JPH0518348B2 - - Google Patents
Info
- Publication number
- JPH0518348B2 JPH0518348B2 JP63102769A JP10276988A JPH0518348B2 JP H0518348 B2 JPH0518348 B2 JP H0518348B2 JP 63102769 A JP63102769 A JP 63102769A JP 10276988 A JP10276988 A JP 10276988A JP H0518348 B2 JPH0518348 B2 JP H0518348B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- microns
- modified polystyrene
- composition
- 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 68
- 239000004793 Polystyrene Substances 0.000 claims description 40
- 229920002223 polystyrene Polymers 0.000 claims description 40
- 229920001971 elastomer Polymers 0.000 claims description 29
- 239000005060 rubber Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- -1 polydimethylsiloxane Polymers 0.000 claims description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 16
- 239000011342 resin composition Substances 0.000 claims description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- 239000002480 mineral oil Substances 0.000 claims description 12
- 235000010446 mineral oil Nutrition 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920005990 polystyrene resin Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 229920002857 polybutadiene Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 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
- 241001237745 Salamis Species 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000015175 salami Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 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耐
衝撃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、剛性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
1.0〜5.0ミクロン程度であり、最近は成形品の光
沢を向上させる為にゴム粒子径の小さいものが開
発上市されて来ているが、1.0ミクロン以下の小
小さいゴム粒子径の場合には衝撃強度の低下が著
しく好ましい樹脂は得られていない。また衝撃強
度と光沢のバランスを改良する為に1.0ミクロン
以下の小さなゴム粒子径を有するゴム変性ポリス
チレンと大きなゴム粒子径を有するゴム変性ポリ
スチレンとのブレンドからなる組成物が特公昭46
−41467号公報59−1519号公報、米国特許第
4146589号明細書、米国特許第4214056号明細書、
米国特許第4493922号明細書などの先行文献に述
べられているが。使用されている大粒子が２ミク
ロン以上と大きい為に成形品の外観が劣り、特に
光沢勾配が大きい（成形品においてゲートからの
遠い個所の光沢の低下が大きい）、金型温度の低
い条件で成形されると光沢が充分でないなどの問
題点があつた。
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
Plastics1972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
径の小さいゴム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、優れた成形品外観（特に光沢値が高く
光沢勾配の少いこと）、着色性、衝撃強度、剛性
の品質バランスのよいゴム変性ポリスチレン樹脂
が必要となる。上記する優れた成形品外観、着色
性、衝撃強度、剛性の品質バランスの優れた安価
な耐衝撃性ポリスチレンン樹脂を得ることが本発
明の目的である。
（問題点を解決するための手段）
本発明の組成物は、特定のミクロ構造を有する
ゴム変性ポリスチレンとポリジメチルシロキサン
及びミネラルオイル及び／または高級脂肪酸の金
属塩、高級脂肪酸のアミド類よりなる。
即ち、本発明は耐衝撃性ポリスチレン樹脂組成
物において、該組成物中のゴム変性ポリスチレン
中にゴム状重合体が粒子状に分散しており、その
分散粒子は小粒子部分と大粒子部分との２つの山
からなる分布を示し、小粒子部分の平均粒子径が
0.1〜0.6ミクロンであり、かつ単一オクルージヨ
ン構造を有し、大粒径部分の平均粒子径が0.7〜
2.0ミクロンにある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。
上記の特定のミクロン構造を有するゴム変性ポ
