JPH0742381B2 - Rubber modified polystyrene resin composition - Google Patents
Rubber modified polystyrene resin compositionInfo
- Publication number
- JPH0742381B2 JPH0742381B2 JP5304787A JP5304787A JPH0742381B2 JP H0742381 B2 JPH0742381 B2 JP H0742381B2 JP 5304787 A JP5304787 A JP 5304787A JP 5304787 A JP5304787 A JP 5304787A JP H0742381 B2 JPH0742381 B2 JP H0742381B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- modified polystyrene
- weight
- resin composition
- acid ester
- 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 - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は表面光沢に優れ、耐衝撃性の良好なゴム変性ポ
リスチレン樹脂組成物に関し、さらに詳しくは特定の粒
径のメタクリル酸エステル系共重合体および/またはア
クリル酸エステル系共重合体を所定割合で配合してなる
ゴム変性ポリスチレン樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a rubber-modified polystyrene resin composition having excellent surface gloss and good impact resistance, and more specifically to a methacrylic acid ester-based copolymer having a specific particle size. The present invention relates to a rubber-modified polystyrene resin composition obtained by blending a polymer and / or an acrylic acid ester-based copolymer in a predetermined ratio.
従来よりポリスチレンの機械的強度を向上させるための
1手段として、ゴム状物質を溶解したスチレンを重合さ
せ、いわゆるグラフトタイプのゴム変性ポリスチレンを
製造する方法が知られている。しかしながら、グラフト
タイプのゴム変性ポリスチレンは、製品を成形する際に
白化やクラックが発生したり、落下の衝撃に弱いうえ、
添加したゴム状物質により表面光沢が低下するという欠
点を有する。近年、ゴム変性ポリスチレンにおいてもア
クリロニトリル−ブタジエン−スチレン樹脂(ABS)同
様の光沢が要求されるようになってきた。これに対して
ゴム変性ポリスチレンのゴム粒子径,ゲル量等のミクロ
構造を検討し、光沢,耐衝撃性を向上させる試みがなさ
れているものの、両者を満足させるほど向上させるには
致っていない。Conventionally, as one means for improving the mechanical strength of polystyrene, a method of polymerizing styrene in which a rubber-like substance is dissolved to produce a so-called graft type rubber-modified polystyrene is known. However, the graft-type rubber-modified polystyrene is vulnerable to whitening and cracks when molding the product, and to the impact of dropping,
It has the drawback that the added rubber-like substance reduces the surface gloss. In recent years, rubber-modified polystyrene has been required to have the same gloss as acrylonitrile-butadiene-styrene resin (ABS). On the other hand, although the microstructure of rubber-modified polystyrene such as rubber particle size and gel amount has been investigated and attempts have been made to improve gloss and impact resistance, it has not been enough to satisfy both of them. .
そこで本発明者らは、鋭意検討した結果、特定のゴム粒
子径を有するゴム変性ポリスチレンに特定の粒子径を有
するメタクリル酸エステル系共重合体およびまたはアク
リル酸エステル系共重合体を配合した樹脂組成物が光
沢,耐衝撃性に優れていることを見出し、かかる知見に
基づいて本発明を完成するに致った。Therefore, as a result of intensive studies, the present inventors have made a resin composition in which a methacrylic acid ester-based copolymer having a specific particle diameter and / or an acrylic acid ester-based copolymer is mixed with a rubber-modified polystyrene having a specific rubber particle diameter. It was found that the product has excellent gloss and impact resistance, and based on such findings, the present invention was completed.
