【発明の詳細な説明】〔産業上の利用分野〕本発明は、耐熱性、耐衝撃性に優れた熱可塑性樹脂組成
物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent heat resistance and impact resistance.
ＡＢＳ樹脂は、その高耐衝撃性、易成形性、塗装、メン
キなどの２次加工が稈易なことなどカラ、汎用またセミ
ニップラ用途を中心に広く使われている。ABS resin is widely used for color, general-purpose, and semi-plastic applications due to its high impact resistance, easy moldability, and ease of secondary processing such as painting and coating.
ＡＢＳ樹脂は、その耐熱性により便宜的に、汎用、準耐
熱、耐熱、超耐熱グレードに分類することができるが、
自動車内装用途を始めとして、近年とみに耐熱性への要
求が高まって来ており、グレードの多様化、ニップラ化
に拍車をかけている。ABS resin can be conveniently classified into general-purpose, semi-heat-resistant, heat-resistant, and super heat-resistant grades depending on its heat resistance.
The demand for heat resistance has increased in recent years, including for automotive interior applications, spurring the diversification of grades and the use of NIPPL.
ＡＢＳ樹脂の耐熱性を向上させる方法としては、共重合
成分としてα−メチルスチレンヲ用いる方法（特公昭３
５−１８１９４月公報）や、イミド結合を導入する方法
（特公昭５６−３９６５１号公報）などが有り、それぞ
れ実用耐熱性、１００℃以１−１１１０℃以−ヒを達成
している。As a method for improving the heat resistance of ABS resin, a method using α-methylstyrene as a copolymerization component (Japanese Patent Publication No. 3
5-1819 April Publication) and a method of introducing an imide bond (Japanese Patent Publication No. 56-39651), each of which has achieved practical heat resistance of 100°C or higher and 1-1110°C or higher.
しかしこれらの而」熱樹脂は、酬＃撃性に重要な影響を
持つゴム成分の最適化を行なっていなし）ために、耐熱
性の向１−に比例して、耐衝撃性の低下、特に落錘衝撃
強度の人［１］な低下を招いているのが実情である。However, these thermal resins do not optimize the rubber components, which have an important effect on impact resistance, and therefore the impact resistance decreases in proportion to the heat resistance. The reality is that this has led to a significant decrease in falling weight impact strength.
発明明考らは、かかる情況に鑑み、耐衝撃性、特に落錘
衝撃強度の優れた耐熱、超耐熱ＡＢＳ系樹脂を提ｆＪＵ
することを口開として、耐熱Ａ Ｉ３８系樹脂における
最適なゴム補強成分について鋭意探索した結果、耐熱（
！１を損なわずに所望の漬れた性状を有する樹脂が得ら
れることを見い出し本発明に到達した。In view of this situation, the inventors proposed a heat-resistant, ultra-heat-resistant ABS resin with excellent impact resistance, especially falling weight impact strength.
As a result of our intensive search for the optimal rubber reinforcing component for heat-resistant A I38 resin, we found that heat-resistant (
! The inventors have discovered that it is possible to obtain a resin having the desired soaked properties without impairing the properties described above, and have arrived at the present invention.
すなわち、本発明は（Ａ）ａ−メチルスチレノおよび／またはマレイミド系
単量体１０〜９０市量％およびシアン化ビニル系ｔｌｌ
量体１０〜５０！１ｌｉｔ％およびこ１１らと基型ａ
可能な単量体８０〜０重量％からなる単１４体または単
量体混合物を重合してなる耐熱性熱ＬＩＪ塑性樹脂、（Ｂ）、；エノ系ゴム状重合体１５〜７５重量部の存在
−トにｇ香族モノビニル糸単徂体わよびシアン化ビニル
系単量体からなる単量体混合物８５〜１５市崖部を乳化
重含させたグラフト共重合体および（Ｃ） ゴム′直市台体４５〜８５市星部の存在トに
、（メタ）アクリルＩＶＩエステル３５〜８０ｔｎＬ％
および芳香族モノビニル系単量体６５〜２０重量％およ
びこれらと共重合可能な単量体０〜２０重Ｍ％からなる
単量体此含物５５〜１５重星部を重合してなる高ゴム含
有グラフト共重合体からなり、（Ａ）１０〜８０重量部、ＦＢ１１０〜８９重量部、お
よび（Ｃ）１，０〜２０重量部でかつ（Ａ）、旧）およ
びＣ）の合８１が１００重量都“となる割合で配合して
なり、全組成物中における前記ジェノ系ゴム状重合体お
よび前記ゴム質重合体からなるゴム成分の含有量が２〜
３５重量％である熱可塑性樹脂組成物である。That is, the present invention provides (A) 10 to 90% by weight of a-methylstyrene and/or maleimide monomer and vinyl cyanide tll.
