JPS612715A - Rubber-reinforced resin with high impact resistance - Google Patents
Rubber-reinforced resin with high impact resistanceInfo
- Publication number
- JPS612715A JPS612715A JP12434284A JP12434284A JPS612715A JP S612715 A JPS612715 A JP S612715A JP 12434284 A JP12434284 A JP 12434284A JP 12434284 A JP12434284 A JP 12434284A JP S612715 A JPS612715 A JP S612715A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- ethylene
- resin
- olefin
- impact resistance
- 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
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】 ■ 発明の目的 〔産業上の利用分野〕 本発明は、耐衝撃性に優nるゴム強化樹脂に関する。[Detailed description of the invention] ■ Purpose of the invention [Industrial application field] The present invention relates to a rubber reinforced resin with excellent impact resistance.
従来より耐衝撃性ポリスチレン(HIPS)、ABS樹
脂などに見ら扛るとおり、樹脂の機械的特性、特に耐衝
撃性を改善するために樹脂中にゴムを導入する技術が用
いられている。父、近年、非共役ジエン系ゴムがボリブ
クジェンなどの共役ジエン系ゴムに比べ耐候性に優nる
ことより、ゴム成分として非共役ジエン系ゴムを用いた
耐衝撃性耐候性樹脂、たとえばABS樹脂、AC8樹脂
、AAS樹脂が注目さnている。BACKGROUND ART Conventionally, as seen in high impact polystyrene (HIPS), ABS resins, etc., techniques have been used to introduce rubber into resins in order to improve the mechanical properties of resins, particularly impact resistance. In recent years, since non-conjugated diene rubber has better weather resistance than conjugated diene rubber such as borobukudene, impact-resistant and weather-resistant resins using non-conjugated diene rubber as the rubber component, such as ABS resin, have been developed. AC8 resin and AAS resin are attracting attention.
一般的VCはゴム含有量の増加にともない耐衝撃性に向
上するが、その反面加工性及び剛性の著しい低下ならび
に外観不良をもたらす。General VC improves impact resistance as the rubber content increases, but on the other hand, it causes a significant decrease in processability and rigidity, as well as poor appearance.
本発明が解決した問題点とは、エチレン−αオレフィン
系ゴムを用いてなるゴム強化樹脂の耐衝撃性である。The problem solved by the present invention is the impact resistance of a rubber reinforced resin made of ethylene-α olefin rubber.
■ 発明の構成
本発明者らは、上述のゴム強化樹脂における問題点に鑑
み鋭意研究した結果、ゴム強化樹脂のグラフト重合体の
テトラヒドロフラン−n −ヘキサン混合溶剤による可
溶分を低く抑えたゴム強化樹脂が従来のゴム強化樹脂に
比較し、耐衝撃性に優nること全見出し、本発明に到達
したものである。■ Structure of the Invention As a result of intensive research in view of the above-mentioned problems with rubber-reinforced resins, the present inventors have developed a rubber-reinforced graft polymer of rubber-reinforced resin in which the soluble content of a tetrahydrofuran-n-hexane mixed solvent is kept low. The present invention was based on the discovery that the resin has superior impact resistance compared to conventional rubber-reinforced resins.
すなわち、本発明は、エチレン−αオレフィン系ゴムに
芳香族ビニル単量体、シアン化ビニル単量体および不飽
和カルボン酸アルキルエステルからなる群より選択さf
′Lタ一種以上の単量体がグラフト重合してなり、かつ
、グラフト重合体ノテトラヒドロフランーn−ヘキサン
混合溶剤(容積比1:4)Kよる可溶分が4ON量係以
下である耐衝撃性および加工性に優扛るゴム強化樹脂を
提供するものである。That is, the present invention provides an ethylene-α olefin rubber containing f selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and an unsaturated carboxylic acid alkyl ester.
Impact resistant, which is obtained by graft polymerization of one or more monomers, and in which the soluble content of the graft polymer in a mixed solvent of notetrahydrofuran and n-hexane (volume ratio 1:4) is 4ON or less. The present invention provides a rubber-reinforced resin with excellent properties and processability.