すなわち本発明は、(A)ゴム含有量が3〜15重量%で
あり、平均ゴム粒子径が0.5〜1.5μを有するゴム変性ポ
リスチレン100重量部に(B)(イ)メタクリル酸エス
テル単量体および/またはアクリル酸エステル単量体,
(ロ)芳香族ビニル単量体および(ハ)ジエン単量体と
からなり、粒子径0.5μ以下である共重合体3〜25重量
部を配合することを特徴とするゴム変性ポリスチレン樹
脂組成物を提供するものである。That is, in the present invention, (A) a rubber content of 3 to 15% by weight, 100 parts by weight of a rubber-modified polystyrene having an average rubber particle diameter of 0.5 to 1.5 μ, and (B) (a) a methacrylic acid ester monomer. And / or acrylic acid ester monomer,
(B) A rubber-modified polystyrene resin composition comprising 3 to 25 parts by weight of a copolymer having an aromatic vinyl monomer and (C) a diene monomer and having a particle diameter of 0.5 μm or less. Is provided.
本発明において(A)成分として用いるゴム変性ポリス
チレンは、ゴム状物質(例えばポリブタジエンゴム,ス
チレン−ブタジエン共重合体ゴムなど)を溶解したスチ
レンを塊状,懸濁または塊状−懸濁二段重合法などの慣
例グラフト重合法によって製造されるものである。この
場合、ゴム含有量は3〜15重量%、好ましくは4〜10重
量%が望ましく、平均ゴム粒子径は0.5〜1.5μが望まし
い。平均ゴム粒子径が1.5μ以上であると、光沢が悪く
なり、0.5μ未満であると、耐衝撃性に劣る樹脂組成物
となってしまう。なお、平均ゴム粒子径は撹拌機の回転
数,連鎖移動剤の使用量,反応温度等によって種々調整
することがてきる。The rubber-modified polystyrene used as the component (A) in the present invention is a bulk, suspension or bulk-suspension two-stage polymerization method of styrene in which a rubber-like substance (for example, polybutadiene rubber, styrene-butadiene copolymer rubber, etc.) is dissolved. It is produced by the conventional graft polymerization method. In this case, the rubber content is preferably 3 to 15% by weight, preferably 4 to 10% by weight, and the average rubber particle size is preferably 0.5 to 1.5 μm. If the average rubber particle diameter is 1.5 μm or more, the gloss is poor, and if it is less than 0.5 μm, the resin composition has poor impact resistance. The average rubber particle diameter can be variously adjusted depending on the number of revolutions of the stirrer, the amount of chain transfer agent used, the reaction temperature, and the like.
次に、本発明の(B)成分である共重合体は、(イ)メ
タクリル酸エステル単量体および/またはアクリル酸エ
ステル単量体,(ロ)芳香族ビニル単量体および(ハ)
ジエン単量体を反応させて得られるものである。Next, the copolymer which is the component (B) of the present invention is (a) a methacrylic acid ester monomer and / or an acrylic acid ester monomer, (b) an aromatic vinyl monomer and (c).
It is obtained by reacting a diene monomer.
ここでメタクリル酸エステル単量体としてはメタクリル
酸メチル,メタクリル酸エチル,メタクリル酸プロピ
ル,メタクリル酸イソプロピル,メタクリル酸ブチル等
があり、アクリル酸エステル単量体としてはアクリル酸
メチル,アクリル酸エチル,アクリル酸ブチルなどがあ
り、これらを単独で、あるいは2種以上を組合せて使用
する。これらの中ではメタクリル酸メチル,メタクリル
酸ブチルなどが好適である。Here, the methacrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, and the like, and the acrylate ester monomers include methyl acrylate, ethyl acrylate, and acrylic acid. Butyl acid and the like are used, and these are used alone or in combination of two or more kinds. Of these, methyl methacrylate and butyl methacrylate are preferable.
芳香族ビニル単量体としてはスチレンのほかα−メチル
スチレン,o−メチルスチレン,m−メチルスチレン,p−メ
チルスチレン,2,4−ジクロルスチレン,2,5−ジクロルス
チレン,ジメチルスチレン等のスチレン誘導体も使用で
きる。Aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dichlorostyrene, 2,5-dichlorostyrene, dimethylstyrene, etc. The styrene derivative of can also be used.
