JPS6333461A - High-gloss rubber-reinforced polystyrene composition - Google Patents
High-gloss rubber-reinforced polystyrene compositionInfo
- Publication number
- JPS6333461A JPS6333461A JP17552486A JP17552486A JPS6333461A JP S6333461 A JPS6333461 A JP S6333461A JP 17552486 A JP17552486 A JP 17552486A JP 17552486 A JP17552486 A JP 17552486A JP S6333461 A JPS6333461 A JP S6333461A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- particles
- reinforced polystyrene
- polystyrene
- gloss
- 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
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 60
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 54
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 17
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920002857 polybutadiene Polymers 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-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
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 241000545067 Venus Species 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
- 150000001408 amides Chemical class 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 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)
Abstract
Description
【発明の詳細な説明】
（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鍋光沢ゴム
補強ポリスチレン組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a pan-gloss rubber-reinforced polystyrene composition having an excellent overall quality balance.
例えば、ゴム補強ポリスチレンは、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
、衝撃強度忙劣り、成形品表面の光沢も低いという欠点
を有していた。最近、ＡＢＳ樹脂の特性忙近づいた改良
されたゴム補強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、市場から強まってきている。For example, rubber-reinforced polystyrene is often used for parts of home appliances, but it has had the disadvantages of lower impact strength and lower gloss of the surface of molded products than conventional ABS resins. Recently, demand for improved rubber-reinforced polystyrene that has improved the characteristics of ABS resin has been increasing in the market due to the desire for cost reduction and thinner walls.
本発明の樹脂組成物は、衝撃強度、光沢、引張強度及び
耐熱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。The resin composition of the present invention exhibits an excellent overall quality balance of impact strength, gloss, tensile strength, and heat resistance in injection molded products, extruded sheets, extruded vacuum molded products, and the like. expensive ABS
It has great value as an economical resin that can be used as a substitute for resins, make products thinner, and reduce costs.
（従来の技術及びその問題点）
ゴム補強ポリスチレンは、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
．０ミクロン（μ）程度であり、１０μ以下の小さいゴ
ム粒子径の場合ては、好ましい樹脂が得られていない。(Prior art and its problems) Rubber-reinforced polystyrene has been widely used industrially, but the dispersed rubber particle size is generally 1.0 to 5.
．． In the case of a small rubber particle size of about 0 micron (μ) and 10 μm or less, a desirable resin cannot be obtained.
また、ゴム補強ポリスチレンは一般に分散ゴム状物質の
粒子中にポリスチレンを粒子状の形状忙て内蔵しており
、その内蔵ポリスチレン粒子の大きさは０．３ミクロン
より大きなものが相当の割合いを占めていることが、上
布されているゴム補強ポリスチレンの電子顕微鏡写真を
示しているＥｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｐｏｌｙ
ｍｅｒ ５ｃｉｅｎｃｅ ａｎｄＴｅｃｈｎｏｌｏｇｙ
Ｖｏｌ、１３の４０２ページのＦｉｇ、２からも明ら
かである。In addition, rubber-reinforced polystyrene generally has polystyrene embedded in particles of a dispersed rubber-like substance, and a considerable proportion of the embedded polystyrene particles are larger than 0.3 microns. The Encyclopedia of Poly shows an electron micrograph of rubber-reinforced polystyrene coated with
mer 5science and Technology
This is clear from Fig. 2 on page 402 of Vol. 13.
また、ゴム補強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１１４〜１１年代１月号１１４〜１
１６ページジ１９７４年２０巻５月号１０７ページ、４
！開昭５５−３４９４号公報、特開昭５３−１２４５６
１号公報、特開昭５７−１８７３４５号公報、特開昭５
７−１８７３４６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ゴム補強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。In addition, a resin composition consisting of a rubber-reinforced styrenic resin and an organic polysiloxane is manufactured by Modern Plastics.
November 1972 issue 114-11 January issue 114-1
Page 16, Volume 20, May 1974, Page 107, 4
! Publication No. 55-3494, Japanese Patent Publication No. 53-12456
Publication No. 1, JP-A-57-187345, JP-A-5
Although described in prior literature such as Japanese Patent No. 7-187346, a preferable resin composition has not been obtained when rubber-reinforced polystyrene with a small rubber particle size is used.
