JPH07316381A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH07316381A JPH07316381A JP11001094A JP11001094A JPH07316381A JP H07316381 A JPH07316381 A JP H07316381A JP 11001094 A JP11001094 A JP 11001094A JP 11001094 A JP11001094 A JP 11001094A JP H07316381 A JPH07316381 A JP H07316381A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- copolymer
- resin composition
- vinyl
- 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.)
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Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、耐熱性、耐衝撃性、耐
薬品性、寸法安定性および成形性が均衡して優れた熱可
塑性樹脂組成物に関する。さらに詳しくは、特定の割合
で不飽和ジカルボン酸無水物単量体残基および不飽和ジ
カルボン酸イミド単量体残基を含有する共重合体、特定
のグラフト共重合体、ポリアミド樹脂、並びに特定の割
合で不飽和ジカルボン酸および/またはその無水物基を
有するエチレン−α−オレフィン系エラストマーを必須
成分とする熱可塑性樹脂組成物に関する。本発明の熱可
塑性樹脂組成物は自動車部品、電気・電子部品、事務用
機器部品、熱器具、食器、冷蔵庫部品、浴槽部品、シャ
ワー部品、浄水器部品、便座等に好ましく用いることが
出来る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, chemical resistance, dimensional stability and moldability. More specifically, a copolymer containing an unsaturated dicarboxylic acid anhydride monomer residue and an unsaturated dicarboxylic acid imide monomer residue in a specific ratio, a specific graft copolymer, a polyamide resin, and a specific The present invention relates to a thermoplastic resin composition containing an ethylene-α-olefin elastomer having an unsaturated dicarboxylic acid and / or an anhydride group thereof at a ratio as an essential component. The thermoplastic resin composition of the present invention can be preferably used for automobile parts, electric / electronic parts, office equipment parts, heat appliances, tableware, refrigerator parts, bath parts, shower parts, water purifier parts, toilet seats and the like.
【0002】[0002]
【従来の技術】従来から、不飽和ジカルボン酸イミド誘
導体残基を有する共重合体の製造方法は知られている
(米国特許第3840499号明細書、米国特許第39
9907号明細書)。しかし、不飽和ジカルボン酸イミ
ド誘導体残基を有する共重合体は耐熱性、寸法安定性は
優れているが、耐衝撃性、耐薬品性、成形性が劣る問題
点があった。2. Description of the Related Art Conventionally, a method for producing a copolymer having an unsaturated dicarboxylic acid imide derivative residue has been known (US Pat. No. 3,840,499, US Pat. No. 39).
9907). However, although the copolymer having an unsaturated dicarboxylic acid imide derivative residue is excellent in heat resistance and dimensional stability, there is a problem that impact resistance, chemical resistance and moldability are poor.
【0003】そこで、不飽和ジカルボン酸イミド誘導体
残基を有する共重合体にABS樹脂をブレンドして、耐
衝撃性を改良した樹脂組成物も知られている(米国特許
第3642949号明細書、米国特許3652726号
明細書、特開昭57−98536号公報、特開昭57−
125241号公報)。しかし、これらのABS樹脂を
ブレンドした樹脂組成物は、耐衝撃性は改良されるもの
の、耐薬品性が充分でないという欠点があった。Therefore, a resin composition in which an ABS resin is blended with a copolymer having an unsaturated dicarboxylic acid imide derivative residue to improve impact resistance is also known (US Pat. No. 3,642,949, US). Japanese Patent No. 3652726, Japanese Unexamined Patent Publication No. 57-98536, Japanese Unexamined Patent Publication No. 57-
No. 125241). However, the resin composition obtained by blending these ABS resins has a drawback that the chemical resistance is not sufficient, although the impact resistance is improved.
【0004】また、不飽和ジカルボン酸イミド誘導体残
基を有する共重合体の耐薬品性を改良する目的で、この
共重合体にポリアミド樹脂をブレンドした樹脂組成物も
提案されている(特開昭58−71952号公報、特開
昭63−17949号公報、特開平3−277648号
公報、特開平1−215843号公報)。ポリアミド樹
脂をブレンドすることにより、耐薬品性を向上させるこ
とは出来るが、種々の問題点が生じている。Further, for the purpose of improving the chemical resistance of a copolymer having an unsaturated dicarboxylic acid imide derivative residue, a resin composition prepared by blending a polyamide resin with this copolymer has also been proposed (Japanese Patent Laid-Open Publication No. Sho. 58-71952, JP-A-63-17949, JP-A-3-277648, and JP-A-1-215843). By blending a polyamide resin, chemical resistance can be improved, but various problems have occurred.
【0005】例えば、特開昭58−71952号公報で
は、この樹脂組成物は耐薬品性は優れているものの、ブ
レンドした樹脂間の相溶性が充分ではなく、成形品に剥
離が生じる欠点がある。また、ポリアミド樹脂量が20
重量%を超える時は耐衝撃性が向上するが、20重量%
以下になると極端に耐衝撃性、耐薬品性が低下してしま
う。また、実施例中にABS樹脂を添加して耐衝撃性を
向上させる例が記載されているが、これはポリアミド樹
脂量が20重量%を超えた場合であり、20重量%以下
の場合はABS樹脂を添加しても、耐衝撃性は低く、全
く実用に適さない。For example, in JP-A-58-71952, although this resin composition has excellent chemical resistance, the compatibility between the blended resins is not sufficient and there is a drawback that peeling occurs in a molded product. . In addition, the amount of polyamide resin is 20
Impact resistance improves when it exceeds 20% by weight, but 20% by weight
If it becomes less than the following, impact resistance and chemical resistance will be extremely lowered. Further, an example in which an ABS resin is added to improve impact resistance is described in the examples. This is when the amount of polyamide resin exceeds 20% by weight, and when the amount is 20% by weight or less, ABS is used. Even if a resin is added, the impact resistance is low and it is not suitable for practical use.
【0006】また、特開昭63−17949号公報で
は、不飽和ジカルボン酸イミド誘導体残基を有する共重
合体、ポリアミド樹脂、およびグラフト共重合体よりな
る樹脂組成物が提案されている。この樹脂組成物はポリ
アミド樹脂の配合量が多いと、耐衝撃性は向上するが寸
法安定性が低下し、ポリアミド樹脂の配合量が少ない
と、寸法安定性が向上するが、耐衝撃性と耐薬品性は低
下する欠点がある。Further, Japanese Patent Laid-Open No. 63-17949 proposes a resin composition comprising a copolymer having an unsaturated dicarboxylic acid imide derivative residue, a polyamide resin, and a graft copolymer. In this resin composition, when the content of the polyamide resin is large, the impact resistance is improved but the dimensional stability is lowered, and when the content of the polyamide resin is small, the dimensional stability is improved, but the impact resistance and the There is a drawback that the chemical properties are lowered.
【0007】さらに、特開平3−277648号公報で
は、不飽和ジカルボン酸イミド誘導体残基を有する共重
合体とポリアミド樹脂の樹脂組成物の相溶性を改良する
ために、不飽和ジカルボン酸イミド誘導体残基を有する
重合体に不飽和ジカルボン酸無水物単量体残基を有する
共重合体とし、この共重合体とポリアミド樹脂との樹脂
組成物が提案されている。この樹脂組成物は相溶性は大
幅に改良されるものの、ポリアミド樹脂配合量は30重
量%以上であるので、寸法安定性が劣る欠点がある。ま
た、この樹脂組成物はポリアミド樹脂量を30重量%未
満にすると、耐衝撃性が大幅に低下してしまう。Further, in JP-A-3-277648, in order to improve the compatibility of the copolymer having an unsaturated dicarboxylic acid imide derivative residue with a resin composition of a polyamide resin, an unsaturated dicarboxylic acid imide derivative residue is used. There has been proposed a resin composition comprising a group-containing polymer and an unsaturated dicarboxylic acid anhydride monomer residue as the copolymer, and the copolymer and a polyamide resin. Although the compatibility of this resin composition is greatly improved, since the polyamide resin content is 30% by weight or more, there is a drawback that the dimensional stability is poor. Further, when the amount of polyamide resin of this resin composition is less than 30% by weight, impact resistance is significantly lowered.
