JP2725330B2 - Rubber modified styrenic resin composition - Google Patents
Rubber modified styrenic resin compositionInfo
- Publication number
- JP2725330B2 JP2725330B2 JP63314180A JP31418088A JP2725330B2 JP 2725330 B2 JP2725330 B2 JP 2725330B2 JP 63314180 A JP63314180 A JP 63314180A JP 31418088 A JP31418088 A JP 31418088A JP 2725330 B2 JP2725330 B2 JP 2725330B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- particle size
- soft component
- resin composition
- particle diameter
- 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
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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、衝撃強度、剛性、光沢のバランスが改良さ
れた耐衝撃性スチレン系樹脂組成物に関するものであ
る。Description: TECHNICAL FIELD The present invention relates to an impact-resistant styrene-based resin composition having an improved balance of impact strength, rigidity, and gloss.
さらに詳しくは、強靭化剤として使用するゴム状物質
の添加量、マトリックス中に分散したゴム状弾性体を含
有してなる軟質成分の粒子径分布と平均粒子径及び樹脂
マトリックスの極限粘度〔η〕を特定の範囲に調節する
ことにより、衝撃強度、剛性、光沢のバランスが優れた
耐衝撃性スチレン系樹脂組成物に関するものであり、該
樹脂組成物は、弱電機器、OA機器、事務機器などのハウ
ジング材等、広い分野において、使用可能である。More specifically, the amount of the rubber-like substance used as a toughening agent, the particle size distribution and average particle size of the soft component containing the rubber-like elastic material dispersed in the matrix, and the intrinsic viscosity of the resin matrix [η] By adjusting to a specific range, impact strength, rigidity, relates to an impact-resistant styrene-based resin composition having an excellent balance of gloss, the resin composition is a weak electric equipment, OA equipment, office equipment and the like It can be used in a wide range of fields such as housing materials.
＜従来の技術＞ 硬く脆いスチレン系樹脂の衝撃強度を改良するため
に、ゴム状物質とスチレン系重合体とをブレンドした
り、ゴム状物質をスチレン系単量体に溶解した後重合し
てゴム変性スチレン系樹脂組成物にすることはよく知ら
れている。<Prior art> In order to improve the impact strength of a hard and brittle styrene resin, a rubber-like substance is blended with a styrene-based polymer, or a rubber-like substance is dissolved in a styrene-based monomer and then polymerized. It is well known to make a modified styrene resin composition.
しかしながら、弱電機器、OA機器等のハウジング材と
して広く使われているABS樹脂と比較すると、衝撃強
度、剛性、光沢のバランスが見劣りする。However, the balance of impact strength, rigidity, and gloss is inferior to that of ABS resin, which is widely used as a housing material for light electrical appliances and OA appliances.
衝撃強度改良のためには、特開昭57−170949号、特開
昭57−172948号、特開昭57−187345号および特開昭61−
85461号公報等に記載されたように、有機ポリシロキサ
ンが添加されたり、特開昭49−354号、特開昭59−66412
号公報等に記載されたように、ポリフェニレンエーテ
ル、アクリロニトリルやα−メチルスチレンとの共重合
が試みられている。しかしながら、そのような衝撃強度
改良方法では、添加剤の購入や供給設備の設置、ポリフ
ェニレンエーテル、アクリロニトリルやα−メチルスチ
レン等の貯蔵の配合設備にコストがかかるという欠点が
生じる。In order to improve the impact strength, JP-A-57-170949, JP-A-57-172948, JP-A-57-187345, and JP-A-61-187345
As described in Japanese Patent No. 85461, an organic polysiloxane may be added, or JP-A-49-354 and JP-A-59-66412 may be used.
As described in Japanese Unexamined Patent Application Publication No. HEI 9-163, copolymerization with polyphenylene ether, acrylonitrile and α-methylstyrene has been attempted. However, such an impact strength improving method has a drawback in that it costs a lot to purchase and install additives, install equipment for supplying additives, and store equipment for storing polyphenylene ether, acrylonitrile, α-methylstyrene, and the like.
