JPH05132605A - Rubber-modified polystyrene composition - Google Patents
Rubber-modified polystyrene compositionInfo
- Publication number
- JPH05132605A JPH05132605A JP3318484A JP31848491A JPH05132605A JP H05132605 A JPH05132605 A JP H05132605A JP 3318484 A JP3318484 A JP 3318484A JP 31848491 A JP31848491 A JP 31848491A JP H05132605 A JPH05132605 A JP H05132605A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- polymer particles
- matrix
- hips
- 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.)
- Withdrawn
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はゴム変成ポリスチレン
（ＨＩＰＳ）組成物に係り、詳しくは、衝撃強度特性と
表面光沢特性とがバランスよく優れたＨＩＰＳ組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-modified polystyrene (HIPS) composition, and more particularly to a HIPS composition having a good balance of impact strength characteristics and surface gloss characteristics.
【０００２】[0002]
【従来の技術】ＨＩＰＳは飲食用容器や家庭電気製品の
部品などに広く用いられている。しかし、一般的には、
ＡＢＳ樹脂に比べて、成形品の表面光沢や衝撃強度の点
で劣っているため用途が限られる場合がある。例えば、
従来から工業的に広く使用されているＨＩＰＳの大部分
はポリスチレンマトリックス中に分散しているゴム状重
合体粒子の平均粒径（ゴム粒径）が１〜５μｍ程度のも
のであり、成形品の衝撃強度は高いが、表面光沢があま
りよくない。一般に、ＨＩＰＳにおいてはゴム粒径が小
さいものほど表面光沢がよいという傾向があり、高光沢
ＨＩＰＳとしてゴム粒径が１μｍ以下のものも開発され
ているが衝撃強度が低いため、特定の用途にしか使用で
きない。2. Description of the Related Art HIPS is widely used for food and drink containers and parts of household electric appliances. But in general,
Compared with ABS resin, the surface gloss of the molded product and the impact strength are inferior, so the application may be limited. For example,
Most of the HIPS that have been widely used in the industry in the past have an average particle size (rubber particle size) of rubber-like polymer particles dispersed in a polystyrene matrix of about 1 to 5 μm. High impact strength, but poor surface gloss. Generally, in HIPS, the smaller the rubber particle size, the better the surface gloss, and the high-gloss HIPS with a rubber particle size of 1 μm or less has been developed. I can not use it.
【０００３】ところが、近年はコストダウン指向により
ＡＢＳ樹脂に近い特性を有するＨＩＰＳの開発が望まれ
ている。そこで、ゴム粒径の大きいＨＩＰＳと小さいＨ
ＩＰＳとを混合することにより衝撃強度特性及び表面光
沢特性が共に優れたＨＩＰＳ組成物を製造することが提
案されている（特開昭６３−１１２６４６号公報、特開
昭６３−２３０７５４号公報、特開平１−２６１４４４
号公報）。しかし、本発明者が種々の試験を行ったとこ
ろ、混合するＨＩＰＳのゴム粒径を特定するだけでは十
分な効果が得られないことが判った。However, in recent years, development of HIPS having characteristics close to those of ABS resin has been desired due to cost reduction. Therefore, HIPS with large rubber particle size and H with small rubber particle size
It has been proposed to produce a HIPS composition which is excellent in both impact strength characteristics and surface gloss characteristics by mixing with IPS (JP-A-63-112646, JP-A-63-230754, Kaihei 1-261444
Publication). However, as a result of various tests conducted by the present inventor, it was found that sufficient effects cannot be obtained only by specifying the rubber particle size of the HIPS to be mixed.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、衝撃
強度特性と表面光沢特性とがバランスよく優れたＨＩＰ
Ｓ組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a HIP having a good balance between impact strength characteristics and surface gloss characteristics.
An S composition is provided.
【０００５】[0005]
【発明を解決するための手段】本発明者は、上記のよう
な課題を解決するために研究を行った結果、マトリック
スの平均分子量がＨＩＰＳ組成物の衝撃強度特性と表面
光沢特性とのバランスの鍵となることを見出して本発明
を完成した。As a result of research conducted to solve the above problems, the present inventor found that the average molecular weight of the matrix is a balance between the impact strength characteristics and the surface gloss characteristics of the HIPS composition. The present invention has been completed by finding out that it is a key.