mass 10 to 50!1 lit% and these 11 and base type a
A heat-resistant thermal LIJ plastic resin obtained by polymerizing a monomer or monomer mixture consisting of 80 to 0% by weight of possible monomers, (B); the presence of 15 to 75 parts by weight of an eno-based rubbery polymer; - A graft copolymer obtained by emulsifying and superimposing a monomer mixture 85 to 15 consisting of an aromatic monovinyl yarn and a vinyl cyanide monomer, and (C) a rubber straight market. In the presence of 45 to 85 parts of the base, 35 to 80 tnL% of (meth)acrylic IVI ester
and 65 to 20% by weight of aromatic monovinyl monomers and 0 to 20% by weight of monomers copolymerizable with these monomers. (A) 10 to 80 parts by weight, FB 110 to 89 parts by weight, and (C) 1,0 to 20 parts by weight, and the sum of (A), old) and C) is 100 parts by weight. The content of the rubber component consisting of the geno-based rubbery polymer and the rubbery polymer in the entire composition is from 2 to 2% by weight.
35% by weight of the thermoplastic resin composition.
以Ｆ、本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained.
本発明の組成物は耐熱性熱可塑性樹脂■、グラフト共重
合体Ｂ）および高ゴム含有グラフト共重合体Ｃ＋よりな
る。The composition of the invention consists of a heat-resistant thermoplastic resin (1), a graft copolymer B) and a high rubber-containing graft copolymer C+.
耐熱Ｆ４［可塑性樹脂（至）はα−メチルスチレンおよ
び／またはマレイミド系単量体およびシアン化ビニル系
小屋体および必要に応じてこれらと共重合可能な単量体
を重合することによって得られる。Heat-resistant F4 [plastic resin (higher) is obtained by polymerizing α-methylstyrene and/or maleimide monomers, vinyl cyanide monomers, and, if necessary, monomers copolymerizable with these.
ここで用いるマレイミド系単量体としては。The maleimide monomer used here is:
例えば＋ｓ記一般式ｆｌｌで示される化合物が挙げられ
る。For example, there may be mentioned a compound represented by the general formula flll in +s.
Ｒ＋ Ｒ２−Ｃ（ただし式中のＲ＋ 、 Ｒ２、Ｒ３は各々独立に水素
、ハロゲン、炭素数１〜２０の置換または非置換のアル
キル基、アリール基などを示す）マレイミド系単量体の
好ましい具体例としては、マレイミド、Ｎ−メチルマレ
イミド、Ｎ−エチルマレイピド、Ｎ−ブチルマレイミド
、Ｎ−ラウリルマレイミド、Ｎ−フェニルマレイミ１’
、Ｎ−（＋）−ブロモフェニル）マレイミドなどが挙げ
られ、これらは２種以上を４〕（用しても良い。R+ R2 -C (R+, R2, R3 in the formula each independently represents hydrogen, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, aryl group, etc.) Preferred specific examples of maleimide monomers Examples include maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-phenylmaleimide 1'
, N-(+)-bromophenyl)maleimide, etc., and two or more of these may be used in combination.
シアン化ビニル系単量体としては、例えばアクリロニト
リル、メタクリロニトリル、エタクリロニトリルなどが
挙げられる。Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile.
ｉ（％ 性−ｆ！１ＩＪＪ塑性樹脂Ａ塑性樹脂下α−メ
チルスチレン、マレイミド系単量体と共重合口Ｊ能な単
量体としては、例えばスチレン、ビニルトルエン、ｐ−
メチルスチレン、ｐ−ｔ−ブチルスチレン、０−エチル
スチレン、ｏ−ｐ−クロロスチレンなどの芳香族モノビ
ニル糸車ｊｔ 体、Ｎ−ビニルピロリトノ、２−ヒドロ
キンエチルメタクリレ−１・、アクリルアミド、スチレ
ンスルホどン酸すトリウムなどの親水性用単体、ジビニルベノセノ
、イノシアヌル酸トリアリルなどの多官能性ビニル系単
量体、無水マレイノ酸、アクリル酸、メタクリル酸など
のビニル系単量体が挙げられる。i (% Characteristic - f!1 IJJ Plastic resin
Aromatic monovinyl spinning wheels such as methylstyrene, pt-butylstyrene, 0-ethylstyrene, op-chlorostyrene, N-vinylpyrrolitono, 2-hydroquinethylmethacrylate-1, acrylamide, styrene Examples include hydrophilic monomers such as sulfonate, polyfunctional vinyl monomers such as divinyl benoceno and triallyl inocyanurate, and vinyl monomers such as maleic anhydride, acrylic acid, and methacrylic acid.
耐熱性熱可塑性樹脂（Ａ）は、上記単里体まｆコは単量
体混合物を塊状、懸濁、乳化重合法などの任意の方法で
重合することにより作ることができる。具体的には、例
えばα−メチルスチレン６５〜９０ｆｆｉ量ｓ、アクリ
ロニ１−リル３５〜１゜重鼠部の割合で、乳化重合法を
用いて作ることもできる。The heat-resistant thermoplastic resin (A) can be produced by polymerizing the monomer mixture described above by any method such as bulk polymerization, suspension polymerization, or emulsion polymerization. Specifically, it can also be produced using an emulsion polymerization method using, for example, a ratio of 65 to 90 ffi of α-methylstyrene and 35 to 1 of acrylonilyl.