また、光沢を改良するためには、軟質成分の粒子径を
光の波長に相当する程度で小さくする必要があるが、小
さな粒子径の軟質成分を使用すると、衝撃強度が低くな
る。粒子径の小さな軟質成分を利用する場合は、一般に
添加量を増し、衝撃強度を高めることがなされるが、ゴ
ム状弾性体量が増えると剛性が低下するという欠点が生
じる。Further, in order to improve the gloss, it is necessary to reduce the particle size of the soft component to an extent corresponding to the wavelength of light. However, when a soft component having a small particle size is used, the impact strength is reduced. When a soft component having a small particle size is used, the amount of addition is generally increased to increase the impact strength. However, when the amount of the rubber-like elastic body increases, the rigidity decreases.
＜発明が解決しようとする課題＞ 本発明者らは、衝撃強度改良剤の添加やスチレン系単
量体と共重合可能な単量体を重合させて連続相を形成さ
せるという手段をとらずに、ゴム状物質の添加量、軟質
成分の粒子径分布と平均粒子径及び樹脂マトリックスの
極限粘度〔η〕を特定の範囲に調節することによって衝
撃強度、剛性、光沢のバランスの優れたゴム変性スチレ
ン系樹脂組成物を得ることを目的とした。<Problems to be Solved by the Invention> The inventors of the present invention have taken measures of adding an impact strength improver and polymerizing a monomer copolymerizable with a styrene monomer to form a continuous phase. , Rubber-modified styrene with excellent balance of impact strength, rigidity and gloss by adjusting the addition amount of rubber-like substance, particle size distribution and average particle size of soft component and intrinsic viscosity [η] of resin matrix to specific ranges The purpose was to obtain a resin composition.
＜課題を解決するための手段＞ すなわち本発明は、 スチレン系樹脂がマトリックスを形成し、ゴム状弾性
体を含有してなる軟質成分が粒子状に分散しているゴム
変性スチレン系樹脂組成物において、 （ａ）該組成物中に分散した軟質成分の粒子径分布が二
峰性であり、 （ｂ）軟質成分の一峰（粒子径の小さい方）の極大粒子
径をD1、他峰（粒子径の大きい方）の極大粒子径をD2と
した場合、 D1≦0.8μ、D2＞0.8μ、10≦D2/D1≦30 の関係を満足し、 （ｃ）軟質成分の平均粒子径が2.6μ以下の範囲にあ
り、 （ｄ）ゴム状弾性体の含有量が4.0wt％以上7.5wt％以下
であり、かつ、 （ｅ）樹脂マトリックスの極限粘度〔η〕が0.70以上で
あることを特徴とする衝撃強度、剛性、光沢のバランス
が著しく改良されたゴム変性スチレン系樹脂組成物に関
するものである。<Means for Solving the Problems> That is, the present invention relates to a rubber-modified styrene-based resin composition in which a styrene-based resin forms a matrix and a soft component containing a rubber-like elastic material is dispersed in particles. (A) the particle size distribution of the soft component dispersed in the composition is bimodal, (b) the maximum particle size of one peak (the smaller particle size) of the soft component is D 1 , and the other peak (particle If the maximum particle size of the larger) diameter was D 2, D 1 ≦ 0.8μ, D 2> 0.8μ, satisfy the 10 ≦ D 2 / D 1 ≦ 30 relationship, the average of (c) the soft component (D) the rubber-like elastic body content is 4.0 wt% or more and 7.5 wt% or less, and (e) the intrinsic viscosity [η] of the resin matrix is 0.70 or more. A rubber-modified styrenic resin composition having a markedly improved balance of impact strength, rigidity, and gloss. It is intended.
本発明の目的を達成するためには、上記のごとく、ゴ
ム状弾性体の添加量、軟質成分の粒子径分布と平均粒子
径及び樹脂マトリックスの極限粘度〔η〕をそれぞれ特
定することが必要であり、これらの要件のうちどの１つ
が欠けても本発明の目的は達成できない。In order to achieve the object of the present invention, it is necessary to specify the addition amount of the rubber-like elastic body, the particle diameter distribution and the average particle diameter of the soft component, and the intrinsic viscosity [η] of the resin matrix, respectively, as described above. Yes, the lack of any one of these requirements will not achieve the objectives of the present invention.
以下さらに詳しく説明する。 The details will be described below.
