JP3525531B2 - Polypropylene resin composite composition - Google Patents
Polypropylene resin composite compositionInfo
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- JP3525531B2 JP3525531B2 JP33093394A JP33093394A JP3525531B2 JP 3525531 B2 JP3525531 B2 JP 3525531B2 JP 33093394 A JP33093394 A JP 33093394A JP 33093394 A JP33093394 A JP 33093394A JP 3525531 B2 JP3525531 B2 JP 3525531B2
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- block copolymer
- polypropylene resin
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリプロピレン樹脂複
合組成物に関し、更に詳しくは、高結晶性ポリプロピレ
ン樹脂を主成分とし、特に射出成形加工性、剛性、耐衝
撃性、脆化温度が低い等の物性バランスに優れており、
家電機器部品、建材、工業部品等の大型成形品に良好に
利用できるポリプロピレン樹脂複合組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composite composition, and more specifically, it contains a highly crystalline polypropylene resin as a main component, and particularly has low injection moldability, rigidity, impact resistance, and brittleness temperature. It has an excellent balance of physical properties,
The present invention relates to a polypropylene resin composite composition that can be favorably used for large-sized molded articles such as home electric appliance parts, building materials, and industrial parts.
【０００２】[0002]
【従来の技術】ポリプロピレン樹脂複合組成物は、デザ
インの自由度、軽量化、リサイクル性等の観点から、家
電機器部品、建材、工業部品等の素材に広く使用されて
いる。各種製品の機能性の追求、経済性の追求から製品
の大型化、薄肉化が進み射出成形加工性、剛性、耐衝撃
性の物性に優れた高流動性のポリプロピレン樹脂複合組
成物が要望されている。2. Description of the Related Art Polypropylene resin composite compositions are widely used as materials for home electric appliances, building materials, industrial parts, etc., from the viewpoints of design freedom, weight reduction, recyclability and the like. In pursuit of functionality and economic efficiency of various products, products are becoming larger and thinner, and there is a demand for highly fluid polypropylene resin composite compositions with excellent injection molding processability, rigidity, and impact resistance. There is.
【０００３】ポリプロピレン樹脂の耐衝撃性を改良する
方法として、ポリプロピレン樹脂に無定型エチレン・プ
ロピレン共重合体や水素添加ブロック共重合体等の熱可
塑性エラストマーをブレンドしたポリプロピレン樹脂組
成物等が多く提案されている。例えば、このような技術
としては、特開昭５８−１７１３９号、特開昭５８−２
０６６４４号、特開昭６１−３４０４８号、特開平１−
２６８７３９号公報等が挙げられる。しかしながら、こ
れら提案組成物は、エラストマーの配合量が少ない場
合、剛性と耐衝撃性の物性バランスが不充分で引張伸び
も低く、高速衝撃性に劣る。或いは、水素添加ブロック
共重合体や軟化剤を多量に含有するエラストマー組成で
は剛性が低く、大型成形品に不適である。As a method for improving the impact resistance of polypropylene resin, many proposals have been made of polypropylene resin compositions in which polypropylene resin is blended with a thermoplastic elastomer such as an amorphous ethylene / propylene copolymer or a hydrogenated block copolymer. ing. For example, such techniques include Japanese Patent Laid-Open Nos. 58-17139 and 58-2.
06644, JP-A-61-34048, JP-A-1-
No. 268739 is cited. However, when the content of the elastomer is small, these proposed compositions have an insufficient balance of physical properties of rigidity and impact resistance, have low tensile elongation, and are inferior in high-speed impact resistance. Alternatively, an elastomer composition containing a large amount of a hydrogenated block copolymer or a softening agent has low rigidity and is not suitable for a large-sized molded product.
【０００４】特開昭５７−７３０３４号、特開昭６１−
２７６８４０号公報等には、結晶性プロピレン重合体に
エチレン重合体とゴム状成分とを配合する組成物、或い
は、エチレン・ポリプロピレン共重合体にゴム状成分、
フィラー、場合によりエチレン重合体を配合する組成物
で物性バランスと成形加工性に良好な組成物が示されて
いる。JP-A-57-73034 and JP-A-61-
No. 276840 discloses a composition in which an ethylene polymer and a rubber-like component are blended with a crystalline propylene polymer, or a rubber-like component with an ethylene / polypropylene copolymer,
A composition having a good balance of physical properties and moldability is shown by a composition containing a filler and optionally an ethylene polymer.