リスチレンとポリジメチルシロキサン及びミネラ
ルオイル及び／または高級脂肪酸の金属塩、高級
脂肪酸のアミド類を組み合わ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耐
衝撃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。
本発明で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
チルスチレン等の該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等が用いられ
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。
本発明においてゴム粒子径の分布が２つの山か
らなる分布を示すゴム変性ポリスチレンは、小粒
子ゴムを含有するゴム変性ポリスチレンと大粒子
ゴムを含有するゴム変性ポリスチレンとを別々に
つくり、押出機などでブレンドすることにより製
造することもできるし、小粒子ゴムと大粒子ゴム
とを重合反応器にて混合することにより製造する
こともできる。小粒子部分の平均粒径は0.1〜0.6
ミクロンであることが必要であり、好ましくは
0.2〜0.5ミクロンであり、より好ましくは0.2〜
0.4ミクロンである。この平均粒子径が、0.1ミク
ロン以下では衝撃強度が低下し、また0.6ミクロ
ン以上では成形品の外観、特に光沢勾配が大きく
なりまた光沢の低下がみられれ好ましくない。更
に小粒子ゴムは単一オクルージヨン構造（シエ
ル／コア形またはカプセル形ともいわれる）を有
していることが良好な光沢と耐衝撃強度のバラン
スを実現するために必要である。このような小粒
子ゴムは、スチレンとブタジエンのブロツク共重
合体の存在下で攪拌下にスチレンを重合すること
によつても効率良く製造することができる。また
大粒子部分の平均粒径は、0.7〜2.0ミクロンであ
ることが必要であり、好ましくは1.0〜1.5ミクロ
ンである。この平均粒子径が0.7ミクロン以下で
は、衝撃強度が低下し、また2.0ミクロン以上で
は、成形品の外観、特に光沢勾配が大きくなり、
また金型温度の低い条件で形成されると光沢が不
充分となるなえどの点で好ましくない。またゴム
粒子径分布は小粒子部分と大粒子部分からなる２
つの山からなる分布を有していることが成形品外
観、衝撃強度、着色性、剛性の品Km2バランスの優
れた樹脂を与える。
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＝ΣniDi4／ΣniDi3
（ここにniは粒子径Diのゴム状重合体粒子の個数
である。
また本発明において、組成物中のゴムの総量の
20〜95重量％、好ましくは50〜90重量％、最も好
ましくは70〜90重量％が小粒子部分であり、５〜
80重量％好ましくは10〜50重量％、最も好ましく
は10〜30重量％が大粒子部分である。小粒子部分
が20重量％以以下では成形品外観が低下し、95重
量％以上では衝撃強度が低下し好ましくない。
また、本発明に用いるゴム変性ポリスチレンは
良好な成形品外観を得る為に、実質上２ミクロン
以上の大きなゴム粒子を含有していないことが好
ましい。実質上含有していないとは２ミクロン以
上のゴム粒子が組成物中のゴムの総量の20重量％
以下、好ましくは５重量％以下であることを示
す。組成物中に２ミクロン以上の大きなゴム粒子
が20重量％以上存在すると光沢勾配が大きくな
り、また低い金型温度で得た成形品の光沢が低下
するなどして、好ましい成形品外観を得ることが
できない。
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 high-impact 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, impact strength, and rigidity in injection molded products, extrusion sheets, extrusion vacuum molding, and the like. It has great value as an economical resin that can replace expensive ABS resin, make products thinner, and reduce costs. (Conventional technology) Rubber-modified polystyrene has been widely used industrially, but the dispersed rubber particle size is generally
The diameter of rubber particles is approximately 1.0 to 5.0 microns, and recently, rubber particles with small particle diameters of 1.0 microns or less have been developed and put on the market to improve the gloss of molded products. No resin has been obtained that exhibits a significant decrease in . In addition, in order to improve the balance between impact strength and gloss, a composition consisting of a blend of rubber-modified polystyrene with a small rubber particle size of 1.0 microns or less and a rubber-modified polystyrene with a large rubber particle size was developed.
-41467 Publication No. 59-1519 Publication, U.S. Patent No.