先に述べた、優れた品質総合バランスを有する改良され
たゴム補強ポリスチレンに対する市場の要望に合致する
には、衝撃強度、光沢、引張強度及び耐熱の品質バラン
スの優れた改良さねたゴム変性ポリスチレンが必要とな
る。上記する衝撃強度、光沢、引張強度、耐熱の品質バ
ランスの優れた安価な高光沢ゴム変性ポリスチレンを得
ることが本発明の目的である。To meet the market demand for improved rubber-reinforced polystyrene with an excellent overall quality balance as mentioned above, an improved rubber-modified polystyrene with an excellent quality balance of impact strength, gloss, tensile strength and heat resistance is required. Is required. It is an object of the present invention to obtain an inexpensive high-gloss rubber-modified polystyrene having an excellent quality balance of impact strength, gloss, tensile strength, and heat resistance.
（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
を有するゴム補強ポリスチレンと、有機ポリシロキサン
の中でも特定のポリジメチルシロキサンよりなる。(Means for Solving the Problems) The present invention consists of rubber-reinforced polystyrene having a specific microstructure that is not common in the prior art, and a specific polydimethylsiloxane among organic polysiloxanes.
即ち、本発明は、ゴム状物質が粒子状に分散しているゴ
ム補強ポリスチレン組成物において囚 分散粒子の平均
粒子径が０．２０〜１．００ミクロンの範囲にあり、
■ 該分散ゴム状物質の粒子中に芳香族モノビニル重合
体を粒子状の形状忙て内蔵しており、その粒子数の８０
％以上が０．３ミクロン以下であり
（Ω 該組成物中和ポリジメチルシロキサンがｏ、ｏ
ｏ ｓ〜０．８重量％含有されているゴム変性ポリスチ
レン組成物である。That is, the present invention provides a rubber-reinforced polystyrene composition in which a rubber-like substance is dispersed in the form of particles, in which: (1) the average particle size of the dispersed particles is in the range of 0.20 to 1.00 microns; (2) the dispersed rubber-like substance; The aromatic monovinyl polymer is incorporated in the particles in a particle-like shape, and the number of particles is 80.
% or more is 0.3 microns or less (Ω)
This is a rubber-modified polystyrene composition containing os~0.8% by weight.
本発明は、要件囚、［Ｆ］）、（Ｏの全てを組み合わせ
ることによって、非常に品質総合バランスが優れた高光
沢ゴム補強ポリスチレン組成物を得ることに成功したも
のである。The present invention has succeeded in obtaining a high-gloss rubber-reinforced polystyrene composition with an excellent overall quality balance by combining all of the requirements, [F]) and (O).
本発明に用いるゴム補強ポリスチレンは、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。The rubber-reinforced 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.
また、該ゴム補強ポリスチレンは、重合工程における撹
拌の状態、ゴム粒子生成時の混合状態などをコントロー
ルするとと忙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０−メチルスチレン
。Furthermore, the rubber-reinforced polystyrene can be easily produced by controlling the stirring state during the polymerization process, the mixing state during rubber particle production, and the like. Styrene and 0-methylstyrene are used as aromatic monovinyl monomers.
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−
プチルスチレン等の芦アルキル置換スチレン。p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-
Alkyl-substituted styrene such as butylstyrene.
α−メチルスチレン、ａ−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、ポリブタジェン、スチレン−
ブタジェン共重合体等であり、ポリブタジェンとしては
シス含有量の高いハイシスポリブタジェン、シス含有量
の低いローシスポリブタジェンともに用いることができ
る。α-alkyl substituted styrenes such as α-methylstyrene and a-methyl-p-methylstyrene are used. In addition, as rubber-like polymers, polybutadiene, styrene-
butadiene copolymers, 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.