本発明に用いるゴム変性スチレン系樹脂組成物は、ゴ
ム状物質を芳香族モノビニル単量体に溶解した後、塊状
重合法又は塊状−懸濁二段重合法によって製造される。The rubber-modified styrenic resin composition used in the present invention is produced by dissolving a rubber-like substance in an aromatic monovinyl monomer and then performing a bulk polymerization method or a bulk-suspension two-stage polymerization method.
芳香族モノビニル単量体としては、スチレンが一般的
ではあるが、α−メチルスチレン、ｍ−メチルスチレ
ン、ｐ−メチルスチレン等のアルキル置換スチレンも利
用できる。Styrene is generally used as the aromatic monovinyl monomer, but alkyl-substituted styrenes such as α-methylstyrene, m-methylstyrene and p-methylstyrene can also be used.
またゴム状物質としては、ポリブタジエン、スチレン
−ブタジエン共重合体類、エチレン−プロピレン系共重
合体類、エチレン−プロピレン−非共役ジエンの三元共
重合体類、イソプレン重合体類、スチレン−イソプレン
共重合体類が使われるがその中でもポリブタジエンが最
も好ましく用いられる。Examples of the rubbery substance include polybutadiene, styrene-butadiene copolymers, ethylene-propylene-based copolymers, terpolymers of ethylene-propylene-nonconjugated dienes, isoprene polymers, and styrene-isoprene copolymers. Polymers are used, and among them, polybutadiene is most preferably used.
ポリブタジエンはシス含有率の高低に関係なく用いる
ことができる。Polybutadiene can be used regardless of the cis content.
製造されたゴム変性スチレン系樹脂組成物は、軟質成
分が粒子状に分散しており、（ａ）その粒子径分布は二
峰性を示していることが必要である。In the manufactured rubber-modified styrene resin composition, the soft component is dispersed in the form of particles, and (a) it is necessary that the particle size distribution is bimodal.
そして、（ｂ）粒子径の小さい一峰の極大粒子径を
D1、他峰（粒子径の大きい方）の極大粒子径をD2とした
場合、 D1≦0.8μ、D2＞0.8μ、10≦D2/D1≦30 の関係を満足することが必要である。Then, (b) the one-peak maximum particle diameter having a small particle diameter
D 1 , when the maximum particle size of the other peak (larger particle size) is D 2 , satisfy the following relationships: D 1 ≦ 0.8 μ, D 2 > 0.8 μ, and 10 ≦ D 2 / D 1 ≦ 30 is required.
D1が0.8μを越える場合には、光沢が低下し、D2が0.8
μ以下の場合には、衝撃強度の改良効果が低下する。さ
らにD2/D1＜10またはD2/D1＞30の場合には、衝撃強度の
改良効果は、発現しないか、又は、小さなものとなる。If the D 1 exceeds 0.8μ are gloss decreases, D 2 is 0.8
In the case of μ or less, the effect of improving the impact strength decreases. Further, when D 2 / D 1 <10 or D 2 / D 1 > 30, the effect of improving the impact strength is not exhibited or is small.
また、（ｃ）軟質成分の平均粒子径は2.6μ以下の範
囲、好ましくは0.2〜2.0μの範囲にあることが必要であ
り、平均粒子径が2.6μを越えると衝撃強度の改良効果
は小さなものとなり、また、光沢も著しく低下する。Further, (c) the average particle size of the soft component needs to be in the range of 2.6 μm or less, preferably in the range of 0.2 to 2.0 μ. If the average particle size exceeds 2.6 μ, the effect of improving the impact strength is small. And the gloss is significantly reduced.
ここで云う粒子径分布と平均粒子径は、ゴム変性スチ
レン系樹脂の超薄切片の透過型電子顕微鏡写真をとり、
写真上の軟質成分粒子500個の粒子径を測定して求めた
ものである。The particle size distribution and average particle size referred to here are taken with a transmission electron micrograph of an ultra-thin section of rubber-modified styrene resin,
It is obtained by measuring the particle diameter of 500 soft component particles on the photograph.
平均粒子径は、次式によって計算する。 The average particle size is calculated by the following equation.
