was added to make a molded piece (height: 89 mm, width: 50 mm, thickness: 2.5 mm) as a black colored product.
Create. As a control sample, black molded pieces made by adding dyes and pigments to high-impact polystyrene containing 9% by weight of polybutadiene rubber were prepared and ranked by comparing the color tone and texture. Control samples A, B, and C are black colored molded pieces made by adding dyes and pigments equivalent to 25 yen, 20 yen, and 15 yen per 1 kg to natural-colored high-impact polystyrene.
【表】
参考例
ゴム変性ポリスチレンの製造：
第一の流れとして2l／時間の供給速度にて、ポ
リブタジエン12重量％、スチレン78重量％、エチ
ルベンゼン10重量％からなる溶液100重量部、1.1
ビス（ｔ−ブチルパーオキシ）３，３，５−トリ
メチルシクロヘキサン0.045重量部からなる混合
物を2.4の第一重合機に連続的に送入する。第
一重合機は温度105℃である。第二の流れとして
ｌ／時間の供給速度にて、スチレン90重量％と
エチルベンゼン10重量％の混合溶液を容量6.2、
温度120〜140℃の第二重合機に送入する。これら
の第一の流れと第二の流れは1.5のダブルヘリ
カルリボン状翼の装着された混合機内に導入さ
れ、100〜300rpmの範囲の回転で混合される。更
に容量6.2、温度110〜130℃の第三重合機、容
量6.2、温度135〜160℃の第四重合機に送入し
混合を進めた後に、未反応モノマー及び溶媒を減
圧下に除去してペレツト状のゴム変性ポリスチレ
ンを得る。
上記の方法にて、ポリブタジエン含有量が10重
量％であり、分散ゴム粒子の平均粒子径が、
1.0μ、0.62μ、0.45μ、0.32μ、0.18μであり、各々
の粒子径分布が3.0、2.2、1.7、1.6、1.4であるゴ
ム変性ポリスチレンを得た。
実施例１〜５及び比較例１〜４
参考例で得た平均粒子径が0.45μのゴム変性ポ
リスチレンに表−１に示した種々の粘度を有する
ポリジメチルシロキサン200ppmを添加し、押出
機にて混練して樹脂組成物を得て、アイゾツト衝
撃強度、引張強度、光沢及び着色性を評価した。
その結果を表−１に示す。ポリジメチルシロキサ
ンの粘度と樹脂組成物のアイゾツト衝撃強度の関
係を図面に示す。ポリジメチルシロキサンの粘度
が10〜800est（センチストークス）の範囲にある
時が好ましいことがわかる。
実施例６〜８及び比較例５〜６
参考例で得た平均粒子径が0.45μのゴム変性ポ
リスチレンに粘度が50センチストークスのポリジ
メチルシロキサンを表−２に示した添加量で、実
施例１と同様な方法にて樹脂組成物を得て、物性
を評価した。その結果を表−２に示す。ポリジメ
チルシロキサンの添加量が1000ppmと多くなると
着色性が低下する。
比較例 ７〜８
実施例４のポリジメチルシロキサンの代りに、
ポリメチルフエニルシロキサン又はα−メチルス
チレン変性シリコーンオイルを用いて同様の試験
を行つた。その結果を表−３に示す。
実施例９及び比較例９〜11
実施例４の平均粒子径が0.45μのゴム変性ポリ
スチレンの代りに、平均粒子径が0.18μ、0.32μ、
0.62μ、1.0μのゴム変性ポリスチレンを用いて同
様の試験を行つた。その結果を表−３に示す。平
均粒子径が0.2μに満たない場合にはアイゾツト衝
撃強度が低下して好ましくない。平均粒子径が
0.5μを越える場合には光沢−アイゾツト衝撃強度
の品質バランスが劣り好ましくない。[Table] Reference example Manufacture of rubber-modified polystyrene: 100 parts by weight of a solution consisting of 12% by weight of polybutadiene, 78% by weight of styrene, and 10% by weight of ethylbenzene, 1.1% by weight, at a feed rate of 2 l/h as the first stream.
A mixture consisting of 0.045 parts by weight of bis(t-butylperoxy)3,3,5-trimethylcyclohexane is continuously fed into the first polymerizer of 2.4. The temperature of the first polymerizer is 105℃. As a second stream, a mixed solution of 90% by weight of styrene and 10% by weight of ethylbenzene was added in a volume of 6.2% at a feed rate of l/h.
The mixture is fed into a second polymerizer at a temperature of 120-140℃. These first and second streams are introduced into a mixer equipped with 1.5 double helical ribbon vanes and mixed at rotations ranging from 100 to 300 rpm. The mixture was further fed into a third polymerizer with a capacity of 6.2 and a temperature of 110 to 130°C, and a fourth polymerizer with a capacity of 6.2 and a temperature of 135 to 160°C to proceed with mixing, and unreacted monomers and solvent were removed under reduced pressure. to obtain pellet-shaped rubber-modified polystyrene. In the above method, the polybutadiene content was 10% by weight, and the average particle diameter of the dispersed rubber particles was
Rubber-modified polystyrenes having particle size distributions of 1.0μ, 0.62μ, 0.45μ, 0.32μ, and 0.18μ and particle size distributions of 3.0, 2.2, 1.7, 1.6, and 1.4 were obtained. Examples 1 to 5 and Comparative Examples 1 to 4 200 ppm of polydimethylsiloxane having various viscosities shown in Table 1 was added to the rubber-modified polystyrene with an average particle diameter of 0.45μ obtained in the reference example, and the mixture was processed using an extruder. A resin composition was obtained by kneading, and its Izot impact strength, tensile strength, gloss, and colorability were evaluated.