この重合における単量体の組成比は、α−＝メチルスチ
レノおよび／またはマレイミド系単量体を１０〜９０重
量％とする必要があり、好ましくは３０〜８５重量％で
ある。α−メチルスチレンおよび／またはマレイミド系
単量体の割合が１０重量％より少ないと、熱可塑性樹脂
組成物の熱変形温度が低くなり好ましくない。The monomer composition ratio in this polymerization needs to be 10 to 90% by weight of α-=methylstyrene and/or maleimide monomer, preferably 30 to 85% by weight. If the proportion of α-methylstyrene and/or maleimide monomer is less than 10% by weight, the heat distortion temperature of the thermoplastic resin composition will become low, which is not preferable.
グラフト共重合体Ｂ）はレニン糸ゴム状重合体の存在下
に芳香族モノビニル系単量体とシアン化ビニル系単量体
を乳化重合させることによって得られる。The graft copolymer B) is obtained by emulsion polymerization of an aromatic monovinyl monomer and a vinyl cyanide monomer in the presence of a renin thread rubbery polymer.
ここで使用する芳香族モノビニル系単量体としては、例
えばスチレン、α−メチルスチレン、ビニルトルエン、
０−エチルスチレン、ｏ−ｐ−レクロロスチレノなどが
挙げられ、ンアノ化ビニル系ＩＮ体としては、例えばア
クリロニ１−リル、メタクリロニトリル、エタクリロニ
！・リルなどが挙げられる。これらは２種以にを４）［
用して用いてもよい。Examples of the aromatic monovinyl monomer used here include styrene, α-methylstyrene, vinyltoluene,
Examples include 0-ethylstyrene and op-lechlorostyrene, and examples of the anodized vinyl IN form include acryloni-1-lyl, methacrylonitrile, ethacrylonitrile!・Lil etc. These include two or more types4) [
You may also use it.
グラフｈ共重合体Ｂ）の乳化グラフト重合における単量
体の組成比は、芳香族モノビニル系単量体とシアン化ビ
ニル系単量体を任意の割合に混合して用いられるが、そ
の割合は、好ましくは芳香族モノビニル系単量体６０〜
８０重里％、シアン化ビニル系単量体４０〜２０重量％
の範囲から選ばれる。The composition ratio of the monomers in the emulsion graft polymerization of graph h copolymer B) is such that aromatic monovinyl monomers and vinyl cyanide monomers are mixed in an arbitrary ratio. , preferably aromatic monovinyl monomer 60~
80% by weight, vinyl cyanide monomer 40-20% by weight
selected from the range.
乳化グラフ１〜共重合体（Ｂ）は、任意の乳化重合法に
より得られるが、例えばまずジェノ系ゴム状重合体１５
〜７５重量部、好ましくは３０〜７０重量部を予め重合
槽に仕込りでおき、しかるのち未反応単量体を連続的に
供給する方法によって得られる。Emulsion graph 1 to copolymer (B) can be obtained by any emulsion polymerization method, but for example, first, geno-based rubbery polymer 15
It is obtained by charging up to 75 parts by weight, preferably 30 to 70 parts by weight, into a polymerization tank in advance, and then continuously feeding unreacted monomer.
重合開始剤は油溶性、水溶性のどちらでも良く、あるい
は併用することもできる。The polymerization initiator may be either oil-soluble or water-soluble, or they may be used in combination.
ここで使用するレニン糸ゴム状重合体は任意のものが使
用できるが、例えばポリブタレエノラテソクス、ポリス
チレンーブタジエノラテックス、ポリアクリコニ１−リ
ルーブタジエノラテカラス等が挙げられる。これらは、
２種以十併用して用いてもよく、その場合それぞれのラ
テックスを単独でグラフト重合しても良いが、予めブレ
ンドしたのちグラフト重合にｆＪＬすることも可能であ
る。Any renin thread rubber-like polymer can be used here, and examples thereof include polybutaleenolatex, polystyrene-butadienolatex, polyacrylic 1-lylubutadienolatecalas, and the like. these are,
Two or more latexes may be used in combination. In that case, each latex may be graft-polymerized alone, but it is also possible to blend them in advance and then perform graft polymerization.
乳化重合後の反応混合物からグラフ１−共重合体（Ｉ３
）を得る方法は任意であり、例えば、ジェノ系ゴム状重
合体ラテックスを鉱酸、電解質などで凝固し、口過、洗
浄、脱水、乾燥を行なって重合体を回収する方法などで
行なうことができる。From the reaction mixture after emulsion polymerization, graph 1-copolymer (I3
) may be obtained by any method; for example, geno-based rubbery polymer latex may be coagulated with mineral acid, electrolyte, etc., and the polymer may be recovered by filtration, washing, dehydration, and drying. can.
