JPS6156252B2 - - Google Patents
Info
- Publication number
- JPS6156252B2 JPS6156252B2 JP16423780A JP16423780A JPS6156252B2 JP S6156252 B2 JPS6156252 B2 JP S6156252B2 JP 16423780 A JP16423780 A JP 16423780A JP 16423780 A JP16423780 A JP 16423780A JP S6156252 B2 JPS6156252 B2 JP S6156252B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- parts
- styrene
- acrylonitrile
- 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
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 238000009757 thermoplastic moulding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明はスチレン／無水マレイン酸共重合物と
スチレン／アクリロニトリル／ブタジエン系重合
物及びスチレン／αメチルスチレン／アクリロニ
トリル／ブタジエン系重合物よりなる耐熱変形
性、耐衝撃性、成形加工性の優れた熱可塑性成形
用組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides heat deformation resistance, impact resistance, The present invention relates to a thermoplastic molding composition with excellent moldability.
スチレンと無水マレイン酸からの共重合物は公
知の通り比較的高温まで耐え成形加工性も良好で
あるが、その機械的特性、例えば剛性及び強靭性
において不満足である。又、スチレンとアクリロ
ニトリルより成る共重合物は良好な加工性を有
し、かつ剛性も高く、ポリスチロールに比較し、
良好な耐溶剤性を有する。しかし、その強靭性は
不充分であり、この欠点を改良するために柔軟な
ゴム成分の存在下にスチレンとアクリロニトリル
混合物を重合させ、単量体の一部分をゴム成分に
グラフトすることにより、耐衝撃性の改善するこ
とは公知である。この成形材料は耐衝撃性を満足
するが、耐熱変形安定性が小さく、90℃以上の加
熱により変形を生じる欠点を有する。 As is known, copolymers of styrene and maleic anhydride can withstand relatively high temperatures and have good moldability, but are unsatisfactory in mechanical properties, such as rigidity and toughness. In addition, copolymers made of styrene and acrylonitrile have good processability and high rigidity, and compared to polystyrene,
Has good solvent resistance. However, its toughness is insufficient, and in order to improve this drawback, a mixture of styrene and acrylonitrile is polymerized in the presence of a flexible rubber component, and a portion of the monomer is grafted onto the rubber component. It is known to improve sex. Although this molding material satisfies impact resistance, it has the disadvantage of low thermal deformation stability and deformation when heated above 90°C.
本発明は高い熱変形安定性と耐衝撃性の良好な
熱可塑性成形材料を製造することを目的に研究を
実施した結果、スチレン／無水マレイン酸共重合
物(A)とスチレン／アクロニトリル／ブタジエン系
重合物(B)及びスチレン／αメチルスチレン／アク
リロニトリル／ブタジエン系重合物(C)よりなる溶
融ブレンド物が、この目的を満足することを見い
出した。 The present invention was developed as a result of research aimed at producing thermoplastic molding materials with high thermal deformation stability and good impact resistance. It has been found that a melt blend consisting of the polymer (B) and the polymer (C) of styrene/α-methylstyrene/acrylonitrile/butadiene satisfies this objective.
成分(A)は、無水マレイン酸５〜30重量％、スチ
レン95〜70重量％。さらに望むならばアクリロニ
トリル又はメチルメタクリレート０〜30重量％か
らの共重合物である。 Component (A) is 5-30% by weight of maleic anhydride and 95-70% by weight of styrene. If desired, it is also a copolymer of 0 to 30% by weight of acrylonitrile or methyl methacrylate.
成分(B)はスチレン95〜60重量％とアクリロニト
リル５〜40重量％との単量体混合物95〜50重量％
とポリブタジエン又はブタジエンを50重量％以上
含むブタジエン系共重合体５〜50重量％の一部グ
ラフト共重合物である。 Component (B) is a 95-50% by weight monomer mixture of 95-60% by weight of styrene and 5-40% by weight of acrylonitrile.
It is a partial graft copolymer of 5 to 50% by weight of polybutadiene or a butadiene copolymer containing 50% by weight or more of butadiene.
成分(C)は、スチレン60〜30重量％、αメチルス
チレン60〜30重量％、アクリロニトリル10〜40重
量％の混合物95〜50重量％とポリブタジエン又は
ブタジエンを50％以上含むブタジエン系共重合体
５〜50重量％との一部グラフト共重合物である。 Component (C) is a mixture of 95 to 50% by weight of 60 to 30% by weight of styrene, 60 to 30% by weight of α-methylstyrene, and 10 to 40% by weight of acrylonitrile and polybutadiene or a butadiene copolymer 5 containing 50% or more of butadiene. It is a partial graft copolymer with ~50% by weight.
これらの共重合物(A)、(B)及び(C)は、その製造法
においてすべて公知の方法、例えば塊状重合、溶
液重合、懸濁重合又は乳化重合のいずれかの方法
で製造されたものである。 These copolymers (A), (B), and (C) are all manufactured by any known method, such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. It is.