4146589 specification, US Patent No. 4214056 specification,
Although described in prior documents such as US Pat. No. 4,493,922. Because the large particles used are larger than 2 microns, the appearance of the molded product is poor, especially when the gloss gradient is large (the gloss decreases greatly in the parts far from the gate) and the mold temperature is low. When molded, there were problems such as insufficient gloss. 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,
As stated in prior documents such as JP-A No. 57-187345 and JP-A No. 57-187346, a preferable resin composition cannot be obtained when rubber-modified polystyrene with a small rubber particle size is used. do not have. (Problems to be Solved by the Invention) In order to meet the market demand for rubber-modified polystyrene with an excellent overall balance of quality as described above, it is necessary to have an excellent molded product appearance (in particular, a high gloss value and a low gloss gradient). A rubber-modified polystyrene resin with a good balance of colorability, impact strength, and rigidity is required. It is an object of the present invention to obtain an inexpensive impact-resistant polystyrene resin having an excellent quality balance among the above-mentioned excellent molded product appearance, colorability, impact strength, and rigidity. (Means for Solving the Problems) The composition of the present invention comprises rubber-modified polystyrene having a specific microstructure, polydimethylsiloxane, mineral oil and/or metal salts of higher fatty acids and amides of higher fatty acids. That is, the present invention provides an impact-resistant polystyrene resin composition in which a rubber-like polymer is dispersed in the form of particles in rubber-modified polystyrene in the composition, and the dispersed particles are composed of a small particle portion and a large particle portion. It shows a distribution consisting of two peaks, and the average particle diameter of the small particle portion is
It is 0.1 to 0.6 micron, has a single occlusion structure, and has an average particle diameter of 0.7 to 0.6 microns.
This is a resin composition made of rubber-modified polystyrene characterized by a particle size of 2.0 microns. By combining the rubber-modified polystyrene with the above-mentioned specific micron structure, polydimethylsiloxane, mineral oil and/or metal salts of higher fatty acids, and amides of higher fatty acids, a surprisingly excellent overall balance of quality can be achieved. We have succeeded in obtaining an impact-resistant polystyrene resin composition. 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, and p-tert-butylstyrene; −
α-alkyl substituted styrenes such as methylstyrene and α-methyl-p-methylstyrene are used. Further, examples of the rubbery polymer include 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. In the present invention, rubber-modified polystyrene having a rubber particle size distribution consisting of two peaks is produced by separately producing rubber-modified polystyrene containing small-particle rubber and rubber-modified polystyrene containing large-particle rubber, and using an extruder or the like. It can also be produced by blending small particle rubber and large particle rubber in a polymerization reactor. The average particle size of the small particle part is 0.1-0.6
microns, preferably
0.2-0.5 micron, more preferably 0.2-0.5 micron
It is 0.4 micron. If the average particle size is less than 0.1 micron, the impact strength will decrease, and if it is more than 0.6 micron, the appearance of the molded product, especially the gloss gradient will become large and the gloss will decrease, which is undesirable. Furthermore, it is necessary for the small particle rubber to have a single occlusion structure (also referred to as shell/core type or capsule type) in order to achieve a good balance between gloss and impact strength. Such small particle rubber can also be efficiently produced by polymerizing styrene under stirring in the presence of a block copolymer of styrene and butadiene. The average particle diameter of the large particle portion must be 0.7 to 2.0 microns, preferably 1.0 to 1.5 microns. If the average particle size is less than 0.7 microns, the impact strength will decrease, and if it is more than 2.0 microns, the appearance of the molded product, especially the gloss gradient, will increase.
Furthermore, if the mold is formed at a low temperature, the gloss will be insufficient, which is undesirable. Furthermore, the rubber particle size distribution consists of a small particle portion and a large particle portion.
Having a distribution consisting of two peaks gives a resin with an excellent balance of molded product appearance, impact strength, colorability, and rigidity. 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 diameter = ΣniDi 4 /ΣniDi 3 (where ni is the number of rubbery polymer particles with a particle diameter Di. In addition, in the present invention, the total amount of rubber in the composition
20-95% by weight, preferably 50-90%, most preferably 70-90% by weight are small particle fractions, and 5-95% by weight are small particle fractions.