【０００５】ゴム状成分に用いる無定型エチレン−プロ
ピレン共重合体は、その配合量が比較的多く、剛性の低
下、或いは流動性の低下から大型薄肉成形に難点があ
る。また、特開昭６３−１５６８４２号公報等には、高
結晶性ポリプロピレン単独重合体に、スチレン−エチレ
ン・ブチレン−スチレンブロック共重合体もしくはスチ
レン−エチレン・プロピレンブロック共重合体、及びエ
チレン・プロピレン系共重合体ゴムもしくはポリエチレ
ンを配合する組成物が示されているが、必ずしも剛性と
耐衝撃性等のバランスを満足していない。ポリプロピレ
ン樹脂の優れた剛性を保持しながら耐衝撃性を改良した
脆化温度の低い大型薄肉成形のできる組成物が得られて
いないのが現状である。The amorphous ethylene-propylene copolymer used as the rubber-like component has a relatively large blending amount, and has a problem in large-sized thin-wall molding due to a decrease in rigidity or a decrease in fluidity. Further, JP-A-63-156842 discloses a highly crystalline polypropylene homopolymer, a styrene-ethylene / butylene-styrene block copolymer or a styrene-ethylene / propylene block copolymer, and an ethylene / propylene-based copolymer. Although a composition containing a copolymer rubber or polyethylene is shown, it does not always satisfy the balance between rigidity and impact resistance. The present situation is that a composition capable of performing large-sized thin-wall molding with a low embrittlement temperature, which has improved impact resistance while maintaining excellent rigidity of polypropylene resin, has not yet been obtained.
【０００６】[0006]
【発明が解決しようとする課題】本発明者等は、先に剛
性、耐衝撃性のバランス向上にエラストマーの分散状態
が大きく依存することを見出し特許出願をした（特願平
５−１４８２７３）。更に、ポリプロピレン樹脂の剛性
の低下が小さく、且つ耐衝撃性改良効果の高いエラスト
マー成分とその分散性を解決課題として鋭意研究した。
その結果、高結晶性ポリプロピレン樹脂に水素添加ブロ
ック共重合体と高密度ポリエチレンを特定の配合比率で
エラストマー成分とし、高結晶性ポリプロピレン樹脂の
プロピレン単独成分の連続相中に分散するエラストマー
凝集相が粒状で微細な分散状態と成し、更に内側に高密
度ポリエチレン、外側に水素添加ブロック共重合体とな
る２相構造を形成させることにより、剛性、耐衝撃性が
飛躍的に向上し脆化温度が低下することを見出し、本発
明を完成した。The present inventors have previously found that the dispersed state of the elastomer largely depends on the improvement of the balance between rigidity and impact resistance, and filed a patent application (Japanese Patent Application No. 5-148273). Further, an intensive study was conducted on the elastomer component having a small decrease in the rigidity of polypropylene resin and having a high impact resistance improving effect and its dispersibility as a problem to be solved.
As a result, high crystalline polypropylene resin to the hydrogenated block copolymer and high density polyethylene down the elastomer component at a specific blending ratio, elastomeric cohesive phase dispersed in the continuous phase of the propylene homopolymer component of the high crystalline polypropylene resin form a fine dispersed state in particulate, higher density polyethylene in to the inside, by forming a two-phase structure comprising a hydrogenated block copolymer outside, rigidity, impact resistance remarkably improved and embrittlement The inventors have found that the temperature decreases and have completed the present invention.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、
〔イ〕メルトフローレートが１０〜１５０ｇ／１０分、
１２０℃における１，２，４−トリクロロベンゼン不溶
分の重量割合が５０％以上の高結晶性ポリプロピレン単
独重合体もしくはエチレン含有量４重量％未満のエチレ
ン−プロピレンブロック共重合体を５０〜９０重量部、
〔ロ〕（ａ）と（ｂ）成分から構成するエラストマー
で、（ａ）成分は、少なくとも１個のビニル芳香族化合
物を主体とする重合体ブロックＡと共役ジエン化合物部
分の不飽和が２０％を越えない程度にまで水素添加され
た少なくとも１個のオレフィン化合物を主体とする重合
体ブロックＢとからなりビニル芳香族化合物の含有量が
１０％以上３０％未満、メルトフローレートが使用する
〔イ〕成分の０．３〜０．６倍の水素添加ブロック共重
合体、（ｂ）成分は、密度が０．９６ｇ／ｃｍ3 以上、
メルトフローレートが使用する〔イ〕成分の０．５〜
０．８倍の高密度ポリエチレン、これら（ａ）と（ｂ）
の配合比率は４０／６０〜８０／２０重量％の範囲のエ