製造されたゴム補強ポリスチレンは、特定のミクロ構造
を有していることが必要であり、ゴム状物質が粒子状に
分散しており、その平均粒子径が０．２０ Ｓｌ、００
ミクロン、好ましくは０．２０〜０．７０ミクロン、最
も好ましくは０．３０〜０．６０ミクロンの範囲にある
ことが必要である。The produced rubber-reinforced polystyrene must have a specific microstructure, in which the rubber-like substance is dispersed in particles with an average particle size of 0.20 Sl, 00
It should be in the range of microns, preferably from 0.20 to 0.70 microns, most preferably from 0.30 to 0.60 microns.
平均粒子径が０．２０ミクロンより小さくなると衝撃強
度が低下し、また１、００ミクロンより大きくなると、
光沢、引張強度が低下して品質総合バランスが優れた樹
脂が得られない。When the average particle size is smaller than 0.20 microns, the impact strength decreases, and when it is larger than 1,00 microns,
The gloss and tensile strength decrease, making it impossible to obtain a resin with an excellent overall balance of quality.
ここで云う平均粒子径とはゴム補強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
ゴム状物質粒子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。The average particle diameter referred to here is calculated by taking a transmission electron micrograph of rubber-reinforced polystyrene using an ultra-thin section method, measuring the particle diameter of 1000 rubber-like material particles in the photograph, and using the following formula. .
（ここにｎｉは粒子径Ｄｉのゴム状重合体粒子の個数で
ある。）
ゴム状物質粒子の平均粒子径は、重合時の撹拌強度、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。(Here, ni is the number of rubbery polymer particles with a particle size Di.) The average particle size of the rubbery substance particles depends on the stirring intensity during polymerization, the solution viscosity of the rubbery polymer used, etc. It can be adjusted by changing.
本発明に用いるゴム補強ポリスチレン中の分散ゴム粒子
中に内蔵されているポリスチレン粒子の大きさは、その
粒子数の８０％以上が０．３ミクロン以下、好ましくは
９０％以上が０．３ミクロン以下という従来になく小さ
な内蔵ポリスチレン粒子であることが必要である。内蔵
ポリスチレン粒子が大きくなると光沢、着色性および剛
性が低下して品質総合バランスが優れた樹脂が得られな
い。The size of the polystyrene particles contained in the dispersed rubber particles in the rubber-reinforced polystyrene used in the present invention is such that 80% or more of the particles are 0.3 microns or less, preferably 90% or more are 0.3 microns or less. It is necessary that the polystyrene particles are smaller than ever before. If the built-in polystyrene particles become large, gloss, colorability, and rigidity will decrease, making it impossible to obtain a resin with an excellent overall balance of quality.
ここで云う内蔵ポリスチレン粒子の大きさは、ゴム補強
ポリスチレンの超薄切片法による透過製電子顕微鏡写真
を撮影し、ゴム粒子忙内蔵されたポリスチレン粒子を測
定することによって求めることができる。The size of the embedded polystyrene particles mentioned here can be determined by taking a transmission electron micrograph of rubber-reinforced polystyrene using an ultra-thin section method and measuring the polystyrene particles embedded in the rubber particles.
本発明に用いるゴム補強ポリスチレンを製造する為の好
ましい方法としては、ゴム状重合体と芳香族モノビニル
単量体からなる溶液を重合させて得た重合溶液と芳香族
モノビニル単量体を重合させて得た重合溶液とを高ぜん
断力下に混合し、支圧重合を進行させることＫよる方法
又はゴム状重合体と芳香族モノビニル単量体とを含む重
合溶液において、ゴム状重合体と芳香族モノビニル単量
体との比率においてゴム状重合体の割合いを従来まで一
般に用いられていたより多くすることによる方法がある
。A preferred method for producing the rubber-reinforced polystyrene used in the present invention is to polymerize a polymer solution obtained by polymerizing a solution consisting of a rubbery polymer and an aromatic monovinyl monomer and an aromatic monovinyl monomer. The rubbery polymer and the aromatic One method involves increasing the proportion of the rubbery polymer in relation to the group monovinyl monomers than has hitherto generally been used.