80% by weight, preferably 10-50% by weight, most preferably 10-30% by weight is the large particle fraction. If the small particle portion is less than 20% by weight, the appearance of the molded product will deteriorate, and if it is more than 95% by weight, the impact strength will be reduced, which is not preferable. Further, in order to obtain a good appearance of the molded product, the rubber-modified polystyrene used in the present invention preferably does not substantially contain large rubber particles of 2 microns or more. Substantially free means that rubber particles larger than 2 microns account for 20% by weight of the total amount of rubber in the composition.
Hereinafter, it will be shown that the content is preferably 5% by weight or less. If 20% by weight or more of large rubber particles of 2 microns or more are present in the composition, the gloss gradient becomes large, and the gloss of molded products obtained at low mold temperatures decreases, making it difficult to obtain a desirable molded product appearance. I can't. 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。更に好ましくは、ポ
リジメチルシロキサンの粘度も25℃で、10〜1000
センチストーククスと比較的分子量の低い範囲に
あることである。
更に耐衝撃性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、0.005〜0.8重量％の
範囲にあることである。含有量が0.005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。このような点からポリジメチルシロキ
サンの含有量が、好ましい耐衝撃性ポリスチレン
組成物を得る為に重要である。
次に本発明に云うミネラルオイルとは、ポリス
チレンの可塑剤として常用のものを示し、粘度等
に特に制約は無い。また本発明に云う高級脂肪酸
の金属塩、高級脂肪酸のアミド類とは、滑剤とし
て常用のものであり、例えばステアリン酸亜鉛、
ステアリン酸マグネシウム、ステアリン酸カルル
シウム、エチレンビスステアリルアミド等を挙げ
ることができる。
本発明にて上記のミネラルオイルおよび／また
は高級脂肪酸の金属塩、高級脂肪酸のアミド類
は、前記のポリジメチルシロキサンと併用して、
前記の特定ミクロ構造のゴム変性ポリスチレンに
添加される場合は、その衝撃強度を著しく高める
効果を奏する。
ポリジメチルロキサンと併用する場合のミネラ
ルオイルの、耐衝撃性ポリスチレン組成物中の含
有量は、0.25〜4.0重量％の範囲にあることとが
必要である。含有量が0.25重量％未満となると衝
撃強度を高める効果に乏しく、4.0重量％を越え
ると、耐熱性を下げ、着色性を損なうようにな
る。
ポリジメチルシロキサンと併用する場合の高級
脂肪酸の金属塩および／または高級脂肪酸のアミ
ド類の、耐衝遇性ポリスチレン組成物中の含有量
は、0.1重量％以上であることが必要であり、0.5
重量％を越えないことが好ましい。含有量が0.1
重量％未満であると、衝撃強度を高める効果に乏
しく、0.5重量％を越えると衝撃強度を高める効
果が頭打ちとなり、経済的でない。
本発明の耐衝撃性ポリスチレン組成物には染顔
料、充填剤、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衝撃強度、光沢、剛性の
物性面での品質総合バランスに優れる。特に、特
殊なミクロ構造を有するゴム変性ポリスチレンと
ポリジメチルシロキサンおよびミネラルオイルま
たは高級脂肪酸の金属塩、アミド類との組合せに
て得た樹脂組成物は、従来のゴム変性ポリスチレ
ンに比べて衝撃強度が大巾に向上し、かつ成形品
外観、特に射出成形された成形品においてゲート
部分から遠く離れた部分の光沢が非常に良好であ