成分(B)及び(C)のグラフト共重合はゴム成分の存
在下でスチレン、アクリロニトリルあるいはαメ
チルスチレン単量体を塊状−懸濁もしくは乳化重
合することによつて得られ、重合した単量体はゴ
ム成分と部分的に化学結合している。このグラフ
ト共重合物は本発明の成形材料の耐衝撃性を生ぜ
しめ、耐熱変形安定性の高い成分(A)とブレンドす
ることにより、耐熱性良好な耐衝撃性の材料を与
える。 The graft copolymerization of components (B) and (C) is obtained by bulk-suspension or emulsion polymerization of styrene, acrylonitrile, or α-methylstyrene monomers in the presence of a rubber component, and the polymerized monomers are is partially chemically bonded to the rubber component. This graft copolymer gives impact resistance to the molding material of the present invention, and by blending it with component (A) having high heat resistance and deformation stability, an impact resistant material with good heat resistance can be obtained.
多くの高分子物質では２種以上の成分の混合物
は互いに融和性がないことは実験的に知られてい
るが、本発明の組成物は互いに融和性があり、(A)
成分の耐熱変形性と(B)又は(C)成分の耐衝撃性が保
持される。 Although it is experimentally known that in many polymeric substances, mixtures of two or more components are mutually incompatible, the composition of the present invention is mutually compatible, and (A)
The heat deformation resistance of the component and the impact resistance of the component (B) or (C) are maintained.
本発明の成形材料は成分(A)、(B)び(C)を混合し、
200〜260℃の温度で一軸又は二軸押出機により溶
融混合することにより得られる。 The molding material of the present invention mixes components (A), (B) and (C),
It is obtained by melt-mixing in a single-screw or twin-screw extruder at a temperature of 200 to 260°C.
この混合物は成分(A)10〜90重量部、成分(B)０〜
90重量部及び成分(C)90〜10重量部を含有する。こ
れはこの他に必要に応じて添加剤、例えば充填
物、顔料、安定剤、滑剤などが配合される。下記
に実施例を示す。 This mixture consists of 10 to 90 parts by weight of component (A) and 0 to 90 parts by weight of component (B).
90 parts by weight and 90 to 10 parts by weight of component (C). In addition to this, additives such as fillers, pigments, stabilizers, and lubricants may be added as necessary. Examples are shown below.
実施例の各成分は次の性状のものである。 Each component in the examples has the following properties.
成分Ａ：スチレン／無水マレイン酸共重合物
無水マレイン酸／スチレン＝14／86
熱変形温度（フアイバーストレス18.56Kg/
cm2）106℃
アイゾツト衝撃強度1.0Kg-cm/cm
成分Ｂ：スチレン／アクリロニトリル／ブタジエ
ン共重合物
スチレン／アクリロニトリル／ブタジエン＝
52.5／17.5／30.0
熱変形温度86℃
アイゾツト衝撃強度37.6Kg-cm/cm
成分Ｃ：スチレン／αメチルスチレン／アクリロ
ニトリル／ブタジエン共重合物
スチレン／αメチルスチレン／アクリロニト
リル／ブタジエン＝35／26／26／13
熱変形温度92℃
アイゾツト衝撃強度7.9Kg-cm/cm
実施例 １
成分(A)40重量部と成分(C)60重量部を混合し、
220℃に設定した40m/m押出機により溶融混合の
後粒状物とし、これを240℃に設定した射出成形
機にてASTM規格試験片を成形した。この成形
品はASTM規格に準じて測定を行い、熱変形温
度（ASTM D648フアイバーストレス18.56Kg/
cm2）101℃、アイゾツト衝撃強度（ASTM
D256）3.8Kg-cm/cmの性状を持ち、耐熱変形性
を比較的高く保持し、耐衝撃性の改善が認められ
た。Component A: Styrene/maleic anhydride copolymer Maleic anhydride/styrene = 14/86 Heat distortion temperature (fiber stress 18.56Kg/
cm 2 ) 106℃ Izot impact strength 1.0Kg-cm/cm Component B: Styrene/acrylonitrile/butadiene copolymer Styrene/acrylonitrile/butadiene =
52.5/17.5/30.0 Heat distortion temperature 86℃ Izot impact strength 37.6Kg-cm/cm Component C: Styrene/α-methylstyrene/acrylonitrile/butadiene copolymer Styrene/α-methylstyrene/acrylonitrile/butadiene = 35/26/26/ 13 Heat deformation temperature 92℃ Izotsu impact strength 7.9Kg-cm/cm Example 1 40 parts by weight of component (A) and 60 parts by weight of component (C) were mixed,
After melt-mixing using a 40 m/m extruder set at 220°C, the mixture was made into granules, which were then molded into ASTM standard test pieces using an injection molding machine set at 240°C. This molded product was measured according to ASTM standards, and the heat distortion temperature (ASTM D648 fiber stress 18.56Kg/
cm 2 ) 101℃, Izot impact strength (ASTM
D256) has a property of 3.8Kg-cm/cm, maintains relatively high heat deformation resistance, and has improved impact resistance.