本発明で用いるポリジメチルシロキサンはいることが必
要である。本発明のような小さなゴム粒子径を有するゴ
ム補強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忙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。更に
好ましくは、ポリジメチルシロキサンの粘度も２５℃で
、ｌＯ〜１０，０００センチストークスの範囲にあるこ
とである。It is necessary that the polydimethylsiloxane used in the present invention be present. In the case of rubber-reinforced polystyrene having a small rubber particle size as in the present invention, a preferred resin composition cannot be obtained with organic polysiloxanes other than polydimethylsiloxane, which have been extensively discussed in the prior art literature. More preferably, the viscosity of the polydimethylsiloxane also ranges from lO to 10,000 centistokes at 25°C.
更に本発明の高光沢ゴム補強ポリスチレン組成物中のポ
リジメチルシロキサンの含有量は、ｏ、ｏ ｏ ｓ〜０
．８重量％の範囲にあることである。含有量がｏ、ｏ
ｏ ｓ重量％未満となると衝撃強度の低下が見られ、０
．８重量％を越えると、着色性および樹脂成形品の二次
加工性（化学接着性、印刷性、塗装性等）の点で好まし
くない。添加量が多（なった場合、着色性及び二次加工
性が悪化する理由は定かでないがゴム補強ポリスチレン
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、ポリジメチ
ルシロキサンの含有量が好ましい高光沢ゴム補強ポリス
チレン組成物を得るためにｊｉ要である。Furthermore, the content of polydimethylsiloxane in the high-gloss rubber-reinforced polystyrene composition of the present invention ranges from o, o o s to 0.
．． It is within the range of 8% by weight. Content is o, o
If it is less than o s weight %, a decrease in impact strength is observed, and 0
．． If it exceeds 8% by weight, it is unfavorable in terms of colorability and secondary processability (chemical adhesion, printability, paintability, etc.) of resin molded products. Although it is not clear why the colorability and secondary processability deteriorate when the amount added is large, it is thought that it is because the compatibility of polydimethylsiloxane in rubber-reinforced polystyrene decreases.These points Therefore, the content of polydimethylsiloxane is necessary to obtain a preferred high-gloss rubber-reinforced polystyrene composition.
本発明の尚光沢ゴム補強ポリスチレン組成物を製造する
方法は、特に限定されることはなく、例エバスチレンモ
ノマー忙ポリジメチルシロキサンを添加して重合を行な
ってもよいし、ゴム補強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なってもよい
。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毘いマスターペレットを製
造し、そのマスターペレットとゴム補強ポリスチレンを
混合し成形物を得てもよい。The method for producing the glossy rubber-reinforced polystyrene composition of the present invention is not particularly limited, and for example, polymerization may be carried out by adding evastyrene monomer to polydimethylsiloxane, or rubber-reinforced polystyrene and polydimethyl The siloxane may be melt-mixed using an extruder or the like. Furthermore, a molded product may be obtained by producing master pellets having a high polydimethylsiloxane concentration from polydimethylsiloxane and polystyrene, and mixing the master pellets with rubber-reinforced polystyrene.
本発明の高光沢ゴム補強ポリスチレン組成物には高級脂
肪酸の金属塩、たとえばステアリン酸亜鉛、ステアリン
酸カルシウムなど高級脂肪酸のアミド類、たとえばエチ
レンビスステアロアミトナど、の滑剤を組み合わせて用
いることにより、衝撃強度及び光沢の点で好ましい結果
が得られる。The high-gloss rubber-reinforced polystyrene composition of the present invention can be used in combination with a lubricant such as metal salts of higher fatty acids, such as amides of higher fatty acids such as zinc stearate and calcium stearate, such as ethylene bisstearoamitona. Favorable results are obtained in terms of strength and gloss.
用いる滑剤の量は０．Ｏ１Ｎ１．０重量％、好ましくは
０．Ｏ２Ｎ２．２重量％である。The amount of lubricant used is 0. O1N 1.0% by weight, preferably 0. The O2N content is 2.2% by weight.
また、本発明の高光沢ゴム補強ポリスチレン組成物には
染顔料、滑剤、充填剤、離型剤、可塑剤。The high-gloss rubber-reinforced polystyrene composition of the present invention also contains dyes and pigments, lubricants, fillers, mold release agents, and plasticizers.
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。Additives such as antistatic agents can be added as necessary.