【0008】さらに、特開平1−215843号公報に
は、不飽和ジカルボン酸イミド誘導体残基を有する共重
合体、ポリアミド樹脂、並びに不飽和ジカルボン酸およ
び/またはその無水物を有するエチレン−α−オレフィ
ン系エラストマー共重合体からなる樹脂組成物が提案さ
れている。この樹脂組成物は耐衝撃性、耐熱性、耐薬品
性が非常に優れているが、ポリアミド樹脂が30重量%
以上であることから、寸法安定性が劣る欠点がある。ま
た、この樹脂組成物のポリアミド樹脂量を30重量%未
満にすると、耐衝撃性が大幅に低下し、実際に使用する
ことは難しい。Further, JP-A 1-215843 discloses a copolymer having an unsaturated dicarboxylic acid imide derivative residue, a polyamide resin, and an ethylene-α-olefin having an unsaturated dicarboxylic acid and / or its anhydride. A resin composition composed of a system elastomer copolymer has been proposed. This resin composition has very good impact resistance, heat resistance and chemical resistance, but the polyamide resin is 30% by weight.
From the above, there is a drawback that the dimensional stability is poor. Further, if the amount of polyamide resin of this resin composition is less than 30% by weight, the impact resistance is significantly lowered and it is difficult to actually use it.
【0009】また、一般にポリアミド樹脂およびポリア
ミド樹脂を含む樹脂組成物の耐薬品性は優れていること
は知られていたが、樹脂組成物中のポリアミド樹脂の量
が多いと、吸水により寸法安定性が低下して、成形品の
組立時に勘合不良、そり、変形が起こり易く、ポリアミ
ド樹脂の量が少ないと、吸湿による寸法安定性は改良さ
れるものの、耐薬品性が低く、かつ耐衝撃性が低下する
欠点がある。ポリアミド樹脂の量が少ない場合、耐衝撃
性を向上させるために、SBRやMBSなどのゴム状重
合体を添加する事も考えられるが、実際には耐衝撃性向
上効果は乏しいものであった。Further, it has been known that a polyamide resin and a resin composition containing a polyamide resin are generally excellent in chemical resistance. However, when the amount of the polyamide resin in the resin composition is large, dimensional stability due to water absorption is obtained. Deteriorates, so that poor fitting, warpage and deformation are likely to occur during the assembly of molded products, and when the amount of polyamide resin is small, the dimensional stability due to moisture absorption is improved, but the chemical resistance is low and the impact resistance is low. There is a drawback to decrease. When the amount of the polyamide resin is small, it may be possible to add a rubber-like polymer such as SBR or MBS in order to improve the impact resistance, but in reality, the impact resistance improving effect was poor.
【0010】[0010]
【発明が解決しようとする課題】本発明は、上記で述べ
たように、不飽和ジカルボン酸イミド誘導体残基を有す
る共重合体を使用した樹脂組成物において、高耐熱、高
耐衝撃でかつ耐薬品性と寸法安定性に優れた樹脂組成物
はいまだ得られておらず、これらの性能を兼備した高性
能な樹脂組成物の開発が強く望まれているのが現状であ
る。そこでこれらの高性能を有する樹脂組成物を提供す
ることを目的に鋭意研究した結果到達したものである。As described above, the present invention provides a resin composition using a copolymer having an unsaturated dicarboxylic acid imide derivative residue, which has high heat resistance, high impact resistance, and high resistance to impact. A resin composition excellent in chemical properties and dimensional stability has not yet been obtained, and under the present circumstances, there is a strong demand for development of a high-performance resin composition having these properties. Therefore, they have arrived as a result of intensive research aimed at providing a resin composition having these high performances.
【0011】[0011]
【問題を解決するための手段】本発明の発明者らは、高
耐熱、高耐衝撃でかつ耐薬品性と寸法安定性に優れた樹
脂の開発を目的に鋭意検討した結果、特定の割合の不飽
和ジカルボン酸無水物単量体残基および不飽和ジカルボ
ン酸イミド単量体残基を有する共重合体、グラフト共重
合体、ポリアミド樹脂、並びに特定の割合で不飽和ジカ
ルボン酸および/またはその無水物基を有するエチレン
−α−オレフィン系エラストマー共重合体を必須成分と
し、特定の割合で配合した場合に上記目的を達成できる
ことを見いだし、本発明の熱可塑性樹脂組成物に達した
ものである。The inventors of the present invention have earnestly studied for the purpose of developing a resin having high heat resistance, high impact resistance, chemical resistance and dimensional stability. Copolymers having unsaturated dicarboxylic acid anhydride monomer residues and unsaturated dicarboxylic acid imide monomer residues, graft copolymers, polyamide resins, and unsaturated dicarboxylic acids and / or their anhydrides in specific proportions It was found that the above object can be achieved when an ethylene-α-olefin elastomer copolymer having a physical group is used as an essential component and blended in a specific ratio, and the present invention has reached the thermoplastic resin composition of the present invention.
【0012】すなわち、本発明は(A)成分:芳香族ビ
ニル単量体残基40〜80重量%、不飽和ジカルボン酸
無水物単量体残基20重量%以下(ただし、0は含ま
ず)、不飽和ジカルボン酸イミド誘導体残基10重量%
以上60重量%未満、およびこれらと共重合可能なビニ
ル単量体残基0〜20重量%からなるマレイミド系共重
合体5〜50重量%、(B)成分:芳香族ビニル単量体
残基60〜80重量%、シアン化ビニル単量体残基20
〜40重量%、およびこれらと共重合可能なビニル単量
体残基0〜20重量%からなるビニル系共重合体0〜5
0重量%、(C)成分:ゴム状重合体35〜65重量部
に、芳香族ビニル単量体50〜80重量%、シアン化ビ
ニル単量体20〜40重量%、およびこれらと共重合可
能なビニル単量体0〜30重量%からなる単量体混合物
35〜65重量部をグラフト重合させたグラフト共重合
体10〜50重量%、(D)成分:ポリアミド樹脂3〜
20重量%と、(E)成分:不飽和ジカルボン酸および
/またはその無水物5重量%以下(ただし、0は含ま
ず)を有するエチレン−αオレフィン系エラストマー共
重合体2〜12重量%とからなる熱可塑性樹脂組成物で
ある。That is, in the present invention, the component (A): aromatic vinyl monomer residue 40 to 80% by weight, unsaturated dicarboxylic acid anhydride monomer residue 20% by weight or less (however, 0 is not included). , Unsaturated dicarboxylic acid imide derivative residue 10% by weight
5 to 50% by weight of a maleimide-based copolymer consisting of 0 to 20% by weight, and 0 to 20% by weight of a vinyl monomer residue copolymerizable therewith, component (B): aromatic vinyl monomer residue 60-80% by weight, vinyl cyanide monomer residue 20
To 40% by weight and 0 to 20% by weight of a vinyl monomer residue copolymerizable therewith, a vinyl-based copolymer 0 to 5
0% by weight, component (C): 35 to 65 parts by weight of a rubbery polymer, 50 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer, and copolymerizable with these Of 50 to 50 wt% of a graft copolymer obtained by graft polymerizing 35 to 65 wt parts of a monomer mixture consisting of 0 to 30 wt% of a vinyl monomer, component (D): polyamide resin 3 to
From 20% by weight and (E) component: 2 to 12% by weight of an ethylene-α-olefin elastomer copolymer having an unsaturated dicarboxylic acid and / or an anhydride thereof in an amount of 5% by weight or less (however, not including 0). It is a thermoplastic resin composition.
【0013】本発明の熱可塑性樹脂組成物の最大の特長
は、ポリアミド樹脂が20重量%以下でありながら、耐
薬品性、耐熱性、耐衝撃性、寸法安定性および成形性が
非常に優れている点である。The greatest feature of the thermoplastic resin composition of the present invention is that the polyamide resin is 20% by weight or less, but the chemical resistance, heat resistance, impact resistance, dimensional stability and moldability are very excellent. That is the point.
【0014】まず、本発明の熱可塑性樹脂組成物に含ま
れる(A)成分のマレイミド系共重合体について説明す
る。(A)成分を構成する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、
t−ブチルスチレン、クロルスチレン等のスチレン系単
量体が挙げられ、これらの中でスチレンが特に好まし
い。First, the maleimide copolymer as the component (A) contained in the thermoplastic resin composition of the present invention will be described. As the aromatic vinyl monomer constituting the component (A), styrene, α-methylstyrene, vinyltoluene,
Examples thereof include styrene-based monomers such as t-butylstyrene and chlorostyrene, and among these, styrene is particularly preferable.
【0015】不飽和ジカルボン酸イミド誘導体としては
マレイミド、N−メチルマレイミド、N−エチルマレイ
ミド、N−シクロヘキシルマレイミド、N−フェニルマ
レイミド、N−ナフチルマレイミド、グルタルイミド等
が挙げられる。Examples of the unsaturated dicarboxylic acid imide derivative include maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide and glutarimide.