【０００６】すなわち、本発明は、重量平均分子量が２
０００００〜３０００００であるマトリックス中にカプ
セル構造をした平均粒径が０．１〜１μｍであるゴム状
重合体粒子とサラミ構造をした平均粒径が１．５〜３μ
ｍであるゴム状重合体粒子とが重量比４０：６０〜９
５：５の割合で分散し、ゴム状重合体に由来するブタジ
エン成分の含有量が３〜１０重量％であるゴム変成ポリ
スチレン組成物である。また、ポリスチレンマトリック
ス中にカプセル構造をした平均粒径が０．１〜１μｍで
あるゴム状重合体粒子が分散したゴム変成ポリスチレン
−Ａ、ポリスチレンマトリックス中にサラミ構造をした
平均粒径が１．５〜３μｍであるゴム状重合体粒子が分
散したゴム変成ポリスチレン−Ｂ及び重量平均分子量が
３０００００〜４０００００であるポリスチレンを配合
してなり、マトリックスの重量平均分子量が２００００
０〜３０００００、ゴム状重合体に由来するポリブタジ
エン成分の含有量が５〜１０重量％、カプセル構造をし
たゴム状重合体とサラミ構造をしたゴム状重合体との重
量比が４０：６０〜９５：５であるゴム変成ポリスチレ
ン組成物である。That is, the present invention has a weight average molecular weight of 2
Rubber-like polymer particles having an average particle size of 0.1 to 1 μm and having a capsule structure in a matrix of 00000 to 300,000, and an average particle size having a salami structure of 1.5 to 3 μ
The weight ratio of the rubber-like polymer particles of m is 40:60 to 9
The rubber-modified polystyrene composition is dispersed at a ratio of 5: 5 and the content of the butadiene component derived from the rubber-like polymer is 3 to 10% by weight. Further, rubber-modified polystyrene-A in which rubber-like polymer particles having a capsule-shaped average particle size of 0.1 to 1 μm are dispersed in a polystyrene matrix, and a salami-structured average particle size of 1.5 in the polystyrene matrix. The rubber-modified polystyrene-B in which rubber-like polymer particles having a particle size of ˜3 μm are dispersed and polystyrene having a weight average molecular weight of 300,000 to 400,000 are blended, and the matrix has a weight average molecular weight of 20,000.
0 to 300000, the content of the polybutadiene component derived from the rubbery polymer is 5 to 10% by weight, and the weight ratio of the rubbery polymer having a capsule structure and the rubbery polymer having a salami structure is 40:60 to 95. The rubber-modified polystyrene composition is 5:
【０００７】以下、本発明を詳細に説明する。本発明Ｈ
ＩＰＳ組成物は、マトリックス中にカプセル構造をした
ゴム状重合体粒子とサラミ構造をしたゴム状重合体粒子
とが分散している。マトリックスはスチレン系樹脂を主
成分とし、好ましくはポリスチレンである。マトリック
スの重量平均分子量は２０００００〜３０００００好ま
しくは２２００００〜２７００００更に好ましくは２４
００００〜２５００００である。また、カプセル構造を
したゴム状重合体粒子の平均粒径は０．１〜１μｍ好ま
しくは０．１〜０．６μｍ更に好ましくは０．２〜０．
４μｍである。サラミ構造をしたゴム状重合体粒子の平
均粒径は１．５〜３μｍ好ましくは２〜３μｍ更に好ま
しくは２．２〜２．７である。そして、カプセル構造を
したゴム状重合体粒子とサラミ構造をしたゴム状重合体
粒子との重量比は４０：６０〜９５：５好ましくは６
０：４０〜９０：１０更に好ましくは７０：３０〜８
０：２０であり、ゴム状重合体に由来するポリブタジエ
ン成分の含有量は５〜１０重量％である。The present invention will be described in detail below. Invention H
In the IPS composition, rubber-like polymer particles having a capsule structure and rubber-like polymer particles having a salami structure are dispersed in a matrix. The matrix is mainly composed of styrene resin, preferably polystyrene. The weight average molecular weight of the matrix is 200,000 to 300,000, preferably 220000 to 270000, and more preferably 24.