0エチレン−αオレフィン系ゴム
本発明におけるエチレン−αオレフィン系ゴムトハ、エ
チレンとプロピレン又はブテンからなる二元共重合体(
EPR)、エチレン、プロピレン又はブテンおよび非共
役ジエンからなる三元共重合体(EPDM)などであり
、一種棟fcは二種以上用いらnる。0 Ethylene-α olefin rubber The ethylene-α olefin rubber in the present invention is a binary copolymer consisting of ethylene and propylene or butene (
EPR), terpolymer (EPDM) consisting of ethylene, propylene or butene and non-conjugated diene, etc., and two or more types of fc are used.
三元共重合体(EPDM)Kおける非共役ジエンとして
は、シンクロペンタジェン、エチリデンノルボルネン、
14−へキサジエン、14−シクロオクタジエン、15
−シクロオクタジエン等が挙けらnる。Non-conjugated dienes in the terpolymer (EPDM) K include synchlopentadiene, ethylidene norbornene,
14-hexadiene, 14-cyclooctadiene, 15
-cyclooctadiene and the like.
二元共重合体(EPR)および三元共重合体(EPDM
)VCおけるエチレンとプロピレン又はブテンのモル比
は5:1から1=3の範囲であることが好櫨しい。Binary copolymers (EPR) and terpolymers (EPDM)
) The molar ratio of ethylene to propylene or butene in the VC is preferably in the range of 5:1 to 1=3.
また、三元共重合体(EPDM)においては非共役ジエ
ンの割合がヨウ素価に換算して2〜50の範囲のものが
好ましい。Further, in the terpolymer (EPDM), it is preferable that the proportion of non-conjugated diene is in the range of 2 to 50 in terms of iodine value.
0単 量 体
また、芳香族ビニル単量体としては、スチレン、α−メ
チルスチレン、ビニルトルエン、メチル−α−メチルス
チレンなどが挙げらnる。Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, and methyl-α-methylstyrene.
シアン化ビニル単量体としてはアクリロニトリル、メタ
クリレートリルなどが挙げらnる。不飽和カルボン酸ア
ルキルエステル単童体としては、メチルアクリレート、
エチルアクリレート、ブチルアクリレート、メチルメタ
クリレート、エチルメタクリレート、ブチルメタクリレ
ート、ヒドロキシエチルアクリレート、ヒドロキシエチ
ルメタクリレート、ヒドロキシエチルアクリレート、更
に、分子中にエポキシ基を有するクリシジルアクリレー
ト、クリシジルメタクリレートなどが挙げら扛る。Examples of vinyl cyanide monomers include acrylonitrile and methacrylate trile. Examples of unsaturated carboxylic acid alkyl esters include methyl acrylate,
Examples include ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, as well as chrycidyl acrylate and chrysidyl methacrylate having an epoxy group in the molecule.
上述の化合物から選択された一種以上の単量体カエチレ
ンーα−オレフィン系ゴムト共K1M脂を構成する。特
にスチレン、アクリロニトリル、メチルメタクリレート
の一種または二種以上が好ましい。One or more monomers selected from the above-mentioned compounds constitute the K1M resin together with a monomeric ethylene-α-olefin rubber. Particularly preferred is one or more of styrene, acrylonitrile, and methyl methacrylate.
ゴム強化樹脂におけるエチレン−αオレフィン系ゴムと
単量体との構成比にも特に制限はないが樹脂の物性面よ
りエチレン−αオレフィン系ゴム5〜95重量%、単量
体95〜5重量%であることが好ましく、特にエチレン
−αオレフィン系ゴム10〜60重量%、単量体90〜
40重量%であることが好ましい。There is no particular restriction on the composition ratio of ethylene-α olefin rubber and monomer in the rubber reinforced resin, but from the physical properties of the resin, ethylene-α olefin rubber 5 to 95% by weight and monomer 95 to 5% by weight. It is preferable that the ethylene-α olefin rubber is 10 to 60% by weight, and the monomer is 90 to 60% by weight.