【0016】不飽和ジカルボン酸無水物としては、マレ
イン酸、イタコン酸、シトラコン酸、アコニット酸等の
無水物が挙げられ、マレイン酸無水物が特に好ましい。Examples of unsaturated dicarboxylic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, with maleic anhydride being particularly preferred.
【0017】これらと共重合可能なビニル単量体として
は、アクリロニトリル、メタクリロニトリル等のシアン
化ビニル単量体、メチルアクリル酸エステル、エチルア
クリル酸エステル、ブチルアクリル酸エステル等のアク
リル酸エステル単量体,メチルメタクリル酸エステル、
エチルメタクリル酸エステル等のメタクリル酸エステル
単量体、アクリル酸、メタクリル酸等のビニルカルボン
酸単量体、アクリル酸アミド、メタクリル酸アミド、お
よびN−ビニルカルバゾール等が挙げられる。これらの
中でアクリロニトリル、アクリル酸エステル、メタクリ
ル酸エステル、アクリル酸、メタクリル酸等の単量体が
特に好ましい。Vinyl monomers copolymerizable with these include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester. Polymer, methyl methacrylate,
Examples thereof include methacrylic acid ester monomers such as ethyl methacrylic acid ester, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, and N-vinylcarbazole. Among these, monomers such as acrylonitrile, acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.
【0018】(A)成分を製造するにあたって、第1の
製法としては、芳香族ビニル単量体、不飽和ジカルボン
酸イミド誘導体、不飽和ジカルボン酸無水物単量体およ
びこれらと共重合可能なビニル単量体混合物を共重合さ
せる方法、第2の製法としては、芳香族ビニル単量体、
不飽和ジカルボン酸無水物単量体およびこれらと共重合
可能なビニル単量体混合物を共重合させた後、この共重
合体中の不飽和ジカルボン酸無水物基をアンモニア、お
よび/または第1級アミンと反応させてイミド基に変換
させる方法が挙げられ、いずれの方法によってもマレイ
ミド系共重合体を得ることができる。In producing the component (A), the first production method is an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic acid anhydride monomer and vinyl copolymerizable with these. A method of copolymerizing a monomer mixture, and a second production method is an aromatic vinyl monomer,
After copolymerizing the unsaturated dicarboxylic acid anhydride monomer and the vinyl monomer mixture copolymerizable therewith, the unsaturated dicarboxylic acid anhydride group in the copolymer is converted into ammonia and / or primary Examples thereof include a method of reacting with an amine to convert to an imide group, and a maleimide-based copolymer can be obtained by any method.
【0019】第1の製法の場合は、塊状−懸濁重合、溶
液重合、塊状重合を、第2の製法の場合は、懸濁重合、
乳化重合、溶液重合、塊状重合等公知の重合方法を用い
ることができる。In the case of the first production method, bulk-suspension polymerization, solution polymerization and bulk polymerization, and in the case of the second production method, suspension polymerization,
Known polymerization methods such as emulsion polymerization, solution polymerization and bulk polymerization can be used.
【0020】第2の製法で、マレイミド系共重合体を得
るためのイミド化反応に用いるアンモニアや第1級アミ
ンは無水または水溶液のいずれの状態でもあってよい。
また、第1級アミンの例としてメチルアミン、エチルア
ミン、シクロヘキシルアミン等のアルキルアミンおよび
アニリン、トルイジン、ナフチルアミン等の芳香族アミ
ンが挙げられる。The ammonia or primary amine used in the imidization reaction to obtain the maleimide-type copolymer in the second production method may be in either anhydrous or aqueous solution.
Examples of primary amines include alkylamines such as methylamine, ethylamine and cyclohexylamine, and aromatic amines such as aniline, toluidine and naphthylamine.
【0021】イミド化反応は溶液状態または懸濁状態で
行う場合は通常の反応容器、例えばオートクレーブ等を
用いるのが好ましく、塊状溶融状態で行う場合には、脱
揮装置の付いた押出機を用いてもよい。When the imidization reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. May be.
【0022】イミド化反応の温度は約80〜350℃で
あり、好ましくは100〜300℃である。80℃未満
の場合には反応速度が遅く、反応に長時間を要して実用
的でない。一方350℃を越える場合には重合体の熱分
解による物性低下をきたす。イミド化反応時に触媒を用
いてもよく、その場合は第3級アミン、例えばトリエチ
ルアミン等が好ましく用いられる。The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 80 ° C, the reaction rate is slow and the reaction requires a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties are deteriorated due to thermal decomposition of the polymer. A catalyst may be used during the imidization reaction, and in this case, a tertiary amine such as triethylamine is preferably used.
【0023】(A)成分に用いられる芳香族ビニル単量
体残基は40〜80重量%であり、好ましくは43〜7
0重量%が好適である。40重量%未満では成形性が低
下し、80重量%を越えると耐熱性が低下してしまう。
不飽和ジカルボン酸無水物単量体残基は20重量%(た
だし、0は含まず)以下であり、特に0.5〜15重量
%が好ましい。0重量%では(A)成分とポリアミド樹
脂との相溶性が低下し、樹脂組成物の成形品の層剥離の
原因となるばかりでなく、衝撃強度、耐薬品性が低下す
る。20重量%を超えると、ポリアミド樹脂中の末端ア
ミノ基との反応が過剰となり、表面外観が損なわれるの
みならず、耐衝撃性、成形性も低下する。また、不飽和
ジカルボン酸イミド誘導体残基は10重量%以上60重
量%未満であり、25〜55重量%が特に好適である。
10重量%未満では耐熱性の向上は充分でなく、60重
量%以上だと組成物の耐衝撃性が大幅に低下する。ま
た、これらと共重合可能なビニル単量体残基は0〜20
重量%であり、20重量%を越えると耐衝撃性が低下す
る。The aromatic vinyl monomer residue used in the component (A) is 40 to 80% by weight, preferably 43 to 7%.
0 wt% is preferred. If it is less than 40% by weight, the moldability is lowered, and if it exceeds 80% by weight, the heat resistance is lowered.
The unsaturated dicarboxylic acid anhydride monomer residue is 20% by weight (however, 0 is not included) or less, and 0.5 to 15% by weight is particularly preferable. When it is 0% by weight, the compatibility between the component (A) and the polyamide resin is lowered, which not only causes the layer separation of the molded article of the resin composition but also the impact strength and the chemical resistance are lowered. If it exceeds 20% by weight, the reaction with the terminal amino groups in the polyamide resin becomes excessive, and not only the surface appearance is impaired, but also impact resistance and moldability are deteriorated. Further, the unsaturated dicarboxylic acid imide derivative residue is 10% by weight or more and less than 60% by weight, and 25 to 55% by weight is particularly preferable.
If it is less than 10% by weight, the heat resistance is not sufficiently improved, and if it is more than 60% by weight, the impact resistance of the composition is significantly lowered. Further, the vinyl monomer residue copolymerizable with these is 0 to 20.
% By weight, and if it exceeds 20% by weight, the impact resistance decreases.
【0024】次に、(B)成分のビニル系共重合体につ
いて説明する。本発明の(B)成分に用いられる芳香族
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、t−ブチルスチレン、クロルスチ
レン等のスチレン系単量体が挙げられ、特にスチレンが
好ましい。シアン化ビニル単量体としては、アクリロニ
トリル、メタクリロニトリル、α−クロルアクリロニト
リル等が挙げられ、特にアクリロニトリルが好ましい。Next, the vinyl copolymer as the component (B) will be described. Examples of the aromatic vinyl monomer used in the component (B) of the present invention include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and styrene is particularly preferable. preferable. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like, and acrylonitrile is particularly preferable.
【0025】また、これらと共重合可能なビニル単量体
としては、メチルアクリル酸エステル、エチルアクリル
酸エステル、ブチルアクリル酸エステル等のアクリル酸
エステル単量体、メチルメタクリル酸エステル、エチル
メタクリル酸エステル等のメタクリル酸エステル単量
体、アクリル酸、メタクリル酸等のビニルカルボン酸単
量体、アクリル酸アミド、メタクリル酸アミド、および
N−ビニルカルバゾール等が挙げられる。これらの中で
メタクリル酸エステル、アクリル酸、メタクリル酸等の
単量体が特に好ましい。As the vinyl monomer copolymerizable with these, acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, etc., methyl methacrylic acid ester, ethyl methacrylic acid ester And other vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, and N-vinylcarbazole. Of these, monomers such as methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.