また、ジエン単量体としてはプロパジエン,1,2−ブタジ
エン,1,3−ブタジエン,イソプレン,クロロプレン,1,3
−ペンタジエンなどがあり、これらの中ではブタジエン
またはその誘導体が好適である。なお、このジエン単量
体は、他の成分と共重合反応させる前に単独に重合させ
てから使用することも可能である。Further, as the diene monomer, propadiene, 1,2-butadiene, 1,3-butadiene, isoprene, chloroprene, 1,3
-Pentadiene and the like, of which butadiene or its derivatives are preferred. The diene monomer may be used after being polymerized alone before the copolymerization reaction with other components.
本発明における(B)成分の共重合体は上記各単量体を
用いて様々な方法で製造することができ、その1例を示
すと、(ハ)ジエン単量体を重合させて得られるジエン
ゴムまたはその混合物の存在下で(イ)メタクリル酸エ
ステル単量体および/またはアクリル酸エステル単量
体,(ロ)芳香族ビニル単量体を乳化重合法,懸濁重合
法,溶液重合法,塊状−懸濁重合法などの公知の手段に
より共重合させる方法がある。その他、例えばメタクリ
ル酸ブチルとブタジエンと共重合させて得られるゴムラ
テックスにスチレンとメタクリル酸メチルを添加しグラ
フト重合させることにより製造することができる。この
ようにして得られる(B)成分の中でも、(イ)メタク
リル酸エステル単量体および/またはアクリル酸エステ
ル単量体含量が5〜40重量%であり、(ロ)芳香族ビニ
ル単量体含量が5〜40重量%であり、(ハ)ジエン単量
体含量が30〜80重量%のものが好ましい。The copolymer of the component (B) in the present invention can be produced by various methods using each of the above monomers, and one example thereof is obtained by polymerizing the (c) diene monomer. In the presence of a diene rubber or a mixture thereof, (a) a methacrylic acid ester monomer and / or an acrylic acid ester monomer, and (b) an aromatic vinyl monomer are subjected to an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, There is a method of copolymerization by a known means such as a bulk-suspension polymerization method. In addition, for example, it can be produced by adding styrene and methyl methacrylate to a rubber latex obtained by copolymerizing butyl methacrylate and butadiene and graft-polymerizing. Among the components (B) thus obtained, the content of (a) methacrylic acid ester monomer and / or acrylic acid ester monomer is 5 to 40% by weight, and (b) aromatic vinyl monomer. It is preferable that the content is 5 to 40% by weight and the content of the (C) diene monomer is 30 to 80% by weight.
また、共重合体の粒径は0.5μ以下でなければならな
い。粒径が0.5μを超えたものであると、高い光沢が得
られず望ましくない。なお、(B)成分の代表例とし
て、メタクリル酸メチル−ブタジエン−スチレン樹脂
(MBS)樹脂)をあげることができる。Further, the particle size of the copolymer must be 0.5 μm or less. If the particle size exceeds 0.5 μ, high gloss cannot be obtained, which is not desirable. A typical example of the component (B) is methyl methacrylate-butadiene-styrene resin (MBS) resin).
上記の如き(B)成分は(A)成分のゴム変性ポリスチ
レン100重量部当り3〜25重量部、好ましくは4〜15重
量部の割合で用いる。ここで(B)成分の配合割合が25
重量部を超えると、溶融粘度が高く成形が難しく、3重
量部未満であると、耐衝撃性が低くなり好ましくない。The component (B) as described above is used in a proportion of 3 to 25 parts by weight, preferably 4 to 15 parts by weight, per 100 parts by weight of the rubber-modified polystyrene of the component (A). Here, the mixing ratio of component (B) is 25
If it exceeds 5 parts by weight, the melt viscosity is high and molding is difficult.