ラストマー成分を５〜２５重量部、〔ハ〕粒状又は板状
の無機充填剤を５〜２５重量部からなり、高結晶性ポリ
プロピレン樹脂のポリプロピレン単独成分の連続相中に
分散するエラストマー凝集分散相が、内側にポリエチレ
ン或いはポリエチレンとエチレン・ポリプロピレン共重
合体の混和状態で、外側に上記（ａ）成分である水素添
加ブロック共重合体となる２相構造を形成することを特
徴とするポリプロピレン樹脂複合組成物、及びそのエラ
ストマー凝集分散相が、粒子状で平均粒子径を０．１〜
１μｍに微細分散し、更にその平均粒子径と２相構造を
形成する外側の水素添加ブロック共重合体の厚みとの比
率（膜厚比）が１０〜３０％であることを特徴するポリ
プロピレン樹脂複合組成物を提供するものである。That is, the present invention is
[A] Melt flow rate is 10 to 150 g / 10 minutes,
50 to 90 parts by weight of a highly crystalline polypropylene homopolymer having a 1,2,4-trichlorobenzene insoluble content at 120 ° C. of 50% or more or an ethylene-propylene block copolymer having an ethylene content of less than 4% by weight. ,
[B] in (a) and (b) formed know configured to elastomer, (a) component, the unsaturated polymer block A and a conjugated diene compound portion consisting mainly of at least one vinyl aromatic compound is 20% A polymer block B mainly composed of at least one olefin compound hydrogenated to an extent not exceeding 10% and a vinyl aromatic compound content of 10% or more and less than 30%, and a melt flow rate is used.
The hydrogenated block copolymer of 0.3 to 0.6 times the component (a), the component (b) has a density of 0.96 g / cm 3 or more,
The melt flow rate of the component (a) used is 0.5 to
0.8 times the high-density polyethylene, these (a) and (b)
The compounding ratio of 5 to 25 parts by weight of an elastomer component in the range of 40/60 to 80/20% by weight and 5 to 25 parts by weight of [c] a granular or plate-like inorganic filler. The elastomer coagulated dispersed phase dispersed in the continuous phase of the polypropylene single component of (1) is polyethylene or a mixture of polyethylene and an ethylene / polypropylene copolymer on the inside, and the hydrogenated block copolymer which is the component (a) on the outside. To form a two-phase structure
Polypropylene resin composite composition and symptoms, and its elastomeric cohesive disperse phase, 0.1 average particle size in the form of particles
Polypropylene resin composite finely dispersed to 1 μm, and the ratio (film thickness ratio) of the average particle diameter to the thickness of the outer hydrogenated block copolymer forming a two-phase structure is 10 to 30%. A composition is provided.
【０００８】本発明で用いる高結晶性ポリプロピレン樹
脂は、高立体規則性触媒の存在下に多段で重合させるこ
とによって得られ、メルトフローレート（以下、本発明
ではＭＦＲと記載）が１０〜１５０ｇ／１０分、１２０
℃における１，２，４−トリクロロベンゼン（以下、本
発明ではＴＣＢと記載）不溶分の重量割合が５０％以上
の高結晶性ポリプロピレン単独重合体もしくはエチレン
含有量４重量％未満のエチレン−プロピレンブロック共
重合体である。かかる高結晶性ポリプロピレン樹脂は、
例えば特開平５−６５３２１号公報に開示された方法に
より製造することができる。The highly crystalline polypropylene resin used in the present invention is obtained by multi-stage polymerization in the presence of a highly stereoregular catalyst, and has a melt flow rate (hereinafter referred to as MFR in the present invention) of 10 to 150 g / 10 minutes, 120
Highly crystalline polypropylene homopolymer having a weight ratio of 1,2,4-trichlorobenzene (hereinafter referred to as TCB in the present invention) insoluble matter at 50 ° C of 50% or more, or an ethylene-propylene block having an ethylene content of less than 4% by weight. It is a copolymer. Such highly crystalline polypropylene resin,
For example, it can be manufactured by the method disclosed in JP-A-5-65321.