【0026】(B)成分も通常の重合方法で製造でき、
例えば懸濁重合、溶液重合、乳化重合等の重合方法が採
用できる。The component (B) can also be produced by a usual polymerization method,
For example, a polymerization method such as suspension polymerization, solution polymerization or emulsion polymerization can be adopted.
【0027】(B)成分中の芳香族ビニル単量体残基は
60〜80重量%であり、好ましくは68〜78重量%
である。60重量%未満では成形性が低下し、80重量
%を越えると耐熱性が低下してしまう。また、シアン化
ビニル単量体残基は20〜40重量%であり、特に22
〜32重量%が望ましい。20重量%未満か40重量%
を越えると熱可塑性樹脂組成物としての(A)成分との
相溶性が低下し、組成物の層剥離や衝撃強度低下の原因
となる。The aromatic vinyl monomer residue in the component (B) is 60 to 80% by weight, preferably 68 to 78% by weight.
Is. If it is less than 60% by weight, the moldability is lowered, and if it exceeds 80% by weight, the heat resistance is lowered. The vinyl cyanide monomer residue is 20 to 40% by weight, and particularly 22
˜32% by weight is desirable. Less than 20% or 40% by weight
When it exceeds the above range, the compatibility with the component (A) as the thermoplastic resin composition decreases, which causes layer peeling of the composition and a decrease in impact strength.
【0028】次に、本発明の(C)成分のグラフト共重
合体について説明する。(C)成分に使用されるゴム状
重合体はブタジエン重合体、ブタジエンと共重合可能な
ビニル単量体との共重合体、エチレン−プロピレン共重
合体、エチレン−プロピレン−ジエン共重合体、および
アクリル酸エステル重合体、アクリル酸エステルと共重
合可能なビニル単量体との共重合体等が挙げられる。Next, the graft copolymer of the component (C) of the present invention will be described. The rubber-like polymer used as the component (C) is a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, and Examples thereof include an acrylic acid ester polymer and a copolymer of an acrylic acid ester and a vinyl monomer copolymerizable with the acrylic acid ester.
【0029】また、(C)成分に用いられる芳香族ビニ
ル単量体にはスチレン、α−メチルスチレン、ビニルト
ルエン、t−ブチルスチレン、クロルスチレン等のスチ
レン系単量体が挙げられ、特にスチレンが好ましい。シ
アン化ビニル単量体としては、アクリロニトリル、メタ
クリロニトリル、α−クロルアクリロニトリル等があ
り、特にアクリロニトリルが好ましい。Examples of the aromatic vinyl monomer used as the component (C) include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and particularly styrene. Is preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like, and acrylonitrile is particularly preferable.
【0030】また、これらと共重合可能なビニル単量体
としては、メチルアクリル酸エステル、エチルアクリル
酸エステル、ブチルアクリル酸エステル等のアクリル酸
エステル単量体、メチルメタクリル酸エステル、エチル
メタクリル酸エステル等のメタクリル酸エステル単量
体、アクリル酸、メタクリル酸等のビニルカルボン酸単
量体、アクリル酸アミド、メタクリル酸アミド、および
N−ビニルカルバゾール等が挙げられ、これらの中でア
クリル酸エステル、メタクリル酸エステル、アクリル
酸、メタクリル酸等の単量体が特に好ましい。As the vinyl monomer copolymerizable with them, acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester, methyl methacrylic acid ester, ethyl methacrylic acid ester And the like, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, and N-vinylcarbazole, and the like. Monomers such as acid esters, acrylic acid and methacrylic acid are particularly preferred.
【0031】このグラフト重合体の製造に当たっては公
知のいずれの重合技術も採用可能であって、例えば懸濁
重合、乳化重合の如き水性不均一重合、塊状重合、溶液
重合および生成重合体の貧溶媒中での沈殿不均一重合
等、並びにこれらの組合せが挙げられる。Any known polymerization technique can be employed in the production of this graft polymer, for example, aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization and a poor solvent for the resulting polymer. Precipitation heterogeneous polymerization, etc., as well as combinations thereof.
【0032】グラフト共重合体のゴム粒径は0.1〜
0.6μmの範囲が、耐衝撃性の面から好ましい。ま
た、グラフト率は20〜80%で、未グラフトコポリマ
ーの重量平均分子量は5〜20万の範囲であると、耐衝
撃性と成形性のバランスが良好である。The rubber particle size of the graft copolymer is 0.1 to
The range of 0.6 μm is preferable from the viewpoint of impact resistance. When the graft ratio is 20 to 80% and the weight average molecular weight of the ungrafted copolymer is in the range of 50,000 to 200,000, the impact resistance and the moldability are well balanced.
【0033】(C)成分は、ゴム状重合体35〜65重
量部存在下に、芳香族ビニル単量体50〜80重量%、
シアン化ビニル単量体20〜40重量%、およびこれら
と共重合可能なビニル単量体0〜30重量%からなる単
量体混合物35〜65重量部をグラフト重合させたもの
である。特に芳香族ビニル単量体65〜70重量%、シ
アン化ビニル単量体22〜32重量%およびこれらと共
重合可能なビニル単量体3〜20重量%が好ましい。芳
香族ビニル単量体が50重量%未満では成形性が低下
し、80重量%を越えると耐熱性が低下してしまう。ま
た、シアン化ビニル単量体は20重量%未満か40重量
%を超えると熱可塑性樹脂組成物としての(A)成分と
の相溶性が低下し、熱可塑性樹脂組成物の層剥離や衝撃
強度低下の原因となる。また、ゴム状重合体が35重量
部未満では耐衝撃性が低下し、65重量部を越えると耐
熱性および成形性が低下する。The component (C) is 50 to 80% by weight of an aromatic vinyl monomer in the presence of 35 to 65 parts by weight of a rubber-like polymer,
It is obtained by graft-polymerizing 35 to 65 parts by weight of a monomer mixture consisting of 20 to 40% by weight of a vinyl cyanide monomer and 0 to 30% by weight of a vinyl monomer copolymerizable therewith. In particular, 65 to 70% by weight of aromatic vinyl monomer, 22 to 32% by weight of vinyl cyanide monomer and 3 to 20% by weight of vinyl monomer copolymerizable therewith are preferable. If the amount of the aromatic vinyl monomer is less than 50% by weight, the moldability will be lowered, and if it exceeds 80% by weight, the heat resistance will be lowered. Further, if the vinyl cyanide monomer is less than 20% by weight or more than 40% by weight, the compatibility with the component (A) as the thermoplastic resin composition decreases, resulting in delamination and impact strength of the thermoplastic resin composition. It causes a decrease. If the amount of the rubber-like polymer is less than 35 parts by weight, the impact resistance will decrease, and if it exceeds 65 parts by weight, the heat resistance and the moldability will decrease.
【0034】なお、グラフト重合においては、通常単量
体全量がゴム状重合体上にグラフトすることは困難であ
り、未グラフト共重合体が副生産される。本発明におい
ては未グラフト共重合体を積極的に分離、除去した真の
グラフト共重合体はもちろんのこと、未グラフト共重合
体を含有したままのグラフト重合でもよく、いずれもグ
ラフト共重合体として取り扱うことができる。In the graft polymerization, it is usually difficult to graft the entire amount of the monomer onto the rubber-like polymer, and an ungrafted copolymer is produced as a by-product. In the present invention, not only the true graft copolymer in which the ungrafted copolymer is positively separated and removed, but also the graft polymerization in which the ungrafted copolymer is contained may be used. It can be handled.
【0035】次に、本発明の(D)成分ポリアミド樹脂
について説明する。(D)成分のポリアミド樹脂として
は、例えばナイロン−6、ナイロン−6,6、ナイロン
−4,6、ナイロン−6,10、ナイロン−12、ナイ
ロン−11等が挙げられ、これらを単独または混合して
用いることもできる。Next, the component (D) polyamide resin of the present invention will be described. Examples of the polyamide resin as the component (D) include nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-12, nylon-11, etc., which may be used alone or in combination. It can also be used.
【0036】次に、本発明の(E)成分のエチレン−α
−オレフィン系エラストマーについて説明する。(E)
成分の不飽和ジカルボン酸および/またはその無水物を
有するエチレン−α−オレフィン系エラストマーとして
は、数平均分子量が10,000〜1,000,000
の範囲にあり、エチレン含有量が50〜80モル%のも
のが好ましい。また、α−オレフィンとしては、プロピ
レン、1−ブテン、1−ペンテンを用いることができ、
特に、プロピレンが好ましい。Next, ethylene-α as the component (E) of the present invention.