（効果）
本発明の高光沢ゴム補強ポリスチレン組成物は衝撃強度
、光沢、引張強度及び耐熱の物性面での品質総合バラン
スに優れる。これらの点は、ＡＢＳ樹脂にかわるものと
しての経済的効果は大であり、また、薄肉化志向の市場
の要望に充分、答えることができるものである。(Effects) The high-gloss rubber-reinforced polystyrene composition of the present invention has an excellent overall quality balance in terms of physical properties such as impact strength, gloss, tensile strength, and heat resistance. These points have a great economic effect as an alternative to ABS resin, and can fully meet the market demand for thinner walls.
本発明の高光沢ゴム補強ポリスチレン組成物は、弱電機
器、雑貨、玩具等の分野において成形品として使用でき
る。The high-gloss rubber-reinforced polystyrene composition of the present invention can be used as molded articles in fields such as light electrical equipment, miscellaneous goods, and toys.
（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。(Example) Examples are shown below. The data shown in the examples were measured based on the following method.
アイゾツト衝撃強度； ＡＳＴＭ Ｄ ２５６によった
。Izod impact strength; according to ASTM D 256.
引張強度； ＡＳＴＭ Ｄ ６３８
光沢：成形時の樹脂温度２２０℃、金星温度４５℃にて
成形したダンベル試験片のゲート部とエンドゲート部の
光沢度をクロスメーターを用いて測定し平均した。Tensile strength; ASTM D 638 Gloss: The gloss of the gate and end gate portions of a dumbbell test piece molded at a resin temperature of 220° C. and a Venus temperature of 45° C. was measured using a crossmeter and averaged.
着色性：樹脂１００重量部に黒糸の染顔料の一定量を添
加して、成形片（たて８９Ｂ、よこ５０ｊＥＩＩｓ厚み
２５闘）を作成し、色の濃さ忙よって着色性を判定する
。Colorability: Add a certain amount of black thread dye and pigment to 100 parts by weight of the resin to create a molded piece (length: 89B, width: 50JEIIs, thickness: 25cm), and determine the colorability based on the depth of the color.
９重量％のポリブタジェンゴムを含有するゴム補強ポリ
スチレン１ｋｌｉ’あたり、２５円、２０円。25 and 20 yen per kli' of rubber-reinforced polystyrene containing 9% by weight of polybutadiene rubber.
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とし、下記に示す定義
によりランクＯ〜５付けして判定する。Black-colored molded pieces prepared by adding dye and pigment worth 15 yen were used as control samples A, B, and C, respectively, and evaluated by ranking them from O to 5 according to the definitions shown below.
参考例１
ゴム補強ポリスチレンの製造
第一の流れとして１．８ Ｊ ／時間の供給速度和て、
ポリブタジェン１２重量％、スチレン８０重量％、エチ
ルベンゼン８重量％からなる溶液１００重量部、１１ビ
ス（ｔ−ブチルパーオキシ） ３，３．５− ）リメチ
ルシクロヘキサン０．０４５重量部からなる混合物を第
−重合機に連続的に送入する。第−重合機は温度１０５
℃である。第二の流れとして１ノ／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、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高ぜん断カ下忙
混合機内で混合される。Reference Example 1 Production of rubber-reinforced polystyrene As the first flow, the total supply rate was 1.8 J/hour,
A mixture of 100 parts by weight of a solution consisting of 12% by weight of polybutadiene, 80% by weight of styrene, and 8% by weight of ethylbenzene, and 0.045 parts by weight of 11bis(t-butylperoxy)3,3.5-)limethylcyclohexane was prepared. - Continuously feed into the polymerization machine. - The temperature of the polymerization machine is 105
It is ℃. As a second stream, a mixed solution of 90% by weight styrene and 10% by weight ethylbenzene is fed into the second polymerizer at a temperature of 120 DEG -140 DEG C. at a feed rate of 1 no/hr. These first and second streams are mixed in a high shear power mixer.
更に、温度１１０〜１３０ ℃の第三重合機、温度−１
３５へ１６０℃の第四重合機に送入し重合を進めた後忙
、未反応上ツマ−及び溶媒を減圧下圧除去してベレット
状のゴム補強ポリスチレンな得る。Furthermore, a third polymerizer with a temperature of 110 to 130 °C, a temperature of -1
After the polymerization was carried out in a fourth polymerizer at 160 DEG C., unreacted polymers and solvent were removed under reduced pressure to obtain pellet-shaped rubber-reinforced polystyrene.