It is 0000 to 250,000. The average particle size of the rubber-like polymer particles having a capsule structure is 0.1 to 1 μm, preferably 0.1 to 0.6 μm, more preferably 0.2 to 0.
It is 4 μm. The average particle size of the rubber-like polymer particles having a salami structure is 1.5 to 3 μm, preferably 2 to 3 μm, and more preferably 2.2 to 2.7. The weight ratio of the rubber polymer particles having a capsule structure to the rubber polymer particles having a salami structure is 40:60 to 95: 5, preferably 6
0:40 to 90:10, more preferably 70:30 to 8
It is 0:20, and the content of the polybutadiene component derived from the rubber-like polymer is 5 to 10% by weight.
【０００８】このようなＨＩＰＳ組成物は、スチレンを
含む単量体に二種類のゴム状重合体を溶解してから、ス
チレン等の単量体を重合させることにより製造できる。
また、ポリスチレンマトリックス中に分散しているゴム
粒子の特性の異なる二種類のＨＩＰＳを混合する混合法
によっても製造できる。ただし、混合法の方がＨＩＰＳ
組成物の特性を調節しやすい。Such a HIPS composition can be produced by dissolving two kinds of rubber-like polymers in a monomer containing styrene and then polymerizing the monomer such as styrene.
It can also be produced by a mixing method in which two types of HIPS having different properties of rubber particles dispersed in a polystyrene matrix are mixed. However, the mixed method is more HIPS
Easy to control the properties of the composition.
【０００９】ゴム状重合体としては、ポリブタジエン、
ＳＢＲがあり、高粘度のゴム状重合体ほど、粒子径の大
きいゴム状重合体粒子を形成させやすい傾向がある。な
お、カプセル構造をしたゴム粒子を形成させるためには
低分子量のポリブタジエンのような低粘度のゴム状重合
体が適している。As the rubber-like polymer, polybutadiene,
A rubbery polymer having SBR and having a high viscosity tends to easily form rubbery polymer particles having a large particle size. A low-viscosity rubber-like polymer such as low-molecular-weight polybutadiene is suitable for forming rubber particles having a capsule structure.
【００１０】本発明のＨＩＰＳ組成物を製造するための
混合法の具体的なものとして、ポリスチレンマトリック
ス中にカプセル構造をしたゴム状重合体粒子が分散した
ＨＩＰＳ−Ａとポリスチレンマトリックス中にサラミ構
造をしたゴム状重合体粒子が分散したＨＩＰＳ−Ｂとの
組成物に、ゴム状重合体含有量及びマトリックスの重量
平均分子量を調節するために重量平均分子量が３０００
００〜４０００００であるポリスチレンを配合する方法
がある。このとき、ＨＩＰＳ−Ａとしてゴム粒径が０．
１〜１μｍ好ましくは０．１〜０．６μｍ更に０．２〜
０．４μｍのものを用い、ＨＩＰＳ−Ｂとしてゴム粒径
が１．５〜３μｍ好ましくは２〜３μｍ更に好ましくは
２．２〜２．７μｍのものを用いる。As a concrete example of the mixing method for producing the HIPS composition of the present invention, a salami structure is formed in HIPS-A in which a rubber-like polymer particle having a capsule structure is dispersed in a polystyrene matrix and in a polystyrene matrix. In the composition with HIPS-B in which the rubber-like polymer particles are dispersed, the weight-average molecular weight is 3000 in order to adjust the rubber-like polymer content and the weight-average molecular weight of the matrix.
There is a method of blending polystyrene of 0400 to 400000. At this time, the rubber particle size of HIPS-A is 0.
1-1 μm, preferably 0.1-0.6 μm, further 0.2-
The HIPS-B having a rubber particle size of 1.5 to 3 μm, preferably 2 to 3 μm, and more preferably 2.2 to 2.7 μm is used.
【００１１】なお、ＨＩＰＳのマトリックスの重量平均
分子量は、例えば、重合反応温度を調節して重合速度を
制御したり、塊状重合又は溶液重合によって製造する場
合は、多官能性の過酸化物開始剤を使用することによっ
て調節できる。The weight average molecular weight of the HIPS matrix is, for example, a polyfunctional peroxide initiator when the polymerization reaction temperature is controlled to control the polymerization rate, or when it is produced by bulk polymerization or solution polymerization. Can be adjusted by using.