これとの比較例として成分(A)40重量部と成分(B)
60重量部を同様な方法で押出溶融混合した粒状物
からの射出成形物の性状は熱変形温度96℃、アイ
ゾツト衝撃強度7.3Kg-cm/cmを有し、耐熱変形性
に於て実施例が優れていた。 As a comparative example, 40 parts by weight of component (A) and component (B)
The properties of an injection molded product made from granules obtained by extruding and melt-mixing 60 parts by weight in the same manner have a heat distortion temperature of 96°C and an Izot impact strength of 7.3 kg-cm/cm. It was excellent.
実施例 ２
成分(A)20重量部と成分(C)80重量部を実施例１と
同様な方法で溶融混合した粒状物からの成形品の
性状は熱変形温度95℃、アイゾツト衝撃強度5.2
Kg-cm/cmを得た。Example 2 A molded product made from granules obtained by melting and mixing 20 parts by weight of component (A) and 80 parts by weight of component (C) in the same manner as in Example 1 had a heat distortion temperature of 95°C and an Izot impact strength of 5.2.
Kg-cm/cm was obtained.
これとの比較例として成分(A)20重量部と成分(B)
80重量部の溶融混合した粒状物からの成形品は熱
変形温度91℃、アイゾツト衝撃強度25.3Kg-cm/
cmの性状を有していた。 As a comparative example, 20 parts by weight of component (A) and component (B)
A molded article made from 80 parts by weight of melt-mixed granules has a heat distortion temperature of 91°C and an Izod impact strength of 25.3 kg-cm/
It had the characteristics of cm.
実施例 ３
成分(A)40重量部と成分(B)40重量部及び成分(C)20
重量部を混合実施例１と同様な方法で押出液融混
合の後粒状物とし、ASTM規格成形品を射出成
形した。Example 3 40 parts by weight of component (A), 40 parts by weight of component (B), and 20 parts by weight of component (C)
Parts by weight were melt-mixed with extrusion liquid in the same manner as in Mixing Example 1, and then made into granules, and an ASTM standard molded product was injection molded.
成形品はそれぞれASTMに準じて性状測定を
行い、熱変形温度96℃、アイゾツト衝撃強度8.2
Kg-cm/cmの物性値を得た。 The properties of each molded product were measured according to ASTM, with a heat distortion temperature of 96°C and an Izot impact strength of 8.2.
Physical property values of Kg-cm/cm were obtained.
Claims (1)
95〜70重量％からの共重合物10〜90重量部。 (B) スチレン95〜60重量％とアクリロニトリル５
〜40重量％との単量体混合物95〜50重量％とポ
リブタジエンまたはブタジエンを50重量％以上
含むブタジエン系共重合体５〜50重量％との一
部グラフト共重合物０〜90重量部。 (C) スチレン60〜30重量％、αメチルスチレン60
〜30重量％及びアクリロニトリル10〜40重量％
の混合物95〜50重量％とポリブタジエン又はブ
タジエンを50重量％以上含むブタジエン系共重
合体５〜50重量％との一部グラフト共重合物10
〜90重量部からなることを特徴とする熱可塑性
成形用組成物。[Claims] 1 (A) 5 to 30% by weight of maleic anhydride and styrene
10-90 parts by weight of copolymer from 95-70% by weight. (B) Styrene 95-60% by weight and acrylonitrile 5
-40% by weight of a monomer mixture of 95-50% by weight and 0-90 parts by weight of a partial graft copolymer of polybutadiene or 5-50% by weight of a butadiene-based copolymer containing 50% by weight or more of butadiene. (C) Styrene 60-30% by weight, α-methylstyrene 60
~30% by weight and acrylonitrile 10-40% by weight
A partial graft copolymer of 95-50% by weight of a mixture of polybutadiene or 5-50% by weight of a butadiene-based copolymer containing 50% by weight or more of butadiene 10
A thermoplastic molding composition comprising ~90 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16423780A JPS5787450A (en) | 1980-11-20 | 1980-11-20 | Thermoplastic composition for molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16423780A JPS5787450A (en) | 1980-11-20 | 1980-11-20 | Thermoplastic composition for molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5787450A JPS5787450A (en) | 1982-05-31 |
| JPS6156252B2 true JPS6156252B2 (en) | 1986-12-01 |
Family
ID=15789270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16423780A Granted JPS5787450A (en) | 1980-11-20 | 1980-11-20 | Thermoplastic composition for molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5787450A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59199745A (en) * | 1983-04-28 | 1984-11-12 | Daicel Chem Ind Ltd | Heat-resistant, shock-resistant composite resin composition |
| JPS59232139A (en) * | 1983-06-15 | 1984-12-26 | Daicel Chem Ind Ltd | High-fluidity, heat- and impact-resistant resin composition |
| NL8501252A (en) * | 1985-05-03 | 1986-12-01 | Stamicarbon | POLYMER COMPOSITION. |
-
1980
- 1980-11-20 JP JP16423780A patent/JPS5787450A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5787450A (en) | 1982-05-31 |
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