高ゴム含有グラフト共重合体（Ｃ）は、ゴム質重合体の
存在下に（メタ）アクリル酸エステルおよび芳香族モノ
ビニル系単量体および必要に応じてこれらと共重合可能
な単量体を重合することによって得られる。The high rubber content graft copolymer (C) is produced by polymerizing (meth)acrylic acid ester and aromatic monovinyl monomer and, if necessary, a monomer copolymerizable with these in the presence of a rubbery polymer. obtained by doing.
ここテ使用するゴム質重合体とは、カラス転移温度が０
℃以下のものが好適であり、具体的には、ポリブタジェ
ノ、ポリスチレン−ブタンエン、ポリアクリロニ］・リ
ルーブタレエノ等のノエノ系ゴム、アクリル酸ブチル、
ポリプロピルアクリレ−、＋、等のアクリル系ゴムおよ
びエチレン−ブｏピレノ−じエン系ゴム（Ｅ Ｐ Ｉ）
Ｍ ）等を用いることができる。The rubbery polymer used here has a glass transition temperature of 0.
℃ or less, and specifically, polybutadieno, polystyrene-butanene, polyacryloni], noeno-based rubbers such as lylubutareeno, butyl acrylate,
Acrylic rubber such as polypropyl acrylate, +, etc. and ethylene-butyrene-diene rubber (EPI)
M) etc. can be used.
（メタ）アクリル酸エステル糸小量（本として１、；Ｉ
、 例えばメタアクリル酸メチル、アクリル酸メチル
などが挙げられ、万香族モノビニル糸車雇体としては、
例えばスチ１７）、α−メチルスチレノ、ビニルトルエ
ノ、０−エチルスチＩエン、０− Ｄ−ジクロロスチレ
ノなどが挙げられる。(meth)acrylic acid ester yarn small amount (1 as a book; I
For example, methyl methacrylate, methyl acrylate, etc. are mentioned, and as a monovinyl spinning wheel,
Examples include Styrene 17), α-methylstyreno, vinyltolueno, 0-ethylstyrene, and 0-D-dichlorostyrene.
これらは２種以−ヒ併用して用いることもできる。Two or more of these can also be used in combination.
高コム含ｓ−グラフト」（重合体（Ｃ）において（メタ
）アクリル酸エステル系Ｉｌ ｉ体および九”香族モノ
ビニル系単量体と共重合ｊｌｉＪ能な単量体としては、
例えばアクリロニ！・リル、メタクリル酸Ｉ・リル、エ
タクリロニＩ・リル等のシアノ化ビニル糸単里体、Ｎ−
ビニルピロリトノ、２−ヒドロキシエチルメタクリレ−
１・、アクリルアミド、スチレノスルポノ酸すトリウム
等の親水性単量体、レビニルベノゼノ、イソシアヌル酸
１−リアリル等の多官能１！１−ビニル系単量体、無水
マレイノ酸、アクリル酸、メタクリル酸等のし一ニル系
単ＩＪｔ体が挙げられる。Examples of monomers capable of copolymerizing with the (meth)acrylic acid ester II isomer and the 9'' aromatic monovinyl monomer in the high comb-containing S-graft (polymer (C)) include:
For example, Acryloni!・Cyanated vinyl monomers such as lylu, methacrylic acid I・lyl, ethacryloni I・lyl, N-
Vinylpyrrolitono, 2-hydroxyethyl methacrylate
1., hydrophilic monomers such as acrylamide and styrenosulfonate, polyfunctional 1!1-vinyl monomers such as levinyl benozeno and 1-realyl isocyanurate, maleinoic anhydride, acrylic acid, methacrylic acid, etc. Examples include mono-IJt units.
尚゛ゴム含有ゲラノ（・共重合体（Ｃ）の爪台における
Ｉｌｌ Ｉ 体のｉＪ１成比は、（メタ）アクリル酸エ
ステル系単ｈｔ体３５〜８０屯量％、Ｊ！Ｓ香ＩＩ）５
モノビニル系単量体６５〜２０市星９０ＪＪ Ｊびこれ
らとＪ（＋ｌｉ合−ｒ＋Ｊ能なｉ、ｌｉ 量体Ｏ〜２０
市星％の範囲から選ばれる。In addition, the iJ1 composition ratio of the Ill I form in the nail base of the rubber-containing gerano copolymer (C) is 35 to 80 tons of the (meth)acrylic acid ester monoht form, J!S fragrance II) 5
Monovinyl monomer 65-20 Ichiboshi 90JJ
Selected from a range of Ichiboshi%.
高ゴノ・含有グラフ１〜共市合体０はゴム質重合体４５
〜８５重量部のイｆ−在ト単量体混合物５５〜１５重量
部を「「怠の重台法に、１り爪台することで得るＣとが
でき、例えばグラフト共重合体Ｂ）と同様の方法で製造
できる。High concentration/containing graph 1 to 0 is rubbery polymer 45
~85 parts by weight of the if-containing monomer mixture can be added to 55 to 15 parts by weight of the monomer mixture in the same manner as in "C", for example, with the graft copolymer B). It can be manufactured in a similar manner.