-The olefin elastomer will be described. (E)
The ethylene-α-olefin elastomer having an unsaturated dicarboxylic acid and / or its anhydride as a component has a number average molecular weight of 10,000 to 1,000,000.
And an ethylene content of 50 to 80 mol% is preferable. As the α-olefin, propylene, 1-butene, 1-pentene can be used,
Particularly, propylene is preferable.
【0037】また、(E)成分の官能基として変性に用
いる不飽和ジカルボン酸および/またはその無水物とし
ては、マレイン酸、イタコン酸、シトラコン酸、アコニ
ット酸およびこれらの酸無水物があり、特に無水マレイ
ン酸が好適である。Further, the unsaturated dicarboxylic acid and / or its anhydride used for modification as the functional group of the component (E) include maleic acid, itaconic acid, citraconic acid, aconitic acid and their acid anhydrides. Maleic anhydride is preferred.
【0038】不飽和ジカルボン酸および/またはその無
水物の含有量としては5重量%以下(ただし、0は含ま
ず)、好ましくは0.5〜5重量%であり、5重量%を
超えると熱可塑性樹脂組成物にゲル等が発生する。また
0.5重量%未満では、この熱可塑性樹脂組成物中の樹
脂間の相溶性が不充分で層剥離の原因となり、また耐薬
品性や衝撃強度が向上しない。この変性されたエチレン
−α−オレフィン系エラストマーは特公昭58−445
号公報に開示されている実施例1の製造方法等を用いる
ことにより得ることが出来る。The content of the unsaturated dicarboxylic acid and / or its anhydride is 5% by weight or less (not including 0), preferably 0.5 to 5% by weight. Gel or the like is generated in the plastic resin composition. On the other hand, if it is less than 0.5% by weight, the compatibility between the resins in the thermoplastic resin composition is insufficient, which causes layer peeling, and the chemical resistance and impact strength are not improved. This modified ethylene-α-olefin-based elastomer is disclosed in Japanese Examined Patent Publication No. 445/445.
It can be obtained by using the manufacturing method and the like of Example 1 disclosed in the publication.
【0039】本発明の熱可塑性樹脂組成物における
(A)成分、(B)成分、(C)成分、(D)成分およ
び(E)成分の配合比は、(A)成分5〜50重量%、
(B)成分0〜50重量%、(C)成分10〜50重量
%、(D)成分3〜20重量%、および(E)成分2〜
12重量%である。好ましくは、(A)成分10〜40
重量%、(B)成分10〜40重量%、(C)成分20
〜45重量%、(D)成分5〜15重量%、および
(E)成分5〜10重量%である。(A)成分が5重量
%未満では、耐熱性が充分でなく、50重量%を超える
と組成物の耐衝撃性および成形性が大幅に低下する。ま
た、(B)成分は50重量%を超えると耐熱性が低下す
る問題点がある。(C)成分が10重量%未満では耐衝
撃性が低下し、50重量%を超えると耐熱性および成形
性が低下する。(D)成分は3重量%未満では耐薬品性
が充分でなく、20重量%を超えると、寸法安定性が低
下する。(E)成分は2重量%未満では、耐衝撃性が充
分ではなく、12重量%を超えると、成形性および耐熱
性が低下する。In the thermoplastic resin composition of the present invention, the component (A) component, the component (B), the component (C), the component (D) and the component (E) are mixed in a proportion of 5 to 50% by weight of the component (A). ,
(B) component 0 to 50 wt%, (C) component 10 to 50 wt%, (D) component 3 to 20 wt%, and (E) component 2
It is 12% by weight. Preferably, component (A) 10-40
% By weight, 10 to 40% by weight of component (B), 20 of component (C)
˜45% by weight, component (D) 5 to 15% by weight, and component (E) 5 to 10% by weight. If the content of the component (A) is less than 5% by weight, the heat resistance is not sufficient, and if it exceeds 50% by weight, the impact resistance and moldability of the composition are significantly reduced. Further, if the component (B) exceeds 50% by weight, there is a problem that the heat resistance is lowered. When the content of the component (C) is less than 10% by weight, impact resistance is lowered, and when it exceeds 50% by weight, heat resistance and moldability are lowered. If the content of the component (D) is less than 3% by weight, the chemical resistance is insufficient, and if it exceeds 20% by weight, the dimensional stability is deteriorated. If the content of the component (E) is less than 2% by weight, the impact resistance is not sufficient, and if it exceeds 12% by weight, the moldability and heat resistance deteriorate.
【0040】本発明の熱可塑性樹脂組成物を得るために
(A)〜(E)成分を混合する方法には特に制限がな
く、公知の手段を使用する事が出来る。その手段として
例えばバンバリーミキサー、タンブラーミキサー、混合
ロール、1軸または2軸押出機等があげられる。混合形
態としては通常の溶融混合、マスターペレット等を用い
る多段階溶融混合、溶液中でのブレンドより組成物を得
る方法がある。特に(D)成分と(E)成分を予め溶融
混合してマスターペレットとしてから、残りの(A)〜
(C)成分と混合すると、耐薬品性、耐衝撃性、成形性
がさらに良好となる。これは、(D)成分中に(E)成
分が島状に取り込まれ、かつ、この(D)成分と(E)
成分からなる海−島粒子が(A)、(B)、(C)成分
のマトリックス樹脂中に、より分散し易くなることによ
るものと推測される。The method of mixing the components (A) to (E) to obtain the thermoplastic resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or twin-screw extruder, and the like. Examples of the mixing form include ordinary melt mixing, multistage melt mixing using master pellets, and a method of obtaining the composition by blending in a solution. In particular, the component (D) and the component (E) are melt-mixed in advance to form a master pellet, and the remaining (A) to
When mixed with the component (C), chemical resistance, impact resistance and moldability are further improved. This is because the component (E) is incorporated into the component (D) in an island shape, and the component (D) and the component (E)
It is speculated that this is because the sea-island particles composed of the components are more easily dispersed in the matrix resin of the components (A), (B) and (C).
【0041】また、本発明の熱可塑性樹脂組成物は、更
に酸化防止剤、紫外線吸収剤、難燃剤、可塑剤、滑剤、
着色剤、およびタルク、シリカ、クレー、マイカ、炭酸
カルシウム等の無機充填剤、ガラス繊維、カーボン繊維
等の繊維補強剤等を添加することも可能である。The thermoplastic resin composition of the present invention further comprises an antioxidant, an ultraviolet absorber, a flame retardant, a plasticizer, a lubricant,
It is also possible to add a colorant, an inorganic filler such as talc, silica, clay, mica and calcium carbonate, and a fiber reinforcing agent such as glass fiber and carbon fiber.
【0042】本発明の熱可塑性樹脂組成物は耐熱性、耐
衝撃性、耐薬品性、寸法安定性および成形性を要求され
る用途に使用される。例えば自動車部品であるドア芯
材、インパネコア、スポイラー、ピラーサンルーフフレ
ーム、デフロスターグリル、ランプハウジング等や、電
気・電子機器部品、食器、熱器具、電気冷蔵庫部品、便
座、電子レンジ部品、OA機器部品、工業用機械部品等
に好適に使用出来る。The thermoplastic resin composition of the present invention is used in applications requiring heat resistance, impact resistance, chemical resistance, dimensional stability and moldability. For example, door core materials, instrument panel cores, spoilers, pillar sunroof frames, defroster grills, lamp housings, etc. which are automobile parts, electric / electronic device parts, tableware, heat appliances, electric refrigerator parts, toilet seats, microwave oven parts, OA equipment parts It can be suitably used for industrial machine parts and the like.
【0043】以下、本発明を更に実施例により説明する
が、本発明はその主旨を越えない限り、以下の実施例に
限定されるものではない。なお、実施例および比較例中
の部、%はいずれも特にことわらない限り重量基準であ
る。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. All parts and% in the examples and comparative examples are based on weight unless otherwise specified.