Preferably it is 40% by weight.
本発明のゴム強化樹脂のクラフト重合体のテトラヒドロ
フラン−〇−ヘキサン混合溶剤(容積比l:4)による
可溶分は40重量係以下である。The soluble content of the kraft polymer of the rubber reinforced resin of the present invention in a tetrahydrofuran-〇-hexane mixed solvent (volume ratio 1:4) is 40% by weight or less.
可溶分が40重量%を超えると加工性が向」ニする反面
、耐衝撃性の低下が著しく好1しくない。耐衝撃性およ
び加工性のバランス面より可溶分が10〜4ON量係で
あることが奸才しく、特I/rC20〜40重量係であ
ることが好ましい。If the soluble content exceeds 40% by weight, processability is improved, but impact resistance is significantly lowered, which is undesirable. In view of the balance between impact resistance and workability, it is advisable for the soluble content to be in the range of 10 to 4 ON, and especially I/rC is preferably in the range of 20 to 40 by weight.
本発明におけるクラフト重合体中の可溶分とは次の条件
下で測定さt′Lだ値を意味する。The soluble content in the kraft polymer in the present invention means the t'L value measured under the following conditions.
ゴム強化樹脂を約100倍量のMEK(メチルエチルケ
トン)K24時間、室温にて浸漬後、遠心分離(12,
OOORPM、20分間)でMEK可溶分と不溶分に分
離し、不溶分(グラフト重合体)を得る。The rubber reinforced resin was immersed in about 100 times the amount of MEK (methyl ethyl ketone) at room temperature for 24 hours, and then centrifuged (12,
OOORPM for 20 minutes) to separate MEK into soluble and insoluble components to obtain an insoluble component (graft polymer).
得ら扛たグラフト重合体を熱プレス(200℃。The obtained graft polymer was heat pressed (200°C).
5分間)Kよって1日厚程度のシートを作成する。クラ
フト重合体シート1ノをテトラヒドロフラン−n−へキ
サン混合溶剤(容積比1 :4)200m/に48時間
、室温にて浸漬後、300メツシユにて口過させゲル分
より可溶分を算出する。5 minutes) Create a sheet with a thickness of about 1 day. One kraft polymer sheet was immersed in 200 m/200 m of tetrahydrofuran-n-hexane mixed solvent (volume ratio 1:4) for 48 hours at room temperature, passed through a 300-mesh mesh, and the soluble content was calculated from the gel content. .
ゴム強化樹脂の重合法としては、従来より公知の乳化重
合法、懸濁重合法、塊状重合法、溶液重合法などが挙げ
らnる。Examples of polymerization methods for rubber-reinforced resins include conventionally known emulsion polymerization methods, suspension polymerization methods, bulk polymerization methods, and solution polymerization methods.
なお、本発明の可溶分が40重量係以下であの変更、開
始剤又は分子量調節剤の種類および利用量の変更、重合
温度の変更などが挙けられる0
本発明のゴム強化樹脂は必要に応じて染顔料、酸化防止
剤、可塑剤、帯電防止剤、紫外線吸収剤、滑剤、充填剤
等の公知の添加剤はもちろんのこと、アクリロニトリル
−スチレン共重合体、スチレン−無水マレイン酸共重合
体、スチレン−メチルメタクリレート共重合体、ポリメ
チルメタクリレート、ポリカーボネートなど他の熱可塑
性樹脂を配合することもできる。In addition, if the soluble content of the present invention is 40% by weight or less, such changes, changes in the type and amount of the initiator or molecular weight regulator, changes in the polymerization temperature, etc. may be made. Depending on the situation, we can add not only known additives such as dyes and pigments, antioxidants, plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, etc., but also acrylonitrile-styrene copolymers, styrene-maleic anhydride copolymers. Other thermoplastic resins such as , styrene-methyl methacrylate copolymer, polymethyl methacrylate, and polycarbonate can also be blended.