The results are shown in Table-1. The drawing shows the relationship between the viscosity of polydimethylsiloxane and the Izod impact strength of the resin composition. It can be seen that it is preferable when the viscosity of the polydimethylsiloxane is in the range of 10 to 800 centistokes. Examples 6 to 8 and Comparative Examples 5 to 6 Example 1 was prepared by adding polydimethylsiloxane having a viscosity of 50 centistokes to the rubber-modified polystyrene having an average particle diameter of 0.45 μ obtained in Reference Example in the amount shown in Table 2. A resin composition was obtained in the same manner as above, and its physical properties were evaluated. The results are shown in Table-2. When the amount of polydimethylsiloxane added is as large as 1000 ppm, the colorability decreases. Comparative Examples 7-8 Instead of polydimethylsiloxane in Example 4,
Similar tests were conducted using polymethylphenylsiloxane or α-methylstyrene modified silicone oil. The results are shown in Table-3. Example 9 and Comparative Examples 9 to 11 Instead of the rubber-modified polystyrene with an average particle diameter of 0.45μ in Example 4, rubber-modified polystyrene with an average particle diameter of 0.18μ, 0.32μ,
Similar tests were conducted using 0.62μ and 1.0μ rubber-modified polystyrene. The results are shown in Table-3. If the average particle diameter is less than 0.2μ, the Izot impact strength decreases, which is undesirable. The average particle size is
If it exceeds 0.5μ, the quality balance between gloss and isot impact strength will be poor, which is not preferable.
【表】【table】
【表】【table】
【表】【table】
図面は、実施例１〜５及び比較例１〜４におけ
るポリジメチルシロキサンの粘度とアイゾツト衝
撃強度の関係のグラフである。
The drawing is a graph of the relationship between the viscosity and Izod impact strength of polydimethylsiloxane in Examples 1 to 5 and Comparative Examples 1 to 4.
Claims (1)
ており、その分散粒子の平均粒子径が0.2〜0.5
ミクロンの範囲にあり、 (B) 該組成物中に25℃での粘度が10〜800センチ
ストークスの範囲にあるポリジメチルシロキサ
ンが50〜500ppm含有されていることを特徴と
する高光沢ゴム変性ポリスチレン樹脂組成物。[Scope of Claims] 1. In a rubber-modified polystyrene resin composition, (A) a rubber-like polymer is dispersed in the composition in the form of particles, and the average particle diameter of the dispersed particles is 0.2 to 0.5.
(B) a high gloss rubber-modified polystyrene characterized in that the composition contains 50 to 500 ppm of polydimethylsiloxane having a viscosity in the range of 10 to 800 centistokes at 25°C; Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20555484A JPS6185461A (en) | 1984-10-02 | 1984-10-02 | Polystyrene resin composition having high glossiness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20555484A JPS6185461A (en) | 1984-10-02 | 1984-10-02 | Polystyrene resin composition having high glossiness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6185461A JPS6185461A (en) | 1986-05-01 |
| JPH0376338B2 true JPH0376338B2 (en) | 1991-12-05 |
Family
ID=16508811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20555484A Granted JPS6185461A (en) | 1984-10-02 | 1984-10-02 | Polystyrene resin composition having high glossiness |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6185461A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01275649A (en) * | 1988-04-27 | 1989-11-06 | Asahi Chem Ind Co Ltd | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
| JPS63112646A (en) * | 1986-10-29 | 1988-05-17 | Asahi Chem Ind Co Ltd | High-gloss, impact-resistant polystyrene resin composition |
| US5356585A (en) * | 1993-07-01 | 1994-10-18 | Dow Corning Corporation | Process of extruding snythetic thermoplastic resins using organosilicon resinous compositions as extrusion lubricants |
| KR19990011442A (en) * | 1997-07-23 | 1999-02-18 | 박홍기 | Styrene-based thermoplastic resin having excellent release property and surface gloss |
| KR100411696B1 (en) * | 2000-10-30 | 2003-12-18 | 제일모직주식회사 | Thermoplastic Resin Compositions With High Gloss And High Impact Resistance And Process For Preparing The Same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51100145A (en) * | 1975-03-01 | 1976-09-03 | Japan Synthetic Rubber Co Ltd | NETSUKASOSEIJUSHISOSEIBUTSU |
| JPS57170949A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57170950A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Improved rubber-moldified styrene resin composition |
| JPS57172948A (en) * | 1981-04-17 | 1982-10-25 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57187346A (en) * | 1981-05-14 | 1982-11-18 | Mitsui Toatsu Chem Inc | Improved rubber-modified styrene resin composition |
-
1984
- 1984-10-02 JP JP20555484A patent/JPS6185461A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51100145A (en) * | 1975-03-01 | 1976-09-03 | Japan Synthetic Rubber Co Ltd | NETSUKASOSEIJUSHISOSEIBUTSU |
| JPS57170949A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57170950A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Improved rubber-moldified styrene resin composition |
| JPS57172948A (en) * | 1981-04-17 | 1982-10-25 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57187346A (en) * | 1981-05-14 | 1982-11-18 | Mitsui Toatsu Chem Inc | Improved rubber-modified styrene resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6185461A (en) | 1986-05-01 |
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