【0044】[0044]
実験例1 (A)成分の製造−1 攪拌機を備えたオートクレーブ中にスチレン60部、メ
チルエチルケトン100部を仕込み、系内を窒素ガスで
置換した後温度を85℃に昇温し、無水マレイン酸40
部とベンゾイルパーオキサイド0.15部をメチルエチ
ルケトン200部に溶解した溶液を8時間で連続的に添
加した。添加後更に3時間温度を85℃に保った。ここ
で得られた共重合体溶液にアニリン38部、トリエチル
アミン0.6部を加え140℃で7時間反応させた。反
応液をベント付き2軸押出機に供給し、脱揮してマレイ
ミド系共重合体を得た。C−13NMR分析より酸無水
物基のイミド基への転化率は92モル%であった。この
マレイミド系共重合体は不飽和ジカルボン酸イミド誘導
体としてのN−フェニルマレイミド単位を52%含む共
重合体でありこれを共重合体A−1とした。他のマレイ
ミド系共重合体A−2およびA−3もアニリンの添加量
を調整することにより、無水マレイン酸基のイミド基へ
の転化率を調整したこと以外はA−1と同様な方法で作
成した。Experimental Example 1 Production of component (A) -1 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and then the temperature was raised to 85 ° C. to give maleic anhydride 40
Parts and 0.15 parts of benzoyl peroxide in 200 parts of methyl ethyl ketone were continuously added over 8 hours. The temperature was kept at 85 ° C. for a further 3 hours after the addition. To the copolymer solution obtained here, 38 parts of aniline and 0.6 part of triethylamine were added and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a twin-screw extruder with a vent and devolatilized to obtain a maleimide-based copolymer. From C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 92 mol%. This maleimide copolymer was a copolymer containing 52% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and this was designated as copolymer A-1. The other maleimide copolymers A-2 and A-3 were also prepared in the same manner as in A-1, except that the conversion rate of maleic anhydride group to imide group was adjusted by adjusting the addition amount of aniline. Created.
【0045】実験例2 (A)成分の製造−2 攪拌機を備えたオートクレーブ中にスチレン60部、メ
チルエチルケトン100部を仕込み、系内を窒素ガスで
置換した後温度を100℃に昇温し、温度を保ちながら
充分攪拌を行った。この中にメチルエチルケトン150
部に溶解したN−フェニルマレイミド40部とベンゾイ
ルパーオキサイド0.25部を8時間で連続的に添加し
ながら、重合を行った。重合終了後、反応液をベント付
き2軸押出機に供給し、脱揮、乾燥し、マレイミド系共
重合体を得た。C−13NMR分析よりこの共重合体は
不飽和ジカルボン酸イミド誘導体としてのN−フェニル
マレイミド単位を42%含む共重合であった。これを共
重合体A−4とした。なお、表−1にA−1〜A−4の
組成分析結果および重量平均分子量を示す。表−1中の
重量平均分子量はゲルパーミエーションクロマトグラフ
イーを用い、標準分子量としてポリスチレンを用いた検
量線を作製して求めた。Experimental Example 2 Preparation of component (A) -2 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and the temperature was raised to 100 ° C. While maintaining the above value, sufficient stirring was performed. Methyl ethyl ketone 150
Polymerization was carried out while continuously adding 40 parts of N-phenylmaleimide and 0.25 part of benzoyl peroxide dissolved therein in 8 hours. After completion of the polymerization, the reaction liquid was supplied to a twin-screw extruder with a vent, devolatilized and dried to obtain a maleimide-based copolymer. According to C-13 NMR analysis, this copolymer was a copolymer containing 42% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative. This was designated as copolymer A-4. Table 1 shows the composition analysis results and weight average molecular weights of A-1 to A-4. The weight average molecular weight in Table 1 was determined by using gel permeation chromatography and preparing a calibration curve using polystyrene as the standard molecular weight.
【0046】[0046]
【表1】 [Table 1]
【0047】実験例3 (B)成分の製造 攪拌機を備えた反応缶中にスチレン70部、アクリロニ
トリル30部、第三リン酸カルシウム2.5部、t−ド
デシルメルカブタン0.5部、ベンゾイルパーオキサイ
ド0.2部および水250部を仕込み、70℃に昇温し
重合を開始した。重合開始から7時間後に温度を75℃
に昇温して3時間保ち重合を完結させた。重合率は97
%に達した。得られた反応液を塩酸にて中和し、脱水、
乾燥後白色ビーズ状の共重合体を得た。これを共重合体
B−1とした。Experimental Example 3 Production of Component (B) In a reaction can equipped with a stirrer, 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of calcium triphosphate, 0.5 part of t-dodecylmercaptan, and 0 benzoyl peroxide were used. .2 parts and 250 parts of water were charged and the temperature was raised to 70 ° C. to start polymerization. 7 hours after the start of polymerization, the temperature is changed to 75 ° C.
The temperature was raised to and kept for 3 hours to complete the polymerization. Polymerization rate is 97
% Has been reached. The obtained reaction solution is neutralized with hydrochloric acid, dehydrated,
After drying, a white bead-shaped copolymer was obtained. This was designated as copolymer B-1.
【0048】実験例4 (C)成分の製造 攪拌機を備えた反応缶中にポリブタジェンラテックス1
43部(固形分35%重量平均粒径0.25μm、ゲル
含率90%)、ステアリン酸ソーダ1部、ソジウムホル
ムアルデヒドスルホキシレート0.1部、テトラソジウ
ムエチレンジアミンテトラアセチックアシッド0.03
部、硫酸第一鉄0.003部、および純水150部を仕
込み、50℃に昇温し、これにスチレン70%およびア
クリロニトリル30%よりなる単量体混合物50部、t
−ドデシルメルカブタン0.2部、キユメンハイドロパ
ーオキサイド0.15部を6時間で連続添加し、添加後
さらに65℃に昇温し2時間重合した。重合率は97%
に達した。得られたラテックスに酸化防止剤を添加した
後、塩化カルシウムで凝固、水洗、乾燥後白色粉末状の
グラフト共重合体を得た。これを共重合体C−1とし
た。Experimental Example 4 Preparation of component (C) Polybutadiene latex 1 was placed in a reaction can equipped with a stirrer.
43 parts (solid content 35% weight average particle size 0.25 μm, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediaminetetraacetic acid 0.03
Parts, 0.003 parts of ferrous sulfate, and 150 parts of pure water were charged, the temperature was raised to 50 ° C., and 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, t.
-0.2 parts of dodecyl mercaptan and 0.15 part of kyuumen hydroperoxide were continuously added over 6 hours, and after the addition, the temperature was further raised to 65 ° C and polymerization was performed for 2 hours. Polymerization rate is 97%
Reached After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a white powdery graft copolymer. This was designated as copolymer C-1.
【0049】次に、C−1のグラフト率と未グラフトコ
ポリマーの分子量を測定する為に、C−1をメチルエチ
ルケトン溶液に膨潤させて、遠心分離した上澄み溶液中
のグラフトされていないスチレン−アクリロニトリル共
重合体の分子量をゲルパーミエーションクロマトグラフ
ィーにて測定したところ、重量平均分子量は8.2万で
あった。また、遠心分離で沈降したゲル分(グラフトコ
ポリマーとポリブタジエンゴム)の組成をケルダール窒
素定量分析と熱分解ガスクロマトグラフィーにより分析
し、スチレンとアクリロニトリル量からグラフトコポリ
マーの重量%を測定した。また臭素付加法によりポリブ
タジエンゴムを分析し、ポリブタジエンゴムの重量を決
定した。このように求められたグラフトコポリマーの重
量%とポリブタジエンゴムの重量から以下の式1よりグ
ラフト率を求めたところグラフト率は33%であった。Next, in order to measure the graft ratio of C-1 and the molecular weight of the ungrafted copolymer, C-1 was swollen in a methyl ethyl ketone solution, and the ungrafted styrene-acrylonitrile copolymer in the centrifuged supernatant solution was used. When the molecular weight of the polymer was measured by gel permeation chromatography, the weight average molecular weight was 82,000. The composition of the gel component (graft copolymer and polybutadiene rubber) precipitated by centrifugation was analyzed by Kjeldahl nitrogen quantitative analysis and pyrolysis gas chromatography, and the weight% of the graft copolymer was determined from the amounts of styrene and acrylonitrile. The polybutadiene rubber was analyzed by the bromine addition method to determine the weight of the polybutadiene rubber. From the weight% of the graft copolymer thus obtained and the weight of the polybutadiene rubber, the grafting rate was calculated from the following equation 1 and the grafting rate was 33%.