【００１２】その他、本発明のＨＩＰＳ組成物の内、サ
ラミ構造をしたゴム粒子の膨潤比が、９〜１３のもの
は、表面光沢特性と衝撃強度特性とが共に優れている。
なお、膨潤比は、例えば、過酸化物開始剤を使用して塊
状重合又は溶液重合によって製造する場合は、その使用
量によって調節できる。また、重合液から未反応物等の
揮発性物質を除去してＨＩＰＳを回収する際の熱履歴の
かけかたを制御することにより調節できる。In addition, among the HIPS compositions of the present invention, rubber particles having a salami structure having a swelling ratio of 9 to 13 are excellent in both surface gloss characteristics and impact strength characteristics.
The swelling ratio can be adjusted depending on the amount used, for example, in the case of producing by bulk polymerization or solution polymerization using a peroxide initiator. In addition, it can be adjusted by removing the volatile substances such as unreacted substances from the polymerization liquid and controlling the way of applying the heat history when recovering HIPS.
【００１３】なお、ＨＩＰＳ組成物、ＨＩＰＳ−Ａ及び
ＨＩＰＳ−Ｂのゴム粒径の値は、超薄切片法により透過
型電子顕微鏡写真を撮影して、写真中のゴム粒子１００
０個の粒径を測定して式１により算出したものである。
ただし、式１中のＮｉは、粒径Ｄｉのゴム粒子の個数で
ある。 〔式１〕 ゴム粒径＝Σ〔（Ｎｉ・Ｄｉ4 ／（Ｎｉ・Ｄ
ｉ3）〕The values of the rubber particle diameters of the HIPS composition, HIPS-A and HIPS-B were taken by a transmission electron microscope photograph by the ultrathin section method, and the rubber particle 100 in the photograph was taken.
It is calculated by the equation 1 by measuring 0 particle diameters.
However, Ni in Formula 1 is the number of rubber particles having a particle diameter Di. [Formula 1] Rubber particle size = Σ [(Ni ・ Di 4 / (Ni ・ D
i 3 )]
【００１４】[0014]
【実施例】重量平均分子量が１９８０００のポリスチレ
ンマトリックス中にカプセル構造をした粒径が０．２μ
ｍであるブロックＳＢＲ粒子が１０重量％分散したＨＩ
ＰＳ−Ａと、重量平均平均分子量が１８６０００のポリ
スチレンマトリックス中にサラミ構造をした粒径が１．
６６μｍ、膨潤比が１２．５であるポリブタジエン粒子
が９．３重量％分散したＨＩＰＳ−Ｂとを、ＨＩＰＳ−
Ａに由来するブロックＳＢＲとＨＩＰＳ−Ｂに由来する
ポリブタジエンとの重量比が７５：２５になる割合で混
合した組成物に、必要に応じて重量平均分子量が３５０
０００のポリスチレン−Ｘ（ＧＰ−Ｘ）又は重量平均分
子量１８００００のポリスチレン−Ｙ（ＧＰ−Ｙ）を１
０〜５０重量％混合してポリブタジエンとブロックＳＢ
Ｒに由来するポリブタジエン成分との合計の含有量を３
〜７重量％に調節し、押出機で押し出してペレット化し
た。得られたペレットを用いて、射出成形により試験片
を作成して、アイゾット衝撃強度試験（ＡＳＴＭ−Ｄ−
６３８）及び光沢試験（ＡＳＴＭ−Ｄ−２５６）を行っ
た。EXAMPLE A polystyrene matrix having a weight average molecular weight of 198,000 and having a capsule structure and a particle size of 0.2 μm.
HI in which 10% by weight of block SBR particles of m are dispersed
PS-A and a polystyrene matrix having a weight average molecular weight of 186000 have a salami structure having a particle size of 1.
HIPS-B in which 9.3 wt% of polybutadiene particles having a swelling ratio of 12.5 and 66 μm were dispersed.
If necessary, the composition obtained by mixing the block SBR derived from A and the polybutadiene derived from HIPS-B in a weight ratio of 75:25 has a weight average molecular weight of 350.