【０００９】エチレン含有量が４重量％以上となると、
エラストマー凝集分散相が微細な粒状に分散しないため
に、剛性及び成形品の表面硬度が大きく低下し、本発明
の効果が得られない。また、ＭＦＲが１０ｇ／１０分未
満では、流動性に劣り射出成形の際の流動距離が短く、
成形品の外観、射出成形加工性が悪く薄肉成形が困難で
ある。ＭＦＲが１５０ｇ／１０分を越える場合には、衝
撃強度が低下し好ましくない。最も好ましいＭＦＲは、
２０〜１００ｇ／１０分の範囲である。更にＴＣＢにて
分別を行った際、３０℃におけるＴＣＢ可溶分の重量割
合が１０％以下で、且つ１２０℃におけるＴＣＢ不溶分
が５０％以上にあることが必要である。When the ethylene content exceeds 4% by weight,
Since the elastomer-aggregated dispersed phase is not dispersed in fine particles, the rigidity and the surface hardness of the molded product are significantly reduced, and the effects of the present invention cannot be obtained. When the MFR is less than 10 g / 10 minutes, the fluidity is poor and the flow distance during injection molding is short,
The appearance of the molded product is poor and the injection molding processability is poor, making thin wall molding difficult. If the MFR exceeds 150 g / 10 minutes, the impact strength decreases, which is not preferable. The most preferred MFR is
It is in the range of 20 to 100 g / 10 minutes. Further, when fractionation is performed by TCB, it is necessary that the weight ratio of the TCB-soluble component at 30 ° C. is 10% or less and the TCB-insoluble component at 120 ° C. is 50% or more.
【００１０】ここで、本発明で用いたＴＣＢによる分別
は、Ｌ．ＷｉｌｄらがＰｏｉｙｍｅｒ Ｐｒｅｐｒｉｎ
ｔｓ Ａｍ．Ｃｈｅｍ．Ｓｏｃ.,１８，１８２（１９７
７）の中で直鎖状低密度ポリエチレンの分別に用いる昇
温溶出分別法に準拠して行った。即ち、所定量のポリプ
ロピレン樹脂と酸化防止剤をＴＣＢに加熱溶解し、この
溶液を海砂を満たし１６０℃の温度に保たれたステンレ
ス製カラム中に充填した後、室温までカラムの温度を下
げて、ポリプロピレン樹脂を結晶化させる。このカラム
を再度３０℃まで昇温した後、カラムに接続された配管
より３０℃に温められたＴＣＢを流入して可溶分を取り
出す。Here, the classification by TCB used in the present invention is as follows. Wild et al. Poimer Preprin
ts Am. Chem. Soc., 18, 182 (197
In 7), it was carried out according to the temperature rising elution fractionation method used for fractionation of linear low density polyethylene. That is, a predetermined amount of polypropylene resin and antioxidant were dissolved in TCB by heating, and the solution was filled in a stainless steel column filled with sea sand and kept at a temperature of 160 ° C., and then the temperature of the column was lowered to room temperature. , Crystallize polypropylene resin. After the temperature of this column was raised to 30 ° C. again, TCB warmed to 30 ° C. was flowed in through a pipe connected to the column to take out a soluble component.
【００１１】この可溶分をＴＣＢ溶液にメチルアルコー
ルを追添し、可溶物を再沈降させ、分別濾過、乾燥して
３０℃における可溶分を得る。更に、１２０℃における
ＴＣＢ不溶分は、３０℃の場合と同様に、１２０℃での
ＴＣＢ可溶分を取り出した後、カラムの温度を１６０℃
まで昇温し、以下同様にして得ることができる。３０℃
におけるＴＣＢ可溶分は、実質的に非晶質であり１０％
を越える場合は剛性に劣り、好ましくは７％以下であ
る。１２０℃におけるＴＣＢ不溶分は、特に高結晶性な
部分であり、５０％以下では剛性、耐熱変形性に劣り、
好ましくは５５％以上である。Methyl alcohol is added to the TCB solution to dissolve the soluble matter, and the soluble matter is reprecipitated, fractionated and dried to obtain the soluble matter at 30 ° C. Further, the TCB-insoluble matter at 120 ° C. is the same as at 30 ° C., after the TCB-soluble matter at 120 ° C. was taken out, the column temperature was changed to 160 ° C.
The temperature can be raised to, and the same can be obtained thereafter. 30 ° C
TCB soluble content in 10% is substantially amorphous.
If it exceeds, the rigidity is poor, and it is preferably 7% or less. The TCB insoluble content at 120 ° C. is a particularly highly crystalline portion, and when it is 50% or less, rigidity and heat distortion resistance are poor,
It is preferably 55% or more.