る。このような特性を有することから特に大型の
射出成形品を得る為の樹脂として非常に好まし
い。更に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大
きな意味をもつものである。
本発明の樹脂は、弱電機器、雑貨等の分野にお
いて成形品として使用できる。
（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に準拠
曲げ弾性率；ASTM D790に準拠
ビカツト軟化点；ASTM 1525に準拠
光沢；ASTM D638の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測定たした。
実施例１〜５及び比較例１〜５
スチレン−ブタジエンブロツク共重合体の存在
下にスチレンモノマーを攪拌下で重合することに
よつて得た平均粒子径が0.2ミクロンで単一オク
ルージヨン構造を有し、樹脂中のポリブタジエン
成分の含有量が９重量％であるゴム変性ポリスチ
レン(A)と、ポリブタジエンの存在下にスチレンモ
ノマーを攪拌下で重合することによつて得た平均
粒子径が1.2ミクロンでサラミ構造を有し、樹脂
中のポリブタジエン成分の含有量が12重量％であ
るゴム変性ポリスチレン(B)とを、(A)：(B)＝90：10
の重量比で混合し、更にゴム変性ポリスチレン
に、500センチストークスの粘度を有するポリジ
メチルシロキサン及びミネラルオイル、ステアリ
ン酸亜鉛を表−１に示す重量比となるよう加え、
押出機にて溶融混練して樹脂組成物を得た。該樹
脂組成物のアイゾツト衝撃強度、曲げ弾性率、ビ
カツト軟化点、光沢及び着色性を評価した。その
結果を表−１に示す。
小粒子径ゴム粒子を含有するゴム変性ポリスチ
レン(A)と大粒子径ゴム粒子を含有するゴム変性ポ
リスチレン(B)とを適当な比率で配合したゴム変性
ポリスチレンが、ポリジメチルシロキサンとミネ
ラルオイルの適量を含有する場合（実施例１及び
２）、ポリジメチルシロキサンとステアアリン酸
亜鉛の適量を含有する場合（実施例３及び４）に
は衝撃強度が著しく高く、かつ光沢、特にエンド
ゲート部の光沢が良好な組成物が得られる。これ
に対し、ゴム変性ポリスチレン(A)とゴム変性ポリ
スチレン(B)を配合したゴム変性ポリスチレンが、
ポリジメチルシロキサンを含有しない場合（比較
例１）や、ポリジメチルシロキサンを含有する
が、ミネラルオイルもしくはステアリン酸亜鉛を
全く含有しないか（比較例２）、含有量が本発明
の範囲に満たない場合（比較例３及び４）には、
衝撃強度が充分でない。またミネラルオイルの含
有量が、本発明の範囲を越えると、耐熱温度の低
下し、着色性も悪化してしまう比較例5.また、ゴ
ム変性ポリスチレン(A)とゴム変性ポリスチレン(B)
を配合したゴム変性ポリスチレンが、ポリジメチ
ルポリシロキサンに加え、適当量のミネラルオイ
ル及びステアリン酸亜鉛を含有すると、極めて高
い衝撃強度を発揮するようになる。
比較例 ６
実施例３において、平均粒子径が0.2ミクロン
で単一オクルージヨン構造を有し、樹脂中のポリ
ブタジエン成分の含有量が９重量％であるゴム変
性ポリスチレンに代えて、ポリブタジエン及びス
チレン−ブタジエンブロツク共重合体の存在下に
スチレンモノマーを撹拌下で重合することによつ
て得た、平均粒子径が0.2ミクロンで大部分が、
単一オクル−ジヨン構造でなく、樹脂中のポリブ
タジエンの含有量が９重量％であるゴム変性ポリ
スチレンを用いる以外は、実施ば例３と同様にし
て樹脂組成物を得た。その結果を表−１に示す。It is necessary to have a structural unit represented by the formula: In the case of rubber-modified polystyrene having the rubber particle size of the present invention, a preferred resin composition cannot be obtained with organic polysiloxanes such as those described in prior art documents other than polydimethylsiloxane. More preferably, the viscosity of the polydimethylsiloxane is also 10 to 1000 at 25°C.
It has a relatively low molecular weight compared to centistokes. Furthermore, the content of polydimethylsiloxane in the impact-resistant polystyrene composition is in the range of 0.005 to 0.8% by weight. When the content is less than 0.005% by weight, a decrease in impact strength is observed, and 0.8% by weight.