000 polystyrene-X (GP-X) or polystyrene-Y (GP-Y) having a weight average molecular weight of 180,000 is 1
Mixing 0-50% by weight, polybutadiene and block SB
The total content with the polybutadiene component derived from R is 3
Adjusted to ~ 7 wt% and extruded with an extruder to pelletize. Using the obtained pellets, a test piece was prepared by injection molding, and the Izod impact strength test (ASTM-D-
638) and gloss test (ASTM-D-256).
【００１５】ＨＩＰＳ−Ｂのゴム粒径及びゴム粒子の膨
潤比とＨＩＰＳ組成物の光沢値及びアイゾット衝撃強度
を表１に示す。なお、膨潤比は以下の手順により求めた
値である。すなわち、１ｇの樹脂に３５ｍｌのトルエン
を加えて十分に溶解又は膨潤させた後、遠心分離機にて
ゲル成分を沈降させ、沈降したゲルをデカンテーション
で分離し秤量する。次に、このようにして得られたトル
エン膨潤ゲルを２００℃、常圧で１時間続いて減圧下で
１時間乾燥させ、デシケータ中で放冷後秤量する。そし
て、トルエン膨潤ゲルの重量を乾燥ゲルの重量で除した
値を膨潤比とした。表１に示した結果より、ポリスチレ
ンマトリックスの分子量が２０００００未満のものでは
ポリブタジエン成分含有量に対してアイゾット衝撃強度
が小さく衝撃強度特性が悪いことがわかる。Table 1 shows the rubber particle size of HIPS-B, the swelling ratio of the rubber particles, the gloss value of the HIPS composition, and the Izod impact strength. The swelling ratio is a value obtained by the following procedure. That is, 35 ml of toluene is added to 1 g of resin to sufficiently dissolve or swell it, and then the gel component is precipitated by a centrifuge, and the precipitated gel is separated by decantation and weighed. Next, the toluene swollen gel thus obtained is dried at 200 ° C. under normal pressure for 1 hour and then under reduced pressure for 1 hour, allowed to cool in a desiccator, and then weighed. The value obtained by dividing the weight of the toluene swollen gel by the weight of the dry gel was taken as the swelling ratio. From the results shown in Table 1, it can be seen that when the polystyrene matrix has a molecular weight of less than 200,000, the Izod impact strength is small and the impact strength characteristics are poor with respect to the polybutadiene component content.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明のＨＩＰＳ組成物は、衝撃強度特
性と表面光沢特性とが共に優れている。また、両者のバ
ランスがよい。The HIPS composition of the present invention is excellent in both impact strength characteristics and surface gloss characteristics. Also, the balance between the two is good.
Claims (2)
０００であるマトリックス中にカプセル構造をした平均
粒径が０．１〜１μｍであるゴム状重合体粒子とサラミ
構造をした平均粒径が１．５〜３μｍであるゴム状重合
体粒子とが重量比４０：６０〜９５：５の割合で分散
し、ゴム状重合体に由来するブタジエン成分の含有量が
３〜１０重量％であるゴム変成ポリスチレン組成物。1. A weight average molecular weight of 200,000 to 300.
Weight of the rubber-like polymer particles having an average particle size of 0.1 to 1 μm and having a salami structure and having an average particle size of 1.5 to 3 μm in a matrix of 000. A rubber-modified polystyrene composition which is dispersed at a ratio of 40:60 to 95: 5 and has a content of a butadiene component derived from a rubber-like polymer of 3 to 10% by weight.
構造をした平均粒径が０．１〜１μｍであるゴム状重合
体粒子が分散したゴム変成ポリスチレン−Ａ、ポリスチ
レンマトリックス中にサラミ構造をした平均粒径が１．
５〜３μｍであるゴム状重合体粒子が分散したゴム変成
ポリスチレン−Ｂ及び重量平均分子量が３０００００〜
４０００００であるポリスチレンを配合してなり、マト
リックスの重量平均分子量が２０００００〜３００００
０、ゴム状重合体に由来するポリブタジエン成分の含有
量が５〜１０重量％、カプセル構造をしたゴム状重合体
とサラミ構造をしたゴム状重合体との重量比が４０：６
０〜９５：５であるゴム変成ポリスチレン組成物。2. A rubber-modified polystyrene-A in which rubber-like polymer particles having a capsule structure and an average particle size of 0.1 to 1 μm are dispersed in a polystyrene matrix, and an average particle size having a salami structure in the polystyrene matrix is 1.