【００１２】本発明のポリプロピレン樹脂複合組成物の
剛性、耐熱性を一層向上させるためには、〔イ〕成分中
のプロピレン単独重合体中のアイソタクチックペンタッ
ド分率の高いことが好ましく、０．９５０以上が推奨さ
れる。アイソタクチックペンタッド分率とは、Ａ．Ｚａ
ｍｂｅｌｌｉらによってＭａｃｒｏｍｏｌｅｃｕｌｅ
ｓ，６，９２５（１９７３）に発表されている方法、す
なわち１３Ｃ−ＮＭＲを使用して測定される結晶性ポリ
プロピレン分子鎖中のペンタッド単位でのアイソタクチ
ック連鎖、すなわちプロピレンモノマー単位が５個連続
してメソ結合した連鎖の中心にあるプロピレンモノマー
単位の分率である。但し、ＮＭＲ吸収ピークの帰属につ
いては、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，８，６８７
（１９７５）によった。In order to further improve the rigidity and heat resistance of the polypropylene resin composite composition of the present invention, it is preferable that the propylene homopolymer in the component (a) has a high isotactic pentad fraction. .950 or higher is recommended. The isotactic pentad fraction means A. Za
Macrobelle et al., Macromolecule
s, 6 , 925 (1973), that is, an isotactic chain of pentad units in a crystalline polypropylene molecular chain measured using 13 C-NMR, that is, five consecutive propylene monomer units. Is the fraction of propylene monomer units at the center of the meso-bonded chains. However, regarding attribution of NMR absorption peaks, Macromolecules, 8 , 687
(1975).
【００１３】本発明で用いる水素添加ブロック共重合体
は、少なくとも１個のビニル芳香族化合物を主体とする
重合体ブロックＡと共役ジエン化合物部分の不飽和が２
０％を越えない程度にまで水素添加された少なくとも１
個のオレフィン化合物を主体とする重合体ブロックＢと
からなりビニル芳香族化合物の含有量が１０％以上３０
％未満、２３０℃におけるＭＦＲが使用する高結晶性ポ
リプロピレン樹脂の０．３〜０．６倍のものである。The hydrogenated block copolymer used in the present invention has a polymer block A containing at least one vinyl aromatic compound as a main component and a conjugated diene compound moiety having an unsaturation of 2 or less.
At least 1 hydrogenated to a degree not exceeding 0%
Composed of a polymer block B mainly composed of individual olefin compounds and having a vinyl aromatic compound content of 10% or more 30
%, The MFR at 230 ° C. is 0.3 to 0.6 times that of the highly crystalline polypropylene resin used.
【００１４】ＭＦＲが使用する高結晶性ポリプロピレン
樹脂より高い場合には、ポリプロピレン成分中に分散す
るとき、粒子状に分散せず、水素添加ブロック共重合体
が単独で層状の分散状態となり易く、又上記範囲より低
い場合には、溶融時の粘度差が大きく本発明の効果が得
られない。When the MFR is higher than that of the highly crystalline polypropylene resin used, it does not disperse into particles when dispersed in the polypropylene component, and the hydrogenated block copolymer alone tends to be in a layered dispersed state, and Lower than the above range
If not, the viscosity difference during melting is large and the effect of the present invention cannot be obtained.
【００１５】ビニル芳香族化合物を主体とする重合体ブ
ロックＡは、ビニル芳香族化合物と共役ジエン化合物と
の重量比が１００／０〜５１／４９、好ましくは１００
／０〜７０／３０の組成範囲からなる重合体ブロックで
あり、ビニル芳香族化合物と共役ジエン化合物が共重合
した場合、このブロックにおける共役ジエン化合物の分
布はランダム、テーパー（分子鎖に沿ってモノマー成分
が増加又は減少するもの）、一部ブロック状又はこれら
の任意の組み合わせのいずれであってもよい。The polymer block A mainly composed of a vinyl aromatic compound has a weight ratio of the vinyl aromatic compound to the conjugated diene compound of 100/0 to 51/49, preferably 100.
A polymer block having a composition range of / 0 to 70/30, and when a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block is random or tapered (monomers along the molecular chain). The composition may be increased or decreased), partially block-shaped, or any combination thereof.