If it exceeds this range, it is unfavorable in terms of colorability and secondary processability (chemical adhesion, printability, paintability, etc.) of the resin molded product. From this point of view, the content of polydimethylsiloxane is important in order to obtain a preferable impact-resistant polystyrene composition. Next, the mineral oil referred to in the present invention refers to one commonly used as a plasticizer for polystyrene, and there are no particular restrictions on viscosity or the like. Furthermore, the metal salts of higher fatty acids and amides of higher fatty acids referred to in the present invention are those commonly used as lubricants, such as zinc stearate,
Examples include magnesium stearate, callucium stearate, and ethylene bisstearylamide. In the present invention, the above-mentioned mineral oil and/or metal salts of higher fatty acids and amides of higher fatty acids are used in combination with the above-mentioned polydimethylsiloxane,
When added to the rubber-modified polystyrene having the specific microstructure described above, it has the effect of significantly increasing its impact strength. The content of mineral oil in the impact-resistant polystyrene composition when used in combination with polydimethyloxane is required to be in the range of 0.25 to 4.0% by weight. If the content is less than 0.25% by weight, the effect of increasing impact strength will be poor, and if it exceeds 4.0% by weight, heat resistance will be lowered and colorability will be impaired. The content of metal salts of higher fatty acids and/or amides of higher fatty acids in the impact-resistant polystyrene composition when used in combination with polydimethylsiloxane must be 0.1% by weight or more, and 0.5% by weight.
It is preferred not to exceed % by weight. Content is 0.1
If it is less than 0.5% by weight, the effect of increasing impact strength will be poor, and if it exceeds 0.5% by weight, the effect of increasing impact strength will reach a plateau, making it uneconomical. Additives such as dyes and pigments, fillers, and antistatic agents may be added to the impact-resistant polystyrene 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 impact strength, gloss, and rigidity. In particular, resin compositions obtained by combining rubber-modified polystyrene with a special microstructure with polydimethylsiloxane and mineral oil or higher fatty acid metal salts and amides have higher impact strength than conventional rubber-modified polystyrene. This greatly improves the appearance of the molded product, especially the gloss of the parts far away from the gate in injection molded molded products. Because it has such characteristics, it is very preferable as a resin particularly for obtaining large injection molded products. Furthermore, good coloring properties are of great industrial significance, as the cost of dyes and pigments used for coloring can be greatly reduced. The resin of the present invention can be used as molded products in fields such as light electrical equipment and miscellaneous goods. (Example) Examples are shown below. The data shown in the examples were measured based on the following method. Izot impact strength: Conforms to ASTM D256 Flexural modulus: Conforms to ASTM D790 Vikatsu softening point: Conforms to ASTM 1525 Gloss: The glossiness of the gate and end gate portions of the ASTM D638 dumbbell test piece was measured. Examples 1 to 5 and Comparative Examples 1 to 5 Polymerization of styrene monomer with stirring in the presence of a styrene-butadiene block copolymer had an average particle diameter of 0.2 microns and a single occlusion structure. , a salami with an average particle size of 1.2 microns obtained by polymerizing rubber-modified polystyrene (A) with a polybutadiene content of 9% by weight and a styrene monomer in the presence of polybutadiene under stirring. Rubber-modified polystyrene (B) which has a structure and the content of the polybutadiene component in the resin is 12% by weight, (A):(B) = 90:10
Further, polydimethylsiloxane having a viscosity of 500 centistokes, mineral oil, and zinc stearate were added to the rubber-modified polystyrene in the weight ratio shown in Table 1,
A resin composition was obtained by melt-kneading using an extruder. The Izot impact strength, flexural modulus, Vicat softening point, gloss and colorability of the resin composition were evaluated. The results are shown in Table-1. Rubber modified polystyrene (A) containing small rubber particles and rubber modified polystyrene (B) containing large rubber particles in an appropriate ratio is mixed with appropriate amounts of polydimethylsiloxane and mineral oil. (Examples 1 and 2), and when appropriate amounts of polydimethylsiloxane and zinc stearate (Examples 3 and 4), the impact strength is extremely high and the gloss, especially the gloss of the end gate area, is extremely high. A good composition is obtained. On the other hand, rubber-modified polystyrene, which is a blend of rubber-modified polystyrene (A) and rubber-modified polystyrene (B),
When it does not contain polydimethylsiloxane (Comparative Example 1), when it contains polydimethylsiloxane but does not contain mineral oil or zinc stearate at all (Comparative Example 2), or when the content is less than the range of the present invention (Comparative Examples 3 and 4)
Impact strength is not sufficient. In addition, if the content of mineral oil exceeds the range of the present invention, the heat resistance temperature will decrease and the coloring property will also deteriorate. Comparative Example 5.