【0050】[0050]
【数1】 [Equation 1]
【0051】実験例5 (E)成分の変性エチレン−α−オレフィン系エラスト
マー共重合体 特開昭52−49289号公報に示される製法(実施例
に準じ)にて、数平均分子量50万のエチレン−プロピ
レンエラストマー共重合体に無水マレイン酸を2%グラ
フトして得た。これをE−1とした。また、無水マレイ
ン酸で変性する前の数平均分子量50万のエチレン−プ
ロピレンエラストマー共重合体をE−2とした。Experimental Example 5 (E) Component Modified Ethylene-α-Olefin Elastomer Copolymer Ethylene having a number average molecular weight of 500,000 according to the production method (according to Example) disclosed in JP-A-52-49289. It was obtained by grafting 2% of maleic anhydride onto a propylene elastomer copolymer. This was designated as E-1. Further, an ethylene-propylene elastomer copolymer having a number average molecular weight of 500,000 before being modified with maleic anhydride was designated as E-2.
【0052】実施例1〜6および比較例1〜7 (A)成分のマレイミド系共重合体としてA−1〜A−
4、(B)成分のビニル系共重合体としてB−1、
(C)成分のグラフト共重合体としてC−1、(D)成
分のポリアミド樹脂としてD−1および(E)成分の酸
変性エチレン−α−オレフィン系エラストマーとしてE
−1および未変性エチレン−α−オレフィン系エラスト
マーとしてE−2を表−2および表−3に示す量比でブ
レンドし、このブレンド物を35m/m脱揮装置付き同
方向回転2軸押出機を使用し、温度250℃で押出し、
ペレット化した。このペレットを使用し射出成形機によ
り、成形温度250℃で物性測定用の試験片を作成し、
各種物性を測定した。その結果を表−2および表−3に
示す。Examples 1 to 6 and Comparative Examples 1 to 7 A-1 to A-as the maleimide copolymers of the component (A)
4, B-1 as a vinyl-based copolymer of the component (B),
C-1 as the graft copolymer of the component (C), D-1 as the polyamide resin of the component (D) and E as the acid-modified ethylene-α-olefin elastomer of the component (E).
-1, and E-2 as an unmodified ethylene-α-olefin-based elastomer were blended in the amount ratios shown in Tables 2 and 3, and the blended product was a co-rotating twin-screw extruder with a devolatilizer of 35 m / m. And extruding at a temperature of 250 ° C.
Pelletized. Using the pellets, an injection molding machine was used to prepare test pieces for measuring physical properties at a molding temperature of 250 ° C.
Various physical properties were measured. The results are shown in Table-2 and Table-3.
【0053】なお、(D)成分のポリアミド樹脂として
は、ε−カプロラクタムを縮合重合して得られた相対粘
度2.65(溶媒に濃硫酸、濃度は0.5g/100ミ
リリットル、温度は25℃で測定した値)のナイロン−
6を用いた。このナイロン−6をD−1とした。The polyamide resin as the component (D) has a relative viscosity of 2.65 obtained by condensation polymerization of ε-caprolactam (concentrated sulfuric acid in the solvent, the concentration is 0.5 g / 100 ml, the temperature is 25 ° C.). Nylon- (value measured by
6 was used. This nylon-6 was designated as D-1.
【0054】また、実施例6では(D)成分60部と
(E)成分40部を、35m/m脱揮装置付き同方向回
転2軸押出機を用い250℃で押出し、マスターペレッ
トを作成し、このペレット15部を残りの(A)成分2
0部、(B)成分30部、(C)成分35部にブレンド
して更に2軸押出機にて温度250℃で押出し、ペレッ
ト化した。In Example 6, 60 parts of component (D) and 40 parts of component (E) were extruded at 250 ° C. using a co-rotating twin-screw extruder equipped with a 35 m / m devolatilizer to prepare master pellets. , 15 parts of these pellets are used as the remaining component (A) 2
The mixture was blended with 0 part, 30 parts of the component (B) and 35 parts of the component (C) and further extruded with a twin-screw extruder at a temperature of 250 ° C. to form pellets.
【0055】実施例のモルフォロジーを透過型電子顕微
鏡(ルテニウム染色、15000倍)で観察したとこ
ろ、エチレン−プロピレン共重合体を内部に取り込んだ
ナイロン樹脂相が分散相として分散していた。When the morphology of the examples was observed with a transmission electron microscope (ruthenium dyeing, 15,000 times), a nylon resin phase having an ethylene-propylene copolymer incorporated therein was dispersed as a dispersed phase.
【0056】[0056]
【表2】 [Table 2]
【0057】[0057]
【表3】 [Table 3]
【0058】物性測定試験方法 (1)熱変形温度(HDT):ASTM D−648に
準じ、1/4インチ厚み試験片を用い、荷重4.6kg/c
m2で測定した。 (2)アイゾット衝撃強度:ASTM−D 256に準
じ、1/4インチ厚みのノッチ付試験片を用いて測定し
た。 (3)メルトフローレート(MFR):ASTM D−
6874に準じ、温度265℃、荷重10kgfで測定
した。 (4)耐薬品性(臨界歪み):試験片は成形歪みの影響
を排除するため、270℃でペレットをプレス成形した
試験片形状330×20×2mmを用い、長半径248m
m、短半径148mmの1/4楕円法により、薬品とし
てサラダ油を用い温度23℃、24時間後の臨界歪み量
を測定した。なお、臨界歪み量が0.6%以上の場合耐
薬品性が良好であると判断できる。 (5)寸法安定性:ASTM D−638の1号ダンベ
ルを80℃の温水に24時間浸し、浸す前後のダンベル
の長手方向の寸法変化を測定した。寸法変化率が0.5
%以下の場合を○とし、0.5%を超える場合を×とし
た。Test method for measuring physical properties (1) Heat distortion temperature (HDT): According to ASTM D-648, a 1/4 inch thickness test piece was used and a load of 4.6 kg / c.
Measured in m 2 . (2) Izod impact strength: measured according to ASTM-D 256 using a notched test piece having a thickness of 1/4 inch. (3) Melt flow rate (MFR): ASTM D-
According to 6874, it was measured at a temperature of 265 ° C. and a load of 10 kgf. (4) Chemical resistance (critical strain): In order to eliminate the influence of molding strain on the test piece, a test piece shape of 330 × 20 × 2 mm obtained by press-molding pellets at 270 ° C. was used, and a long radius of 248 m.
The critical strain amount after 24 hours at a temperature of 23 ° C. was measured by using a salad oil as a chemical by a 1/4 ellipse method with m and a minor radius of 148 mm. When the critical strain amount is 0.6% or more, it can be judged that the chemical resistance is good. (5) Dimensional stability: ASTM D-638 No. 1 dumbbell was immersed in warm water at 80 ° C. for 24 hours, and the dimensional change in the longitudinal direction of the dumbbell before and after the immersion was measured. Dimensional change rate is 0.5
% Or less was rated as ◯, and more than 0.5% was rated as x.
【0059】表−2に示す結果から明らかなように、実
施例1〜6の組成物は薬品に対する臨界歪みが大きく、
耐薬品性に優れており、しかも優れた耐熱性、耐衝撃
性、成形性および寸法安定性を有している。As is clear from the results shown in Table 2, the compositions of Examples 1 to 6 had a large critical strain with respect to chemicals,
It has excellent chemical resistance, as well as excellent heat resistance, impact resistance, moldability, and dimensional stability.
【0060】これに対して、表−3に示すように、比較
例1の組成物はマレイミド系共重合体を含まないため、
耐衝撃性に劣り、また、耐熱性、耐薬品性も劣る。On the other hand, as shown in Table 3, since the composition of Comparative Example 1 contains no maleimide-based copolymer,
Poor impact resistance, heat resistance, and chemical resistance.
【0061】比較例2の組成物は、無水マレイン酸変性
エチレン−プロピレン共重合体を含まないため、耐衝撃
性に劣り、耐薬品性も劣る。The composition of Comparative Example 2 does not contain a maleic anhydride-modified ethylene-propylene copolymer, and therefore has poor impact resistance and chemical resistance.
【0062】比較例3の組成物は、ナイロン−6の量が
多く、耐薬品性は十分なものの、寸法安定性に劣る。The composition of Comparative Example 3 contained a large amount of nylon-6 and had sufficient chemical resistance, but was inferior in dimensional stability.
【0063】比較例4の組成物は、マレイミド系共重合
体の組成が本発明の範囲外(マレイミド系共重合体中の
無水マレイン酸残基が多い)であり、成形性(MFR)
が極端に劣る。In the composition of Comparative Example 4, the composition of the maleimide copolymer was outside the scope of the present invention (the maleimide anhydride residue was large in the maleimide copolymer) and the moldability (MFR) was high.
Is extremely inferior.