本発明の組成物は、かくして得られた面］熱性熱可塑性
樹脂（Ａ）１０〜８０重量部、グラフト共重合体ｆｆ３
１１０御８９１゛」（重合体ｔｅｌ １．、 ０〜２ ０ ｊｆ＠量
部を混合ｌ−′１専ら ガれる。
（かくし−
Ｃ得られた組成物中におけるレエノ系＝ １１ ＝ゴム状重合体およびゴム質重合体からなるゴム成分の含
自址は２〜３５重Ｍ９６であることが必要である。ゴム
成分の含有量が２重里％未満では、衝撃強度が十分でな
く、３５重Ｍ９ｏを越えると、流動性が低下する上に、
熱変形温度が下がり好ましくない。The composition of the present invention contains the thus obtained surface] 10 to 80 parts by weight of thermal thermoplastic resin (A), graft copolymer ff3
110 89 1 ゛'' (polymer tel 1., 0~20 jf @ amount part mixed 1-'1 exclusively).
(Hidden-
C The content of the rubber component consisting of the leeno-based = 11 = rubbery polymer and the rubbery polymer in the obtained composition is required to be 2 to 35 times M96. If the content of the rubber component is less than 2% by weight, the impact strength will not be sufficient, and if it exceeds 35% by weight, the fluidity will decrease and
This is not preferable because the heat distortion temperature decreases.
混合はげ意の方法で実施でき、例えば、パンバリーミキ
１ノー、ロール、エクスｉ・ルーダ−などで混練するこ
とによって製品化される。It can be carried out by a mixing method, for example, by kneading with a Panbury mixer, roll, exi-ruder, etc. to produce a product.
本発明の組成物はさらに他の熱可塑性重合体、例エハス
チレノーアクリロニトリル其ｆｉ 合体、スチレノー無
水マレイノ酸共重合体、ポリカーボネ− １・、ボリア
εド、ポリブチレノテレフタレート、およびポリフェニ
レンオキサイドなどを混合して、望ましい性能に調鈴す
ることができる。よた混練時または混練後に酸化防止剤
などの熱安定剤、紫外線吸収剤などの各種添加剤やガラ
ス繊維、金属繊維などの補強剤、および充填剤などを混
合することもできる。The compositions of the present invention may further contain other thermoplastic polymers, such as styrene-acrylonitrile polymer, styrene-maleino acid anhydride copolymer, polycarbonate, boria ester, polybutylene terephthalate, and polyphenylene oxide. Can be mixed and tuned to desired performance. During or after the kneading, heat stabilizers such as antioxidants, various additives such as ultraviolet absorbers, reinforcing agents such as glass fibers and metal fibers, fillers, and the like may be mixed.
＝ １２ 一本発明において耐熱ＡＢＳ系樹脂のゴム補強成分として
異なった組成を持つ２種類のゴム含有グラフト共重合体
を併用した樹脂が、高い耐衝撃性、とり１）は優れた落
鍾衝撃強度を持つとは予期しえなかった事であり、その
作用機構は必ずしも明らかでない。しかしグラフト共重
合体Ｂ）を単独で使用すると、落錘強度は出ないものの
アイゾツト衝撃強さは満足のいくレベル近くまで発現す
ることが分かり、高ゴム含有グラフト共重合体Ｃ＋単独
の場合にはこの逆の結果となることが分かったので、両
者の相剰作用により止揚された樹脂が生まれたものと推
察される。= 12 In the present invention, the resin in which two types of rubber-containing graft copolymers with different compositions are used in combination as the rubber reinforcing component of the heat-resistant ABS resin has high impact resistance, and 1) has excellent impact strength against falling stones. This was unexpected, and its mechanism of action is not necessarily clear. However, when graft copolymer B) was used alone, the Izot impact strength was found to be close to a satisfactory level, although the falling weight strength was not achieved, and when the high rubber content graft copolymer C+ was used alone, Since it was found that the opposite result was obtained, it is inferred that the suspended resin was produced by the mutual action of the two.
本発明をさらに具体的に説明するために、以ト、実施例
及び比較例を挙げて説明する。なお、最終的に得られた
樹脂組成物は、射出成形、押出成形、その他の成形法に
よって成形されたのち、前記の試験法により諸物性を測
定した。In order to explain the present invention more specifically, the present invention will be described below with reference to Examples and Comparative Examples. In addition, the finally obtained resin composition was molded by injection molding, extrusion molding, or other molding methods, and then various physical properties were measured by the above-mentioned test methods.