【００１６】ここで供するビニル芳香族化合物として
は、スチレン、α−メチルスチレン、ｐ−メチルスチレ
ン、ｐ−ターシャリブチルスチレン等のアルキルスチレ
ン、ｐ−メトキシスチレン、ビニルナフタレン等のうち
から１種又は２種以上が選ばれ中でもスチレン、ｐ−メ
チルスチレンが特に好ましい。また、共役ジエン化合物
としては、ブタジエン、イソプレン、ピペリレン、メチ
ルペンタジエン、フェニルブタジエン、３，４−ジメチ
ル−１，３−ヘキサジエン、４，５−ジエチル−１，３
−オクタジエン等のうちから１種又は２種以上が選ばれ
中でもブタジエン及び／又はイソプレンが特に好まし
い。The vinyl aromatic compound provided here is one or more of alkyl styrenes such as styrene, α-methyl styrene, p-methyl styrene and p-tert-butyl styrene, p-methoxy styrene and vinyl naphthalene. Among two or more selected, styrene and p-methylstyrene are particularly preferable. Further, as the conjugated diene compound, butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3
Of these, one or more selected from octadiene and the like, butadiene and / or isoprene are particularly preferable.
【００１７】ビニル芳香族化合物の含有量は、１０％以
上３０％未満であることが必要であり、１０％未満で
は、剛性が低下し、３０％を越える場合は、粗大な分散
状態となり、衝撃強度が低下する。The content of the vinyl aromatic compound is required to be 10% or more and less than 30%. If it is less than 10%, the rigidity is lowered, and if it exceeds 30%, a coarse dispersion state is formed and the impact is generated. Strength is reduced.
【００１８】上記ブロック共重合体の製造方法として
は、例えば特公昭３６−１９２８６号、特公昭４３−１
４９７９号、特公昭４９−３６９５７号公報等に記載さ
れた方法が挙げられる。更に、上記のブロック共重合体
を公知の方法、例えば特公昭４２−８７０４号、特公昭
６３−４８４１号、特公平１−３７９７０号公報に記載
された方法で水素添加させる必要がある。水素添加率が
低いとポリプロピレン樹脂との相溶性が不充分となり耐
衝撃性に劣り、また混合や成形時の熱劣化を受けやすく
好ましくない。水素添加率は、核磁気共鳴装置（ＮＭ
Ｒ）を用いた機器分析により分析できる。As the method for producing the block copolymer, for example, Japanese Patent Publication No. 36-19286 and Japanese Patent Publication No. 43-1.
Methods described in Japanese Patent Publication No. 4979, Japanese Patent Publication No. 49-36957 and the like can be mentioned. Further, it is necessary to hydrogenate the above block copolymer by a known method, for example, a method described in JP-B-42-8704, JP-B-63-4841, or JP-B-1-37970. When the hydrogenation rate is low, the compatibility with the polypropylene resin is insufficient and the impact resistance is poor, and it is not preferable because it is easily deteriorated by heat during mixing and molding. The hydrogenation rate is measured by the nuclear magnetic resonance apparatus (NM
It can be analyzed by instrumental analysis using R).
【００１９】本発明で用いる高密度ポリエチレンは、密
度が０．９６ｇ／ｃｍ3 以上で、ＭＦＲが使用する高結
晶性ポリプロピレン樹脂の０．５〜０．８倍の流動性の
高いものである。密度が０．９６ｇ／ｃｍ3 以下では、
剛性が低下し好ましくない。またＭＦＲが上記範囲以外
では、ポリプロピレン成分中に分散するとき、大粒な粒
子の分散状態となり本発明の効果が得られにくくなった
り、脆くなり耐衝撃性を悪化し好ましくない。The high-density polyethylene used in the present invention has a density of 0.96 g / cm 3 or more and is 0.5 to 0.8 times as fluid as the highly crystalline polypropylene resin used in MFR. When the density is 0.96 g / cm 3 or less,
It is not preferable because the rigidity decreases. In addition the MFR is <br/> than the above range, when dispersed in the polypropylene component, the effect of the present invention become dispersed state of the large particles became Kuku to obtain
And becomes brittle and the impact resistance deteriorates, which is not preferable.