【0064】比較例5の組成物は、マレイミド系共重合
体の組成が本発明の範囲外(マレイミド系共重合体中に
不飽和ジカルボン酸無水物残基量を有しない)であり、
耐衝撃性と耐薬品性に劣る。In the composition of Comparative Example 5, the composition of the maleimide copolymer is outside the scope of the present invention (the maleimide copolymer does not have the amount of unsaturated dicarboxylic acid anhydride residues),
Poor impact resistance and chemical resistance.
【0065】比較例6の組成物は、マレイミド系共重合
体の配合量が本発明の範囲外であり、耐衝撃性と成形性
(MFR)に劣る。The composition of Comparative Example 6 had a maleimide copolymer content outside the range of the present invention, and was inferior in impact resistance and moldability (MFR).
【0066】比較例7の組成物は、(E)成分の変性エ
チレン−α−オレフィン系エラストマー共重合体の代わ
りに未変性エチレン−プロピレンエラストマー共重合体
を用いたものであり、耐衝撃性に劣る。The composition of Comparative Example 7 was prepared by using an unmodified ethylene-propylene elastomer copolymer in place of the modified ethylene-α-olefin elastomer copolymer as the component (E), and was excellent in impact resistance. Inferior.
【0067】[0067]
【発明の効果】本発明の熱可塑性樹脂組成物は、特定の
マレイミド系共重合体、特定のグラフト共重合体、ビニ
ル系共重合体、ポリアミド樹脂、および変性されたエチ
レン−α−オレフィン系共重合体からなり、かつこの熱
可塑性樹脂組成物は、耐薬品性に優れ、しかも耐衝撃
性、耐熱性、成形性、寸法安定性の物性バランスにも優
れている。本発明の組成物は、これらの性能が要求され
る自動車部品、電気・電子部品、事務用機器部品、熱器
具、食器、冷蔵庫部品、浴槽部品、シャワー部品、浄水
機部品、便座等の材料として特に有効に適用できるもの
である。The thermoplastic resin composition of the present invention comprises a specific maleimide-based copolymer, a specific graft copolymer, a vinyl-based copolymer, a polyamide resin, and a modified ethylene-α-olefin-based copolymer. This thermoplastic resin composition, which is made of a polymer, has excellent chemical resistance and also has an excellent balance of physical properties such as impact resistance, heat resistance, moldability, and dimensional stability. The composition of the present invention is used as a material for automobile parts, electric / electronic parts, office equipment parts, heat appliances, tableware, refrigerator parts, bath parts, shower parts, water purifier parts, toilet seats, etc., which are required to have these properties. It can be applied particularly effectively.
Claims (3)
0〜80重量%、不飽和ジカルボン酸無水物単量体残基
20重量%以下(ただし、0は含まず)、不飽和ジカル
ボン酸イミド誘導体残基10重量%以上60重量%未
満、およびこれらと共重合可能なビニル単量体残基0〜
20重量%からなるマレイミド系共重合体5〜50重量
%、(B)成分:芳香族ビニル単量体残基60〜80重
量%、シアン化ビニル単量体残基20〜40重量%、お
よびこれらと共重合可能なビニル単量体残基0〜20重
量%からなるビニル系共重合体0〜50重量%、(C)
成分:ゴム状重合体35〜65重量部に、芳香族ビニル
単量体50〜80重量%、シアン化ビニル単量体20〜
40重量%、およびこれらと共重合可能なビニル単量体
0〜30重量%からなる単量体混合物35〜65重量部
をグラフト重合させたグラフト共重合体10〜50重量
%、(D)成分:ポリアミド樹脂3〜20重量%と、
(E)成分:不飽和ジカルボン酸および/またはその無
水物5重量%以下(ただし、0は含まず)を有するエチ
レン−α−オレフィン系エラストマー共重合体2〜12
重量%とからなることを特徴とする熱可塑性樹脂組成
物。1. Component (A): aromatic vinyl monomer residue 4
0 to 80% by weight, unsaturated dicarboxylic acid anhydride monomer residue 20% by weight or less (however, 0 is not included), unsaturated dicarboxylic acid imide derivative residue 10% by weight or more and less than 60% by weight, and these Copolymerizable vinyl monomer residue 0 to
5 to 50% by weight of a maleimide-based copolymer consisting of 20% by weight, component (B): 60 to 80% by weight of aromatic vinyl monomer residue, 20 to 40% by weight of vinyl cyanide monomer residue, and 0 to 50% by weight of a vinyl-based copolymer comprising 0 to 20% by weight of a vinyl monomer residue copolymerizable with these, (C)
Ingredients: 35 to 65 parts by weight of a rubber-like polymer, 50 to 80% by weight of an aromatic vinyl monomer, and 20 to 20 parts of a vinyl cyanide monomer.
40% by weight and 10 to 50% by weight of a graft copolymer obtained by graft polymerizing 35 to 65 parts by weight of a monomer mixture consisting of 0 to 30% by weight of a vinyl monomer copolymerizable therewith, component (D) : Polyamide resin 3 to 20% by weight,
Component (E): Ethylene-α-olefin elastomer copolymers 2 to 12 containing 5% by weight or less of unsaturated dicarboxylic acid and / or anhydride thereof (not including 0).
And a thermoplastic resin composition.
(E)/(D)=30/70〜60/40である請求項
1記載の熱可塑性樹脂組成物。2. The thermoplastic resin composition according to claim 1, wherein the weight ratio of the component (D) and the component (E) is (E) / (D) = 30/70 to 60/40.
成物をあらかじめ溶融混合し、更に(A)成分、(B)
成分および(C)成分を混合する請求項1記載の熱可塑
性樹脂組成物。3. A resin composition comprising a component (D) and a component (E) is melt-mixed in advance, and the component (A) and the component (B) are further mixed.
The thermoplastic resin composition according to claim 1, wherein the component and the component (C) are mixed.
Priority Applications (1)
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JP11001094A JP3405478B2 (en) | 1994-05-24 | 1994-05-24 | Thermoplastic resin composition |
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JP11001094A JP3405478B2 (en) | 1994-05-24 | 1994-05-24 | Thermoplastic resin composition |
Publications (2)
Publication Number | Publication Date |
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JPH07316381A true JPH07316381A (en) | 1995-12-05 |
JP3405478B2 JP3405478B2 (en) | 2003-05-12 |
Family
ID=14524834
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JP11001094A Expired - Fee Related JP3405478B2 (en) | 1994-05-24 | 1994-05-24 | Thermoplastic resin composition |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002088220A (en) * | 2000-09-14 | 2002-03-27 | Denki Kagaku Kogyo Kk | Permanent antistatic thermoplastic resin composition |
CN1091454C (en) * | 1996-06-11 | 2002-09-25 | 电气化学工业株式会社 | Thermoplastic resin composition, molded product and method for its production |
KR100461524B1 (en) * | 1998-12-30 | 2005-04-06 | 제일모직주식회사 | Thermoplastic composition with excellent steam resistance |
JP2007217621A (en) * | 2006-02-20 | 2007-08-30 | Denki Kagaku Kogyo Kk | Resin composition and molded article thereof |
JP2008247984A (en) * | 2007-03-29 | 2008-10-16 | Daicel Polymer Ltd | Master batch for nylon resin addition |
JP2010043204A (en) * | 2008-08-14 | 2010-02-25 | Daicel Polymer Ltd | Resin composition |
-
1994
- 1994-05-24 JP JP11001094A patent/JP3405478B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1091454C (en) * | 1996-06-11 | 2002-09-25 | 电气化学工业株式会社 | Thermoplastic resin composition, molded product and method for its production |
KR100461524B1 (en) * | 1998-12-30 | 2005-04-06 | 제일모직주식회사 | Thermoplastic composition with excellent steam resistance |
JP2002088220A (en) * | 2000-09-14 | 2002-03-27 | Denki Kagaku Kogyo Kk | Permanent antistatic thermoplastic resin composition |
JP4702989B2 (en) * | 2000-09-14 | 2011-06-15 | 電気化学工業株式会社 | Permanent antistatic thermoplastic resin composition |
JP2007217621A (en) * | 2006-02-20 | 2007-08-30 | Denki Kagaku Kogyo Kk | Resin composition and molded article thereof |
JP2008247984A (en) * | 2007-03-29 | 2008-10-16 | Daicel Polymer Ltd | Master batch for nylon resin addition |
JP2010043204A (en) * | 2008-08-14 | 2010-02-25 | Daicel Polymer Ltd | Resin composition |
Also Published As
Publication number | Publication date |
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JP3405478B2 (en) | 2003-05-12 |
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