実施例をあげて本発明を説明するが、本発明は実施例に
よって何ら限定さnるものではない。The present invention will be explained with reference to Examples, but the present invention is not limited to the Examples in any way.
実 施 例
エチレン−αオレフィン系共重合体50重量部、スチレ
ン34重量部およびアクリロニトリル16重量部を公知
の懸濁重合法に基づきクラフト重合金行った。EXAMPLE A kraft polymer was prepared using a known suspension polymerization method using 50 parts by weight of an ethylene-α olefin copolymer, 34 parts by weight of styrene, and 16 parts by weight of acrylonitrile.
なお、重合においてはムーニー粘度の異なる共重合体の
利用、開始剤の利用量の変更ならびに重合温度の変更に
より可溶分の異なるグラフト重合体を得た。In the polymerization, graft polymers with different soluble contents were obtained by using copolymers with different Mooney viscosities, changing the amount of initiator used, and changing the polymerization temperature.
マタ、エチレン−αオレフィン系共重合体20重量部、
スチレン60重量部およびアクリロニトリル20重量部
を公知の溶液重合法に基づきグラフト重合を行った。Mata, 20 parts by weight of ethylene-α-olefin copolymer,
Graft polymerization was carried out using 60 parts by weight of styrene and 20 parts by weight of acrylonitrile based on a known solution polymerization method.
なお、重合においては、ムーニー粘度の異なる共重合体
の利用により可溶分の異なるクラフト重合体を得た。In addition, in the polymerization, kraft polymers with different soluble contents were obtained by using copolymers with different Mooney viscosities.
グラフト重合処方と重合結果を表−1に示す。The graft polymerization recipe and polymerization results are shown in Table 1.
得ら′t′したグラフト重合体と別途製造されたスチレ
ン−アクリロニトリル共重合体(70/30)とを混合
し、ゴム含有量22重量%の組成物を得たO
得らnた組成物を用いて射出成形し、衝撃強度ならびに
加工性を評価した。The obtained graft polymer was mixed with a separately produced styrene-acrylonitrile copolymer (70/30) to obtain a composition with a rubber content of 22% by weight. The impact strength and processability were evaluated.
評価結果を表−1に示す。The evaluation results are shown in Table-1.
一成形条件一
8精樹脂製射出成形機FS−75(3,5オンス)成形
温度 : 240℃
金型温度 二 60℃
1 発明の効果
エチレン−αオレフィン系ゴムを用いてなるゴム強化樹
脂のグラフト重合体のテトラヒドロフラン−n−ヘキサ
ン混合溶剤による可溶分が40重量係以下であnば、優
1f”した耐衝撃性を有する。1. Molding conditions 1. 8-precision resin injection molding machine FS-75 (3.5 oz.) Molding temperature: 240°C Mold temperature 2. 60°C 1. Effects of the invention Grafting of rubber reinforced resin using ethylene-α olefin rubber If the soluble content of the polymer in the tetrahydrofuran-n-hexane mixed solvent is 40% by weight or less, it has impact resistance of excellent 1f''.