上記の方法にて、ポリブタジェン含有量が１０重量％で
あり、分散ゴム粒子の平均粒子径が０．５４゜０．８１
、０．６０ 、０．４９ 、０．１８ 、１．２３で
、０．３ミクロン以下の内蔵ポリスチレン粒子の割合が
９３％、８７％、９０％、９５％、９５％。In the above method, the polybutadiene content was 10% by weight, and the average particle diameter of the dispersed rubber particles was 0.54° and 0.81°.
, 0.60, 0.49, 0.18, 1.23, and the percentage of built-in polystyrene particles of 0.3 microns or less is 93%, 87%, 90%, 95%, 95%.
８５％である６８１類のゴム補強ポリスチレンを得た。Rubber-reinforced polystyrene of type 681 with a content of 85% was obtained.
参考例２
ゴム補強ポリスチレンの製造
ポリブタジェン７重量％、スチレン８３重量％、エチル
ベンゼン１０重量％からなる溶液１００重量部と、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重量部とからなる混合物
を第−重合機に連続的に送入し、撹拌下に重合を進め、
その後第二重合機、第三重合機にて更に重合を進行させ
た後に、未反応モノマー及び溶媒を減圧下に除去してベ
レット状のゴム補強ポリスチレンを得る。Reference Example 2 Production of Rubber Reinforced Polystyrene 100 parts by weight of a solution consisting of 7% by weight of polybutadiene, 83% by weight of styrene, and 10% by weight of ethylbenzene, 1.
A mixture consisting of 1bis(t-butylperoxy) and 0.045 parts by weight of 3,3.5-trimethylcyclohexane was continuously fed into the first polymerization machine, and the polymerization was proceeded with stirring,
After that, polymerization is further advanced in a second polymerization machine and a third polymerization machine, and then unreacted monomers and solvent are removed under reduced pressure to obtain a pellet-shaped rubber-reinforced polystyrene.
上記の方法にて、ポリブタジェン含有量が１０重量％で
あり、分散ゴム粒子の平均粒径が０．５５μと０．８０
μでかつ０．３μ以下の内蔵ポリスチレン粒子の割合い
が各々７０％と６２％の２種類のゴム補強ポリスチレン
を得た。In the above method, the polybutadiene content was 10% by weight, and the average particle diameter of the dispersed rubber particles was 0.55μ and 0.80μ.
Two types of rubber-reinforced polystyrene were obtained in which the proportion of built-in polystyrene particles having a particle diameter of 70% and 62%, respectively, was 70% and 62%.
実施例１〜４及び比較例１〜４
参考例１及び参考例２で得た各種のゴム変性ポリスチレ
ン忙粘度が５００センチストークスのポリジメチルシロ
キサン０．２重量％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。Examples 1 to 4 and Comparative Examples 1 to 4 0.2% by weight of polydimethylsiloxane having a viscosity of 500 centistokes was added to the various rubber-modified polystyrene obtained in Reference Example 1 and Reference Example 2, and kneaded in an extruder. A resin composition was obtained, and its Izot impact strength, tensile strength, gloss, and colorability were evaluated.
七の結果を表−１に示す。平均粒子径が０．２０μ未満
ではアイゾツト衝準強度が低下し、また１、００μを越
えると光沢及び引張強度が低下することがわかる。また
０、３μ以下の内蔵ポリスチレン粒子の割合いが８０％
より少くなると光沢、着色性及び引張強度が低下するこ
とがわかる。平均粒子径が０．２０〜１．００μの範囲
にあり、かつ０．３μ以下の内蔵ポリスチレン粒子の割
合いが８０％以上である時が好ましいことがわかる。The results of 7 are shown in Table 1. It can be seen that if the average particle diameter is less than 0.20μ, the Izot impact strength decreases, and if it exceeds 1,00μ, the gloss and tensile strength decrease. Also, the proportion of built-in polystyrene particles of 0.3μ or less is 80%.