熱変形温間 ＡＳＴＭ Ｄ６４８−５６アイ
ゾツト衝撃強度 ＡＳＴＭ Ｄ２５６−５６Ａ落錘衝
撃強ｊ扶 Ｊ Ｉ Ｓ Ｋ ７２１ ］副速度）実施例１ポリブタノエンラテックス ＢＲ−］（東し製、’Ｖ均
粒径０．３６ ｐ ） 、 ピロリン酸すトリウム、ブ
ドウ糖、硫酸第１鉄を表１の組成で２０１の反応槽へ仕
込Ａ、ｔご。Heat deformation warm ASTM D648-56 Izot impact strength ASTM D256-56A Falling weight impact strength J I S K 721 ] Sub-speed) Example 1 Polybutanoene latex BR-] (made by Toshi, 'V uniform grain (diameter: 0.36 p), sodium pyrophosphate, glucose, and ferrous sulfate were charged into reaction tank A and 201 with the composition shown in Table 1.
６０℃まで昇温し、連鎖移動剤を含む単量体モノマと乳
化された油溶性開始剤を連続的に添加し、７時間で重合
を完ｒした。重合したラテックスは酸化防止剤を加えた
のち硫酸で凝固後、苛１イ１．ノー ダで中和し、口過
、洗浄、脱水、乾燥し、均一なパウダ ＰＢ−］を回収
した。The temperature was raised to 60° C., a monomer containing a chain transfer agent and an emulsified oil-soluble initiator were continuously added, and the polymerization was completed in 7 hours. After adding an antioxidant to the polymerized latex, it is coagulated with sulfuric acid and then washed with water. The powder was neutralized with powder, passed through the mouth, washed, dehydrated, and dried to recover a uniform powder PB-].
共重合体（（Ｃ）は、ｆ（Ｒ−１を用い、表１１こ示し
たＫＪ１成で、ＰＢ−１と同様の方法で作られた。（パ
ウダをＰＣ−］と呼ぶことにする。以Ｆ同様に命リン酸
すトリウム、ブドウ糖、硫酸第１鉄を表１の組成で２０
ｅの反応槽−＼仕込んｔごのち、７０℃まで昇温し、連
鎖移動剤を含むｌｌｉ 吊体モノマと乳化された曲Ｍ性
開始剤を連続的に添加し７、］００時間合した。しかる
のら未反応のα−メチルスチレンを重合させるために、
数回アクリロニトリルをバッチＣ仕込み６時１ｊｌで重
合を完了した。重合したラテックスは、Ｐ Ｂ −１と
Ｎ （Ｍの方法で回収し、均一なパウダＰＡ−１を回収
しＩこ。The copolymer ((C) was made using f(R-1 and the KJ1 composition shown in Table 11) in the same manner as PB-1 (the powder will be referred to as PC-). Similarly to F, 20% of thorium phosphate, glucose, and ferrous sulfate were added with the composition shown in Table 1.
After the reaction tank e was charged, the temperature was raised to 70°C, and the suspended monomer containing a chain transfer agent and the emulsified bendable initiator were continuously added and allowed to combine for 7,00 hours. However, in order to polymerize unreacted α-methylstyrene,
Acrylonitrile was added to Batch C several times and the polymerization was completed at 6:00 1Jl. The polymerized latex was recovered by the method of PB-1 and N (M), and a uniform powder PA-1 was recovered.
マレイミド系ｊ（重合体は次の様にして得られた。ビ■
コリン酸す［・リウム、ブドウ糖、硫酸第１鉄を表１の
組成で２０１の反応槽へ仕込んだのち、８５”０まで昇
ｎｒＡ シ、単量体モノマｄル自物と乳化された曲ｍ性
開始剤を連続的に添加し、１２時間で爪音を完了した。Maleimide-based j (polymer was obtained as follows.
After charging phosphoric acid, glucose, and ferrous sulfate into the reaction tank of 201 with the composition shown in Table 1, the temperature was increased to 85"0, and the mixture was emulsified with the monomer monomer itself. The initiator was added continuously and the rattling was completed in 12 hours.
重合したラテックｙ、ｔｉ、ＰＢ−１．！：同様のＢ法
で回収し、均一なパウダＩ） Ａ −２を回収した。Polymerized latex y, ti, PB-1. ! : A uniform powder I) A-2 was recovered using the same method B.
したのち、射出成形法により＋Ｊノプルを作成した。After that, +J noples were created by injection molding.
表２番こ実施例の酪合比および評価結果をまとめｔこ。Table 2 summarizes the butt ratio and evaluation results of this example.
実施例２マレイミド系共重合体のマレゴミ１ζ量単星体としてＮ
−フェニルマレイミ１〜を用いて重合した。重合条件は
ＰＡ−２と同一であった。回収したパウダはＩ）Ａ−３
と命名した。Example 2 Maleimide copolymer malegomi 1ζ amount N as a single star
- Polymerization was carried out using phenylmaleimi 1~. Polymerization conditions were the same as for PA-2. The collected powder is I)A-3
It was named.
実施例の評価結果はすべて表２にまとめて示しｔこ。All evaluation results of the examples are summarized in Table 2.