Rubber-modified polystyrene-B having rubber-like polymer particles of 5 to 3 μm dispersed therein and a weight average molecular weight of 300,000 to
The weight average molecular weight of the matrix is 200,000 to 30,000.
0, the content of the polybutadiene component derived from the rubber-like polymer is 5 to 10% by weight, and the weight ratio of the rubber-like polymer having a capsule structure and the rubber-like polymer having a salami structure is 40: 6.
A rubber-modified polystyrene composition having a ratio of 0 to 95: 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3318484A JPH05132605A (en) | 1991-11-06 | 1991-11-06 | Rubber-modified polystyrene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3318484A JPH05132605A (en) | 1991-11-06 | 1991-11-06 | Rubber-modified polystyrene composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05132605A true JPH05132605A (en) | 1993-05-28 |
Family
ID=18099637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3318484A Withdrawn JPH05132605A (en) | 1991-11-06 | 1991-11-06 | Rubber-modified polystyrene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05132605A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08199021A (en) * | 1995-01-26 | 1996-08-06 | Daicel Chem Ind Ltd | Rubber-modified styrene resin composition excellent in moldability |
| WO1999023157A1 (en) * | 1997-10-31 | 1999-05-14 | The Dow Chemical Company | Rubber modified monovinylidene aromatic polymer blends |
| US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
| US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
| US9061900B2 (en) | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
| US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
-
1991
- 1991-11-06 JP JP3318484A patent/JPH05132605A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08199021A (en) * | 1995-01-26 | 1996-08-06 | Daicel Chem Ind Ltd | Rubber-modified styrene resin composition excellent in moldability |
| WO1999023157A1 (en) * | 1997-10-31 | 1999-05-14 | The Dow Chemical Company | Rubber modified monovinylidene aromatic polymer blends |
| US6221471B1 (en) | 1997-10-31 | 2001-04-24 | The Dow Chemical Company | Rubber modified monovinylidene aromatic polymer blends |
| AU737796B2 (en) * | 1997-10-31 | 2001-08-30 | Dow Chemical Company, The | Rubber modified monovinylidene aromatic polymer blends |
| US9061900B2 (en) | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
| US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
| US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
| US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3906057A (en) | Compatible polymer alloys | |
| JPS6346106B2 (en) | ||
| US3907931A (en) | High impact two-component polystyrene blends | |
| JPH0468326B2 (en) | ||
| JP3612074B2 (en) | Composition comprising vinyl aromatic polymer and rubber and process for producing the same | |
| JPS6356895B2 (en) | ||
| JP3686681B2 (en) | Rubber-modified styrenic resin composition | |
| JPS6330948B2 (en) | ||
| JPH05132605A (en) | Rubber-modified polystyrene composition | |
| JP3201206B2 (en) | Rubber-modified styrenic resin composition and molded article thereof | |
| JP5607065B2 (en) | Rubber reinforced vinyl aromatic (co) polymer with optimal balance of physical / mechanical properties and high gloss | |
| JP2637176B2 (en) | Rubber-modified styrenic resin | |
| JPH0660273B2 (en) | Rubber modified polystyrene resin composition | |
| JP2655689B2 (en) | Rubber-modified styrenic resin | |
| JP3655374B2 (en) | Method for producing rubber-modified styrenic resin composition | |
| JPS5813650A (en) | Thermoplastic resin composition | |
| KR900002532B1 (en) | Polyblend of styrene/alpha-methyl styrene copolymers with interpolymerized styrene-grafted rubber concentrates | |
| JPS59193950A (en) | Delustered polycarbonate based resin composition | |
| JP2725330B2 (en) | Rubber modified styrenic resin composition | |
| JPH0318647B2 (en) | ||
| JPS58168650A (en) | Thermoplastic resin composition | |
| JPS5893711A (en) | Production of matted thermoplastic resin | |
| JP3411987B2 (en) | Rubber-modified styrenic resin composition | |
| JP3657370B2 (en) | Rubber-modified aromatic vinyl resin composition | |
| JPS63221147A (en) | Rubber-modified polystyrene resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990204 |