本発明のゴム変性ポリスチレン樹脂組成物は上記の
(A)成分と(B)成分を常法により混練することによ
って製造することができる。なお、必要に応じて酸化防
止剤,離型剤,シリコンオイルなどの補助的成分を適宜
加えることができる。The rubber-modified polystyrene resin composition of the present invention can be produced by kneading the above-mentioned components (A) and (B) by a conventional method. In addition, if necessary, an auxiliary component such as an antioxidant, a release agent, and silicone oil can be added as appropriate.
次に、本発明を実施例により詳しく説明する。 Next, the present invention will be described in detail with reference to Examples.
製造例 本発明に使用するゴム変性ポリスチレンの製造を以下の
如く行った。4のステンレス製オートクレーブにスチ
レン92重量部,ポリブタジエン(旭化成(株)製、NF35
AS)8重量部および連鎖移動剤としてノルマルドデシル
メルカプタン250ppmを入れ、温度140℃,回転数500rpm
にて2時間反応させてスチレン転化率42重量%のプレポ
リマーを得た。Production Example A rubber-modified polystyrene used in the present invention was produced as follows. 92 parts by weight of styrene, polybutadiene (made by Asahi Kasei Corp., NF35)
AS) 8 parts by weight and 250 ppm of normal dodecyl mercaptan as a chain transfer agent are added, and the temperature is 140 ° C and the rotation speed is 500 rpm.
Was reacted for 2 hours to obtain a prepolymer having a styrene conversion of 42% by weight.
次いで、10のスチンレス製オートクレーブに前記で製
造したプレポリマーをプレポリマー/水相比を1/1で入
れ、またポリビニルアルコールを水相に対して0.25重量
%,ベンゾイルパーオキサイド2000ppm(プレポリマー
に対して),ジクミルパーオキサイド1000ppm(プレポ
リマーに対して)をそれぞれ加え、撹拌翼の回転数を50
0rpmとし、60℃から1時間当り20℃の割合で昇温し、14
0℃で3時間反応を行った。反応終了後、降温して水相
を分離後、ゴム変性ポリスチレンを得た。Then, the prepolymer prepared above was put into a 10 stainless steel autoclave at a prepolymer / water phase ratio of 1/1, and polyvinyl alcohol was added in an amount of 0.25% by weight based on the water phase and benzoyl peroxide 2000 ppm (based on the prepolymer). ), 1000 ppm of dicumyl peroxide (relative to the prepolymer) were added, and the rotation speed of the stirring blade was 50
At 0 rpm, the temperature is raised from 60 ℃ at a rate of 20 ℃ per hour, and
The reaction was carried out at 0 ° C for 3 hours. After the reaction was completed, the temperature was lowered and the aqueous phase was separated to obtain rubber-modified polystyrene.
このゴム変性ポリスチレン中の平均ゴム粒子径を電子顕
微鏡写真にて測定したところ0.9μであった(長径と短
径の平均を1000個測定した平均値)。The average rubber particle diameter in this rubber-modified polystyrene was measured by an electron microscope photograph and found to be 0.9 μ (the average value of 1000 averages of the major axis and the minor axis).
上記製造方法において連鎖移動剤の量,撹拌の回転数,
ゴム添加量を調整することにより、実施例,比較例で使
用した種々の平均ゴム粒子径,ゴム含有量を有するゴム
変性ポリスチレンを製造した。In the above manufacturing method, the amount of the chain transfer agent, the rotation speed of stirring,
By adjusting the amount of rubber added, rubber-modified polystyrene having various average rubber particle diameters and rubber contents used in Examples and Comparative Examples was produced.
実施例1 平均ゴム粒子径0.9μ,ゴム含有量8重量%を有するゴ
ム変性ポリスチレン100重量部に、メタクリル酸メチル
−ブタジエン−スチレン樹脂(MBS樹脂)〔鐘淵化学工
業(株)製、カネエースB56、平均粒径0.2μ〕5重量部
を配合し、単軸押出機にて180℃で混練して樹脂組成物
を得た。Example 1 100 parts by weight of rubber-modified polystyrene having an average rubber particle diameter of 0.9 μ and a rubber content of 8% by weight was mixed with methyl methacrylate-butadiene-styrene resin (MBS resin) [Kaneace B56 manufactured by Kanegafuchi Chemical Industry Co., Ltd.]. , Average particle size 0.2 μ] were mixed and kneaded at 180 ° C. with a single-screw extruder to obtain a resin composition.