実施例３マレイミド系共重合体のマレイミド系単量体としてＮ−
フェニルマレイミドを、また芳香族モノビニル系中ｉ
Ｋとしてスチレンとα−メチルスチレンを表１の割合で
併用した。α−メチルスチレンの添加により重合時間を
２０時間に延Ｎ ｌノ、アクリロニｉ・リルを数回に分
は合＃ｌ’ ２部を、追加仕込した。（ＰＡ〜４）実施例４マレイミド系共重合体を実施例３の組成で、一杯−懸濁重合１１ζて製造しｔコ。懸濁重合法はＳ Ａ Ｎ
ｏ）重合に用いられる公知の方法で行ない、転化率９
８９ｖの透明なヒースを得た。（ＢＡ−１，）実施例５高ゴム含有グラフト基型合体Ｃ）として県別化学工業（
株）製のＰＶＣ改質剤Ｂ′ＦＡ −ＩＩＩ ＯＲヲ用い
た。Example 3 N- as a maleimide monomer of a maleimide copolymer
Phenylmaleimide is also used in aromatic monovinyl
As K, styrene and α-methylstyrene were used together in the proportions shown in Table 1. The polymerization time was extended to 20 hours by adding α-methylstyrene, and 2 parts of acrylonitrile was added several times. (PA~4) Example 4 A maleimide copolymer having the composition of Example 3 was produced by suspension polymerization 11ζ. Suspension polymerization method is SAN
o) Performed by a known method used for polymerization, with a conversion rate of 9
Obtained 89v clear heather. (BA-1,) Example 5 High-rubber-containing graft group combination C) was prepared by prefectural chemical industry (
PVC modifier B'FA-III OR manufactured by Co., Ltd. was used.
比較例１実施例１に対応して、高コム含冶グラフト共重合体Ｃ）
を含まない場合（配合１．３．４）および少量のみ含む
場合について表３に示した。Comparative Example 1 Corresponding to Example 1, high comb-containing graft copolymer C)
Table 3 shows cases in which it does not contain (formulation 1.3.4) and cases in which it contains only a small amount.
高ゴム含有グラフト共重合体Ｃ］の添加量が１０部木満
である組成物は、劇ＷＪ撃１１１：、特に落錘衝撃強さ
が著しく低かった。The composition in which the amount of the high-rubber-containing graft copolymer C] added was 10 parts was extremely low in WJ impact 111, particularly in the falling weight impact strength.
比較例２実施例２に対応しくＣ）成分を含まない組成物を試作し
たが、１／２１ＺＯＤ、落錘強度１Ｌ低いものであった
。Comparative Example 2 Corresponding to Example 2, a composition that did not contain component C) was produced as a trial, but it had a 1/21 ZOD and a falling weight strength of 1 L lower.
比較例３実施例５で使用り、ｊ：ＰＶＣ改質剤ＢＴＡ−ｍＯＲを
３０部添加１７だ所、耐熱性が低士するばかりか、耐衝
撃性の改良効果も発現しなか−）だ。Comparative Example 3 When 30 parts of the PVC modifier BTA-mOR used in Example 5 was added, the heat resistance was not only lowered, but also the effect of improving impact resistance was not exhibited.
比較例４ 。Comparative example 4.
ゴム成分として、高ゴム含有グラフ１−共重合体（Ｃ）
のみを使用した所、落錘衝撃強度は改良さ一］だが、ア
イノット衝撃強さが大巾に低ドした。As a rubber component, high rubber content graph 1-copolymer (C)
When using a chisel, the falling weight impact strength was improved, but the eye knot impact strength was significantly lower.
比較例５ａ−メチルスチレン系共重合体、フレイミド系共重合体
の替わり１こ基体樹脂とし−Ｃ塊状重合５ＡＮ（東し製
、ＡＮ／Ｓ ＝ ２８／７２ ）を用いｔコ所、耐熱性
が大巾に下がって、耐熱、耐衝撃としての特性バランス
が失われてしまった。Comparative Example 5 Using -C bulk polymerization 5AN (manufactured by Toshi, AN/S = 28/72) as a base resin instead of a-methylstyrene copolymer and Flaimide copolymer, heat resistance was obtained. However, the balance between heat resistance and impact resistance has been lost.
本発明の組成物は１１ｉＪ熱性と同時に耐向撃性、特に
落錘衝撃強度がともに護れたものである。The composition of the present invention has both 11iJ heat resistance and counter-impact resistance, especially falling weight impact strength.