It can be seen that as the amount decreases, gloss, colorability, and tensile strength decrease. It can be seen that it is preferable that the average particle diameter is in the range of 0.20 to 1.00 μ and the proportion of built-in polystyrene particles of 0.3 μ or less is 80% or more.
実施例５〜７及び比較例５〜６
参考例１で得た平均粒子径が０．５４μ、０．３μ以下
の内蔵ポリスチレン粒子の割合いが９３％であるゴム補
強ポリスチレンに実施例１で用いたポリジメチルシロキ
サン及びステアリン酸亜鉛を表−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に示した。ポリジメチルシロキ
サンの添加量が０．００２重量％と少なくなるとアイゾ
ツト衝撃強度が低下する。ポリジメチルシロキサンの添
加量が０．９ｍ−ｆ１％を越えて多い場合は着色性が低
下し好ましくない。Examples 5 to 7 and Comparative Examples 5 to 6 The rubber-reinforced polystyrene obtained in Reference Example 1 with an average particle diameter of 0.54 μ and a proportion of built-in polystyrene particles of 0.3 μ or less was used in Example 1. At the addition amounts of polydimethylsiloxane and zinc stearate shown in Table 2,
A resin composition was obtained in the same manner as in Example 1, and its physical properties were evaluated. The results are shown in Table-2. When the amount of polydimethylsiloxane added is as small as 0.002% by weight, the Izod impact strength decreases. If the amount of polydimethylsiloxane added is more than 0.9 m-f1%, the coloring properties will deteriorate, which is not preferable.
（桐）白）(paulownia) white)
Claims (1)
ン組成物において （Ａ）分散粒子の平均粒子径が０．２０〜１．００ミク
ロンの範囲にあり、 （Ｂ）該分散ゴム状物質の粒子中に芳香族モノビニル重
合体を粒子状の形状にて内蔵しており、その粒子数の８
０％以上が０．３ミクロン以下であり、 （Ｃ）該組成物中にポリジメチルシロキサンが０．００
５〜０．８重量％含有されている ことを特徴とする高光沢ゴム補強ポリスチレン組成物[Claims] A rubber-reinforced polystyrene composition in which a rubber-like substance is dispersed in the form of particles, in which (A) the average particle diameter of the dispersed particles is in the range of 0.20 to 1.00 microns; The aromatic monovinyl polymer is incorporated in the particles of the dispersed rubber-like substance in the form of particles, and the number of particles is 8.
0% or more is 0.3 microns or less, and (C) the composition contains 0.00% polydimethylsiloxane.
High-gloss rubber-reinforced polystyrene composition characterized by containing 5 to 0.8% by weight
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17552486A JPS6333461A (en) | 1986-07-28 | 1986-07-28 | High-gloss rubber-reinforced polystyrene composition |
| NL8602634A NL193458C (en) | 1985-10-22 | 1986-10-21 | Process for the continuous preparation of a rubber-reinforced polystyrene composition with a high impact strength. |
| DE19863635943 DE3635943A1 (en) | 1985-10-22 | 1986-10-22 | HIGH-GLOSSY, RUBBER-REINFORCED POLYSTYRENE COMPOSITION AND METHOD FOR THEIR CONTINUOUS PRODUCTION |
| US07/303,066 US4975486A (en) | 1985-10-22 | 1989-01-30 | High-gloss rubber-reinforced polystyrene composition and method for continuous production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17552486A JPS6333461A (en) | 1986-07-28 | 1986-07-28 | High-gloss rubber-reinforced polystyrene composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6333461A true JPS6333461A (en) | 1988-02-13 |
Family
ID=15997567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17552486A Pending JPS6333461A (en) | 1985-10-22 | 1986-07-28 | High-gloss rubber-reinforced polystyrene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6333461A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031050A (en) * | 1995-02-08 | 2000-02-29 | Nippon Steel Chemical Co., Ltd | Rubber-modified styrenic resin composition |
-
1986
- 1986-07-28 JP JP17552486A patent/JPS6333461A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031050A (en) * | 1995-02-08 | 2000-02-29 | Nippon Steel Chemical Co., Ltd | Rubber-modified styrenic resin composition |
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