得られた樹脂組成物を幅70mm×厚さ3mm×長さ270mmの成
形品に成形し、光沢測定および落錘強度試験を行った。
この結果を第1表に示す。実施例2〜9および比較例1
〜4 実施例1において、ゴム変性ポリスチレンにおける平均
ゴム粒子径およびゴム含有量を変化させ、かつMBS樹脂
の配合割合を第1表に示すように変えたこと以外は、実
施例1と同様にして樹脂組成物を得、この樹脂組成物を
同様に成形して試験をした。この結果を第1表に示す。The obtained resin composition was molded into a molded product having a width of 70 mm, a thickness of 3 mm and a length of 270 mm, and the gloss measurement and the falling weight strength test were performed.
The results are shown in Table 1. Examples 2-9 and Comparative Example 1
4 In the same manner as in Example 1 except that the average rubber particle diameter and the rubber content in the rubber-modified polystyrene were changed and the mixing ratio of the MBS resin was changed as shown in Table 1. A resin composition was obtained, and this resin composition was similarly molded and tested. The results are shown in Table 1.
〔発明の効果〕 本発明のゴム変性ポリスチレン樹脂組成物は光沢に優
れ、かつ耐衝撃性も優れたものである。 [Advantages of the Invention] The rubber-modified polystyrene resin composition of the present invention has excellent gloss and impact resistance.
したがって、本発明のゴム変性ポリスチレン樹脂組成物
は押出し成形,射出成形等により家電,OA機器ハウジン
グなどの分野において有用な製品の製造に幅広く利用さ
れる。Therefore, the rubber-modified polystyrene resin composition of the present invention is widely used in the production of products useful in the fields of home appliances, office equipment housings, etc. by extrusion molding, injection molding and the like.
Claims (1)
平均ゴム粒子径が0.5〜1.5μを有するゴム変性ポリスチ
レン100重量部に(B)(イ)メタクリル酸エステル単
量体および/またはアクリル酸エステル単量体,(ロ)
芳香族ビニル単量体および(ハ)ジエン単量体とからな
り、粒子径0.5μ以下である共重合体3〜25重量部を配
合することを特徴とするゴム変性ポリスチレン樹脂組成
物。1. A rubber content of (A) is 3 to 15% by weight,
(B) (a) methacrylic acid ester monomer and / or acrylic acid ester monomer, (b) in 100 parts by weight of rubber-modified polystyrene having an average rubber particle diameter of 0.5 to 1.5 μm
A rubber-modified polystyrene resin composition comprising 3 to 25 parts by weight of a copolymer comprising an aromatic vinyl monomer and a (c) diene monomer and having a particle diameter of 0.5 µ or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5304787A JPH0742381B2 (en) | 1987-03-10 | 1987-03-10 | Rubber modified polystyrene resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5304787A JPH0742381B2 (en) | 1987-03-10 | 1987-03-10 | Rubber modified polystyrene resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63221147A JPS63221147A (en) | 1988-09-14 |
JPH0742381B2 true JPH0742381B2 (en) | 1995-05-10 |
Family
ID=12931953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5304787A Expired - Fee Related JPH0742381B2 (en) | 1987-03-10 | 1987-03-10 | Rubber modified polystyrene resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0742381B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3974225B2 (en) * | 1997-07-07 | 2007-09-12 | 新日鐵化学株式会社 | Process for producing rubber-modified aromatic vinyl resin composition |
CN104619771A (en) * | 2012-09-13 | 2015-05-13 | 株式会社钟化 | Acrylic resin film |
-
1987
- 1987-03-10 JP JP5304787A patent/JPH0742381B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPS63221147A (en) | 1988-09-14 |
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