特許出願人 東 し 株 式 会 社−３
４４〜Patent applicant Toshi Co., Ltd.-3
44～
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26632784AJPS61145244A (en) | 1984-12-19 | 1984-12-19 | Thermoplastic resin composition |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26632784AJPS61145244A (en) | 1984-12-19 | 1984-12-19 | Thermoplastic resin composition |
| Publication Number | Publication Date |
|---|---|
| JPS61145244Atrue JPS61145244A (en) | 1986-07-02 |
| JPS6347744B2 JPS6347744B2 (en) | 1988-09-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26632784AGrantedJPS61145244A (en) | 1984-12-19 | 1984-12-19 | Thermoplastic resin composition |
| Country | Link |
|---|---|
| JP (1) | JPS61145244A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61250008A (en)* | 1985-04-30 | 1986-11-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of fine particle of heat-resistant resin |
| JPS62177054A (en)* | 1986-01-30 | 1987-08-03 | Sumitomo Naugatuck Co Ltd | Heat-resistant resin composition having improved falling ball impact strength |
| JPS62199645A (en)* | 1986-02-27 | 1987-09-03 | Sumitomo Naugatuck Co Ltd | Heat-resistant resin composition having improved impact resistance and processing properties |
| JPS62252447A (en)* | 1986-04-25 | 1987-11-04 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JPH0366741A (en)* | 1989-08-07 | 1991-03-22 | Mitsubishi Rayon Co Ltd | Heat-resistant thermoplastic resin composition |
| US5088646A (en)* | 1989-12-06 | 1992-02-18 | Kabushiki Kaisha Toshiba | Heat pump type heating apparatus and control method thereof |
| US5170936A (en)* | 1989-07-06 | 1992-12-15 | Kabushiki Kaisha Toshiba | Heat pump type heating apparatus and control method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3074906A (en)* | 1959-04-27 | 1963-01-22 | Borg Warner | Blends of (a) conjugated diolefine-alkyl aryl vinylidenes-acrylonitrile graft copolymer with (b) conjugated aliphatic diolefine-monovinyl aromatic hydrocarbon/alkyl alkacrylate graft copolymer |
| JPS5578043A (en)* | 1978-12-06 | 1980-06-12 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3074906A (en)* | 1959-04-27 | 1963-01-22 | Borg Warner | Blends of (a) conjugated diolefine-alkyl aryl vinylidenes-acrylonitrile graft copolymer with (b) conjugated aliphatic diolefine-monovinyl aromatic hydrocarbon/alkyl alkacrylate graft copolymer |
| JPS5578043A (en)* | 1978-12-06 | 1980-06-12 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61250008A (en)* | 1985-04-30 | 1986-11-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of fine particle of heat-resistant resin |
| JPS62177054A (en)* | 1986-01-30 | 1987-08-03 | Sumitomo Naugatuck Co Ltd | Heat-resistant resin composition having improved falling ball impact strength |
| JPS62199645A (en)* | 1986-02-27 | 1987-09-03 | Sumitomo Naugatuck Co Ltd | Heat-resistant resin composition having improved impact resistance and processing properties |
| JPS62252447A (en)* | 1986-04-25 | 1987-11-04 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| US5170936A (en)* | 1989-07-06 | 1992-12-15 | Kabushiki Kaisha Toshiba | Heat pump type heating apparatus and control method thereof |
| JPH0366741A (en)* | 1989-08-07 | 1991-03-22 | Mitsubishi Rayon Co Ltd | Heat-resistant thermoplastic resin composition |
| US5088646A (en)* | 1989-12-06 | 1992-02-18 | Kabushiki Kaisha Toshiba | Heat pump type heating apparatus and control method thereof |
| Publication number | Publication date |
|---|---|
| JPS6347744B2 (en) | 1988-09-26 |
| Publication | Publication Date | Title |
|---|---|---|
| CN107075214B (en) | Thermoplastic resin composition and molded article using same | |
| JP2726918B2 (en) | Impact resistant thermoplastic resin composition | |
| JPS59147009A (en) | Abs-molding composition | |
| JPS58162616A (en) | Production of maleimide copolymer | |
| JPS61145244A (en) | Thermoplastic resin composition | |
| JPS604544A (en) | Thermoplastic resin composition | |
| JPH0530861B2 (en) | ||
| JP3626288B2 (en) | Low rigidity styrenic resin composition with excellent pigment dispersibility | |
| JPH0417230B2 (en) | ||
| JP2699945B2 (en) | Thermoplastic resin composition | |
| JP3340631B2 (en) | Thermoplastic resin composition | |
| JP3059201B2 (en) | Thermoplastic resin composition and multi-stage rigid polymer suitable for the same | |
| JP2004256744A (en) | Impact resistant reinforcing material, method for producing the same and high-impact reinforced polystyrene | |
| JPS61166807A (en) | Production of copolymer | |
| JPH0273841A (en) | Reinforced thermoplastic resin composition | |
| JPS63304042A (en) | Heat-resistant thermoplastic polymer composition | |
| JPS61162510A (en) | Production of heat-resistant polymer | |
| JPS6134046A (en) | Thermoplastic resin composition | |
| JPS6236442A (en) | Heat-resistant resin composition | |
| JPH0428749A (en) | Thermoplastic resin composition having excellent appearance and high heat resistance and molded article | |
| JPS61246217A (en) | Production of thermoplastic resin excellent in heat distortion resistance and impact resistance | |
| JPS6386756A (en) | Modifying agent for thermoplastic resin | |
| JPH0376712A (en) | Thermoplastic resin excellent in resistance to heat and its impact, preparation, and thermoplastic resin composition excellent in resistance to heat and impact prepared therefrom | |
| JPH06287379A (en) | Maleimide resin composition | |
| JPS6123617A (en) | Production of n-substituted maleimide copolymer |