ここで云うn1は粒子径D1のゴム状弾性体粒子の個数で
ある。 Here, n 1 is the number of rubber-like elastic particles having a particle diameter D 1 .
粒子径分布及び平均粒子径は、コールターカウンター
の如き分析装置を用いて測定しても良いが、その時に
は、電子顕微鏡写真による測定値との差を考慮しなけれ
ばならない。The particle size distribution and the average particle size may be measured using an analyzer such as a Coulter counter, but at that time, the difference from the measured value by an electron micrograph must be considered.
また、（ｄ）ゴム状物質の含有量は、4.0wt％以上、
7.5wt％以下、好ましくは4.5wt％以上7.0wt％以下にし
なければならない。(D) The content of the rubber-like substance is 4.0 wt% or more,
It must be not more than 7.5 wt%, preferably not less than 4.5 wt% and not more than 7.0 wt%.
ゴム状物質の含有量が、4.0wt％未満の場合は衝撃強
度が低下し、7.5wt％を越えると剛性が低下し、また光
沢も低下するため好ましくない。If the content of the rubber-like substance is less than 4.0% by weight, the impact strength is reduced, and if it exceeds 7.5% by weight, the rigidity is reduced and the gloss is also reduced.
さらに、（ｅ）樹脂マトリックスの極限粘度〔η〕が
0.70以上であることが必要である。〔η〕が0.70未満の
場合もまた剛性が低下し好ましくない。Furthermore, (e) the intrinsic viscosity [η] of the resin matrix is
It must be at least 0.70. When [η] is less than 0.70, the rigidity also decreases, which is not preferable.
ここで云う樹脂マトリックスの極限粘度〔η〕は、樹
脂成分0.5grをメチルエチルケトン／メタノール＝10/1
溶液50mlに溶解し、遠心分離によって不溶ゲル分を沈澱
させた後、上澄液をメタノール１に移し、樹脂成分を
再沈澱させて、ロ過後、乾燥した沈澱物100mgを精秤
し、30mlのトルエンに溶解し、30℃の温度でウベローデ
型毛管粘度計を使って測定した値である。The limiting viscosity [η] of the resin matrix referred to here is such that 0.5 gr of the resin component is methyl ethyl ketone / methanol = 10/1.
After dissolving in 50 ml of the solution and precipitating an insoluble gel by centrifugation, the supernatant was transferred to methanol 1 to reprecipitate the resin component. After filtration, 100 mg of the dried precipitate was precisely weighed, and 30 ml of It is a value measured by dissolving in toluene and using a Ubbelohde capillary viscometer at a temperature of 30 ° C.
本発明において、特定された軟質成分の粒子径分布と
平均粒子径及び樹脂マトリックスの極限粘度〔η〕は、
重合工程における撹拌強度、重合温度、重合時間、重合
開始剤や連鎖移動剤の量を加減することや重合の進んだ
重合液の一部を原料単量体にフィードバックしたり、あ
るいは重合度の異なる重合液を所定量抜きとって混合し
た後、重合を完成させる等の方法により調節することが
できる。In the present invention, the intrinsic viscosity (η) of the particle size distribution and the average particle size of the specified soft component and the resin matrix,
Stirring strength in the polymerization process, polymerization temperature, polymerization time, adjust the amount of polymerization initiator and chain transfer agent, and feed back a part of the polymerization solution with advanced polymerization to the raw material monomer, or different polymerization degree After a predetermined amount of the polymerization liquid is taken out and mixed, it can be adjusted by a method such as completing the polymerization.
また、簡易的には、ゴム状物質の含有量、軟質成分の
平均粒子径と粒子径分布及び樹脂マトリックスの〔η〕
が異なる二種以上のゴム変性スチレン系樹脂またはスチ
レン系樹脂を所定量混合することにより、本発明で特定
したゴム状物質の含有量、軟質成分の粒子径分布と平均
粒子径及び樹脂マトリックスの極限粘度〔η〕を持つ樹
脂組成物を得ることもできる。In addition, simply, the content of the rubber-like substance, the average particle size and particle size distribution of the soft component and [η] of the resin matrix
By mixing a predetermined amount of two or more types of rubber-modified styrene-based resins or styrene-based resins different from each other, the content of the rubbery substance specified in the present invention, the particle size distribution and the average particle size of the soft component and the limit of the resin matrix are limited. A resin composition having a viscosity [η] can also be obtained.