【００２０】なお、本発明では、必要によりエチレン・
ブテン−１共重合体を用いてもよい。その共重合体は、
エチレンとブテン−１を、通常の触媒いわゆるチーグラ
ーナッタ触媒を用いて重合した共重合体であって、共重
合体中のブテン−１含量は、赤外線分光法によって測定
される値で、１５〜２５重量％、好ましくは１７〜２２
重量％。２３０℃におけるＭＦＲは使用する高結晶性ポ
リプロピレン樹脂と同等以下乃至１／２０以上のもので
ある。ＭＦＲが使用する高結晶性ポリプロピレン樹脂よ
り高い場合には、ポリプロピレン成分中に分散すると
き、粒子状に分散せず、単独で層状の分散状態となり易
く、又１／２０以下では、溶融時の粘度差が大きく微細
に分散することが困難となり本発明の効果が得られな
い。共重合体中のブテン−１含量が１５重量％未満で
は、衝撃強度の改良効果が低く、２５重量％を越えると
剛性、硬度が低下し、剛性、耐衝撃強度のバランスが悪
くなる。[0020] It should be noted that, in the present invention, ethylene, if necessary
Butene-1 copolymer may be used. The copolymer is
A copolymer obtained by polymerizing ethylene and butene-1 using a normal catalyst, a so-called Ziegler-Natta catalyst, wherein the butene-1 content in the copolymer is 15 to 25 as measured by infrared spectroscopy. % By weight, preferably 17-22
weight%. The MFR at 230 ° C. is equal to or lower than that of the highly crystalline polypropylene resin used and equal to or higher than 1/20. When the MFR is higher than that of the highly crystalline polypropylene resin used, when it is dispersed in the polypropylene component, it does not disperse in the form of particles, and tends to be in a layered dispersed state by itself. Since the difference is large and it is difficult to disperse finely, the effect of the present invention cannot be obtained. When the butene-1 content in the copolymer is less than 15% by weight, the effect of improving impact strength is low, and when it exceeds 25% by weight, the rigidity and hardness are lowered, and the balance between rigidity and impact strength is deteriorated.
【００２１】本発明で用いられる粒状又は板状の無機充
填剤の具体例としては、タルク、マイカ、クレー、ワラ
ストナイト、炭酸カルシウム、硫酸バリウム、ケイソウ
土、塩基性硫酸マグネシウム等が挙げられ、これら１種
以上を適宜使用することができる。更に、無機充填剤
は、各種処理剤で表面処理されても良い。表面処理とし
ては、例えば、シランカップリング剤系、高級脂肪酸塩
系、有機チタネート系等の各種処理が挙げられる。Specific examples of the granular or plate-like inorganic filler used in the present invention include talc, mica, clay, wollastonite, calcium carbonate, barium sulfate, diatomaceous earth, basic magnesium sulfate, and the like. These 1 or more types can be used suitably. Further, the inorganic filler may be surface-treated with various treatment agents. Examples of the surface treatment include various treatments such as a silane coupling agent type, a higher fatty acid salt type, and an organic titanate type.
【００２２】好ましい無機充填剤としては、平均粒子径
が０．３〜５μｍの微粉タルクである。最も好ましいの
は、平均粒子径が０．５〜２μｍである。平均粒子径が
０．３μｍ以下ではタルクの２次凝集が起こり分散性が
悪くなり、５μｍを越えると剛性と衝撃強度が低下す
る。ここで平均粒子径は、液相沈降方式の光透過法によ
る粒度分布測定装置により測定した粒度の累積分布曲線
における５０％の点での粒径値である。この無機充填剤
は、５〜２５重量部配合される。好ましくは、７〜２０
重量部であり、２５重量部を越えると衝撃強度が低下
し、剛性と衝撃強度のバランスが悪くなり好ましくな
い。A preferable inorganic filler is fine talc having an average particle size of 0.3 to 5 μm. Most preferably, the average particle size is 0.5 to 2 μm. When the average particle size is 0.3 μm or less, talc secondary aggregation occurs and the dispersibility deteriorates, and when it exceeds 5 μm, rigidity and impact strength decrease. Here, the average particle size is a particle size value at a point of 50% in a cumulative distribution curve of particle size measured by a particle size distribution measuring device by a liquid phase sedimentation light transmission method. This inorganic filler is mixed in 5 to 25 parts by weight. Preferably 7-20
If the amount exceeds 25 parts by weight, the impact strength is lowered and the balance between rigidity and impact strength is deteriorated, which is not preferable.