Claims (1)
体、シアン化ビニル単量体および不飽和カルボン酸アル
キルエステルからなる群より選択された一種以上の単量
体がグラフト重合してなり、かつ、グラフト体のテトラ
ヒドロフラン−n−ヘキサン混合溶剤(容積比1:4)
による可溶分が40重量%以下であることを特徴とする
耐衝撃性に優れるゴム強化樹脂。1. One or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl esters are graft-polymerized to ethylene-α-olefin rubber, and , grafted tetrahydrofuran-n-hexane mixed solvent (volume ratio 1:4)
A rubber-reinforced resin with excellent impact resistance, characterized by having a soluble content of 40% by weight or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12434284A JPS612715A (en) | 1984-06-15 | 1984-06-15 | Rubber-reinforced resin with high impact resistance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12434284A JPS612715A (en) | 1984-06-15 | 1984-06-15 | Rubber-reinforced resin with high impact resistance |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS612715A true JPS612715A (en) | 1986-01-08 |
Family
ID=14882981
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12434284A Pending JPS612715A (en) | 1984-06-15 | 1984-06-15 | Rubber-reinforced resin with high impact resistance |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS612715A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5189108A (en) * | 1989-12-27 | 1993-02-23 | Sumitomo Chemical Company, Limited | Modified polymer rubber and process for preparing the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5598214A (en) * | 1979-01-19 | 1980-07-26 | Japan Synthetic Rubber Co Ltd | Production of rubber-modified thermoplastic resin |
JPS5650906A (en) * | 1979-10-01 | 1981-05-08 | Japan Synthetic Rubber Co Ltd | Continuous manufacture of rubber-modified thermoplastic resin |
JPS5884810A (en) * | 1981-11-16 | 1983-05-21 | Japan Synthetic Rubber Co Ltd | Rubber-modified thermoplastic resin composition |
JPS58168642A (en) * | 1982-03-30 | 1983-10-05 | Mitsui Petrochem Ind Ltd | Additive for styrene polymer |
-
1984
- 1984-06-15 JP JP12434284A patent/JPS612715A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5598214A (en) * | 1979-01-19 | 1980-07-26 | Japan Synthetic Rubber Co Ltd | Production of rubber-modified thermoplastic resin |
JPS5650906A (en) * | 1979-10-01 | 1981-05-08 | Japan Synthetic Rubber Co Ltd | Continuous manufacture of rubber-modified thermoplastic resin |
JPS5884810A (en) * | 1981-11-16 | 1983-05-21 | Japan Synthetic Rubber Co Ltd | Rubber-modified thermoplastic resin composition |
JPS58168642A (en) * | 1982-03-30 | 1983-10-05 | Mitsui Petrochem Ind Ltd | Additive for styrene polymer |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5189108A (en) * | 1989-12-27 | 1993-02-23 | Sumitomo Chemical Company, Limited | Modified polymer rubber and process for preparing the same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0060042B1 (en) | Multi-layer structure polymer composition | |
KR0177813B1 (en) | Particulate graft polymer with improved adhesion between grafting base and graft sheath | |
JPS6036177B2 (en) | polyblend composition | |
US4585832A (en) | Weather and impact resistant resin composition and process for its preparation | |
US4766175A (en) | Blend comprising EPDM graft terpolymer and acrylate rubber | |
JPS6112711A (en) | Weather-resistant resin of high shock resistance, processability, and good appearance | |
AU595933B2 (en) | Thermoplastic resin composition | |
US4902745A (en) | Rubber-like thermoplastic polymer mixtures | |
US4701495A (en) | Thermoplastic resin composition | |
CA2010257C (en) | Multi-layer structure polymer and resin composition | |
JPS612715A (en) | Rubber-reinforced resin with high impact resistance | |
JPS612714A (en) | Rubber-reinforced resin | |
JP2796595B2 (en) | Multilayer polymer and resin composition | |
JP3340631B2 (en) | Thermoplastic resin composition | |
JPS62205149A (en) | Weather-resistant resin composition having improved impact resistance and rib strength | |
JPH04220409A (en) | Copolymer resin and thermoplastic resin composition containing the resin | |
JPH0291147A (en) | Blend comprising large amount of epdm graft terpolymer and relatively small amount of acrylate rubber | |
JPH04185663A (en) | High-impact high-rigidity aas resin composition | |
JPH04146910A (en) | Multilayer graft copolymer | |
JPH02294348A (en) | Thermoplastic resin composition | |
JPH0559247A (en) | Weather-resistant, high-impact polymer composition excellent in heat resistance | |
US6072002A (en) | Weatherable resinous composition | |
JPS62235349A (en) | Thermoplastic resin composition | |
JPS63137910A (en) | Weather-resistant resin having excellent rib strength | |
JPS62151442A (en) | Weather-resistant resin composition having improved coloring property, chemical resistance and rib strength |