When rubber-modified polystyrene blended with polydimethylpolysiloxane contains appropriate amounts of mineral oil and zinc stearate, it exhibits extremely high impact strength. Comparative Example 6 In Example 3, polybutadiene and styrene-butadiene block were used instead of rubber-modified polystyrene having an average particle size of 0.2 microns and a single occlusion structure, and the content of the polybutadiene component in the resin was 9% by weight. Obtained by polymerizing styrene monomer under stirring in the presence of a copolymer, the average particle size is 0.2 microns, and most of the particles are
A resin composition was obtained in the same manner as in Example 3, except that rubber-modified polystyrene having a polybutadiene content of 9% by weight was used instead of having a single occlusion structure. The results are shown in Table-1.
【表】
＊ 着色性ランクは、黒着色品において、染顔料添加
量を低減できる程度に応じて、比較例５を、
ランク３としてランク付けを行つた。４は、やや低
減できる。５は、かなり低減できることを示
す。
[Table] * The colorability ranking is based on the degree to which the amount of dye and pigment added can be reduced for black colored products.
It was ranked as rank 3. 4 can be reduced somewhat. 5 indicates that it can be significantly reduced.
Claims (1)
状重合体が粒子状に分散しており、その分散粒
子は小粒子部分と大粒子部分との２つの山から
なる分布を示し、小粒子部分の平均粒子径が
0.1〜0.6ミクロンであり、かつ単一オクルージ
ヨン構造を有し、大粒子部分の平均粒子径が
0.7〜2.0ミクロンであり、 (ii) 該組成物中に (A) ポリジメチルシロキサンが0.005〜0.8重量
％ (B) 下記より選ばれる少なくとも１種以上の添
加剤； （ｂ−１） ミネラルオイルが0.25〜4.0重
量％または／および （ｂ−２） 高級脂肪酸の金属塩および／ま
たは高級脂肪酸のアミドが0.1〜0.5重量％ 含有されている事を特徴とする高光沢耐衝撃性
ゴム変性ポリスチレン樹脂組成物。 ２ 組成物中のゴムの総量の20〜95重量％が小粒
子部分であり、５〜80重量％が大粒子部分である
ことを特徴とする特許請求の範囲第１項記載の組
成物。 ３ 小粒子部分の平均粒子径が、0.2〜0.5ミクロ
ンであることを特徴とする特許請求の範囲第１項
又は第２項記載の組成物。 ４ 大粒子部分の平均粒子径が、1.0〜1.5ミクロ
ンであることを特徴とする特許請求の範囲第１項
又は第２項記載の組成物。[Scope of Claims] 1. In an impact-resistant polystyrene resin composition, (i) a rubber-like polymer is dispersed in the form of particles in rubber-modified polystyrene in the composition, and the dispersed particles are divided into small particle portions. It shows a distribution consisting of two peaks with a large particle part, and the average particle diameter of the small particle part is
It is 0.1 to 0.6 microns, has a single occlusion structure, and has an average particle size of the large particle part.