＜実施例＞ 以下の実施例及び比較例は、表−１に示すＡ〜Ｇのゴ
ム変性ポリスチレンを表−２の割合にブレンドして物性
値を測定し、その結果を表−３に示した。<Examples> In the following Examples and Comparative Examples, physical properties were measured by blending the rubber-modified polystyrenes A to G shown in Table 1 in proportions shown in Table 2, and the results were shown in Table 3. .
ただし、本発明は、これらの実施例に限定されるもの
ではない。However, the present invention is not limited to these examples.
＜発明の効果＞ 以上説明したように、本発明の樹脂組成物は、衝撃強
度、剛性、光沢のバランスが良く、これまでABS樹脂が
使用されてきた弱電機器、OA機器、事務機器のハウジン
グ材等にABS樹脂の代替品として使用でき、コストダウ
ンにかかわる経済的価値は、きわめて大であると云え
る。<Effects of the Invention> As described above, the resin composition of the present invention has a good balance of impact strength, rigidity, and gloss, and is a housing material of light electric equipment, OA equipment, and office equipment in which ABS resin has been used so far. It can be used as a substitute for ABS resin, etc., and the economic value related to cost reduction is extremely large.
Claims (1)
ゴム状弾性体を含有してなる軟質成分が粒子状に分散し
ているゴム変性スチレン系樹脂組成物において、 （ａ）該組成物中に分散した軟質成分の粒子径分布が二
峰性であり、 （ｂ）軟質成分の一峰（粒子径の小さい方）の極大粒子
径をD1、他峰（粒子径の大きい方）の極大粒子径をD2と
した場合、 D1≦0.8μ、D2＞0.8μ、10≦D2/D1≦30 の関係を満足し、 （ｃ）軟質成分の平均粒子径が2.6μ以下の範囲にあ
り、 （ｄ）ゴム状弾性体の含有量が4.0wt％以上7.5wt％以下
であり、かつ、 （ｅ）樹脂マトリックスの極限粘度〔η〕が0.70以上で
あることを特徴とするゴム変性スチレン系樹脂組成物。1. A styrene resin forms a matrix,
In a rubber-modified styrenic resin composition in which a soft component containing a rubber-like elastic material is dispersed in the form of particles, (a) the particle size distribution of the soft component dispersed in the composition is bimodal. (B) When the maximum particle diameter of one peak (smaller particle diameter) of the soft component is D 1 and the maximum particle diameter of the other peak (larger particle diameter) is D 2 , D 1 ≦ 0.8 μ, D 2 > 0.8 μ, 10 ≦ D 2 / D 1 ≦ 30, (c) the average particle diameter of the soft component is in the range of 2.6 μ or less, and (d) the content of the rubber-like elastic body is 4.0 (e) a limiting viscosity [η] of the resin matrix is 0.70 or more;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63314180A JP2725330B2 (en) | 1988-01-29 | 1988-12-12 | Rubber modified styrenic resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2090488 | 1988-01-29 | ||
| JP63-20904 | 1988-01-29 | ||
| JP63314180A JP2725330B2 (en) | 1988-01-29 | 1988-12-12 | Rubber modified styrenic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01279945A JPH01279945A (en) | 1989-11-10 |
| JP2725330B2 true JP2725330B2 (en) | 1998-03-11 |
Family
ID=26357905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63314180A Expired - Lifetime JP2725330B2 (en) | 1988-01-29 | 1988-12-12 | Rubber modified styrenic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2725330B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| ITMI20042401A1 (en) | 2004-12-16 | 2005-03-16 | Polimeri Europa Spa | PROCEDURE FOR THE PREPARATION OF VINYLAROMATIC SEALED SHOCKFORM CO-POLYMERS ON ELASTOMER |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1518412A (en) * | 1975-05-15 | 1978-07-19 | Labofina Sa | High-impact polystyrene and process for the production thereof |
-
1988
- 1988-12-12 JP JP63314180A patent/JP2725330B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01279945A (en) | 1989-11-10 |
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