0.7 to 2.0 microns, (ii) the composition contains (A) 0.005 to 0.8% by weight of polydimethylsiloxane; (B) at least one or more additives selected from the following; (b-1) mineral oil; 0.25 to 4.0% by weight or/and (b-2) A high-gloss impact-resistant rubber-modified polystyrene resin composition characterized by containing 0.1 to 0.5% by weight of a metal salt of a higher fatty acid and/or an amide of a higher fatty acid. thing. 2. The composition according to claim 1, wherein 20 to 95% by weight of the total amount of rubber in the composition is a small particle portion and 5 to 80% by weight is a large particle portion. 3. The composition according to claim 1 or 2, wherein the average particle diameter of the small particle portion is 0.2 to 0.5 microns. 4. The composition according to claim 1 or 2, wherein the average particle diameter of the large particle portion is 1.0 to 1.5 microns.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63102769A JPH01275649A (en) | 1988-04-27 | 1988-04-27 | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
| CA000595991A CA1335524C (en) | 1988-04-11 | 1989-04-07 | Rubber-modified polystyrene resin composition |
| DE1989604796 DE68904796T2 (en) | 1988-04-11 | 1989-04-10 | Rubber modified polystyrene resin composition. |
| US07/335,373 US5039714A (en) | 1988-04-11 | 1989-04-10 | Rubber-modified polystyrene resin composition |
| EP89200897A EP0337569B2 (en) | 1988-04-11 | 1989-04-10 | Rubber-modified polystyrene resin composition |
| KR1019890004774A KR920001046B1 (en) | 1986-10-29 | 1989-04-11 | Rubber-modified polystyrene resin composition |
| TW078102842A TW197460B (en) | 1986-10-29 | 1989-04-17 | |
| SG113094A SG113094G (en) | 1988-04-11 | 1994-08-13 | Rubber-modified polystyrene resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63102769A JPH01275649A (en) | 1988-04-27 | 1988-04-27 | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
| SG113094A SG113094G (en) | 1988-04-11 | 1994-08-13 | Rubber-modified polystyrene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01275649A JPH01275649A (en) | 1989-11-06 |
| JPH0518348B2 true JPH0518348B2 (en) | 1993-03-11 |
Family
ID=26443445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63102769A Granted JPH01275649A (en) | 1986-10-29 | 1988-04-27 | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01275649A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2676261B2 (en) * | 1988-07-28 | 1997-11-12 | 出光石油化学 株式会社 | Rubber modified styrenic resin composition |
| KR100455102B1 (en) * | 2001-11-23 | 2004-11-06 | 제일모직주식회사 | High Impact Polystyrene Resin with Good Heat Resistance and Falling Dart Impact Prepared by Continuous Mass Polymerization Process |
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| JPS51139850A (en) * | 1975-05-15 | 1976-12-02 | Labofina Sa | High impact polystylene composition and process for production thereof |
| JPS5453A (en) * | 1977-04-04 | 1979-01-05 | Dow Chemical Co | Clear and impacttresistant polystylene |
| JPS53124561A (en) * | 1977-04-06 | 1978-10-31 | Japan Synthetic Rubber Co Ltd | Preparation of rubber-modified thermoplastic resin composition |
| JPS553494A (en) * | 1978-06-23 | 1980-01-11 | Bayer Ag | Abs polymer having high notchhshock strength |
| US4493922A (en) * | 1980-09-20 | 1985-01-15 | Basf Aktiengesellschaft | Impact-resistant thermoplastic molding material |
| JPS57170949A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57172948A (en) * | 1981-04-17 | 1982-10-25 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57187345A (en) * | 1981-05-12 | 1982-11-18 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS60156709A (en) * | 1984-01-25 | 1985-08-16 | Asahi Chem Ind Co Ltd | Rubber-modified styrenic resin composition having improved appearance characteristics and impact resistance |
| JPS6185461A (en) * | 1984-10-02 | 1986-05-01 | Asahi Chem Ind Co Ltd | Polystyrene resin composition having high glossiness |
| JPS61183339A (en) * | 1985-02-12 | 1986-08-16 | Asahi Chem Ind Co Ltd | Improved rubber-modified polystyrene composition |
| JPS6281443A (en) * | 1985-10-03 | 1987-04-14 | Sumitomo Chem Co Ltd | Thermoplastic elastomer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01275649A (en) | 1989-11-06 |
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