【００２３】本発明の大きな特徴は、特定の高結晶性ポ
リプロピレン樹脂に配合するエラストマー成分として、
水素添加ブロック共重合体と高密度ポリエチレンを特定
の配合比率で併用し、さらにＭＦＲを限定することにあ
る。すなわち、水素添加ブロック共重合体と高密度ポリ
エチレンを４０／６０〜８０／２０の配合比率範囲にあ
り、更にこれらのＭＦＲを相互に適当に限定することに
より、高結晶性ポリプロピレン樹脂のポリプロピレン単
独相中に分散するエラストマー凝集分散相が２相構造を
形成し、且つ粒子状で平均粒子径が１μｍ以下に微分散
していることである。A major feature of the present invention is that, as an elastomer component to be blended with a specific highly crystalline polypropylene resin,
The hydrogenated block copolymer and high density polyethylene emissions in combination with a specific blending ratio, it is an further limiting the MFR. That is, there hydrogenated block copolymer and high density polyethylene <br/> ethylene in to the mixing ratio range of 40 / 60-80 / 20, by further appropriately limited to one another these MFR, high crystallinity That is, the elastomer aggregate dispersion phase dispersed in the polypropylene single phase of the polypropylene resin forms a two-phase structure and is finely dispersed in the form of particles having an average particle diameter of 1 μm or less.
【００２４】水素添加ブロック共重合体は、耐衝撃性改
良効果が高いのに対し、ポリプロピレン樹脂の特徴であ
る剛性、硬度の低下が大きい。対して高密度ポリエチレ
ンは、耐衝撃性改良効果が低いのに対し、剛性、硬度が
高い。これら各々の特徴を引き出すために、２相構造を
形成し、且つ微分散化を計ったものである。While the hydrogenated block copolymer has a high impact resistance improving effect, it has a large decrease in rigidity and hardness which are characteristics of polypropylene resin. On the other hand, high density polyethylene
In contrast, the impact resistance improving effect is low, but the rigidity and hardness are high. In order to bring out each of these characteristics, a two-phase structure was formed and finely dispersed.
【００２５】エラストマー成分の水素添加ブロック共重
合体と高密度ポリエチレンの配合比率が４０／６０以下
では、エラストマー凝集分散相におけるポリエチレン相
を囲む水素添加ブロック共重合体相の厚みが薄くなり、
耐衝撃性の改良効果が低く、８０／２０以上では、水素
添加ブロック共重合体相の厚みが厚くなり剛性が低下
し、本発明の水素添加ブロック共重合体と高密度ポリエ
チレンの併用効果が得られない。好ましい配合比率は、
５０／５０〜７０／３０である。[0025] In the mixing ratio of the hydrogenated block copolymer and high density polyethylene emissions of the elastomer component is 40/60 or less, the thickness of the hydrogenated block copolymer phase surrounding the polyethylene emission phase <br/> in the elastomeric cohesive disperse phase Becomes thin,
The effect of improving the impact resistance is low, and at 80/20 or more, the hydrogenated block copolymer phase becomes thick and the rigidity is lowered, and the hydrogenated block copolymer of the present invention and the high density polyethylene are obtained. The combined effect of The preferred blending ratio is
It is 50/50 to 70/30.
【００２６】更に、水素添加ブロック共重合体と高密度
ポリエチレンの配合比率により、２相構造を形成する外
側の水素添加ブロック共重合体部分の膜厚が変化し、エ
ラストマー凝集分散相の平均粒子径の１０〜３０％の厚
みを持つ範囲が耐衝撃性の改良に効果的である。最も好
ましくは、１２〜２５％である。このエラストマー成分
は、５〜２５重量部配合される。好ましくは７〜２２重
量部であり、５重量部未満では、衝撃強度の改良効果が
小さく、２５重量部を越えると大きく剛性が低下し、剛
性と衝撃強度のバランスが悪く好ましくない。Furthermore, the mixing ratio of the hydrogenated block copolymer and high density <br/> polyethylene emissions, the thickness of the hydrogenated block copolymer portion of the outer forming a two-phase structure changes, elastomeric cohesive dispersion A range having a thickness of 10 to 30% of the average particle diameter of the phase is effective for improving impact resistance. Most preferably, it is 12 to 25%. This elastomer component is blended in an amount of 5 to 25 parts by weight. It is preferably from 7 to 22 parts by weight, and when it is less than 5 parts by weight, the effect of improving the impact strength is small, and when it exceeds 25 parts by weight, the rigidity is largely lowered, and the balance between the rigidity and the impact strength is unfavorable.
【００２７】本発明でいうエラストマー凝集分散相（ド
メイン）の平均粒子径とは、樹脂の超薄切片法による透
過型電子顕微鏡写真（拡大率×１００００）を撮影して
求めた。電子顕微鏡写真に写った分散粒子は完全な円形
でないため、画像処理装置（旭化成製：ＩＰ−１００
０）を用い、規定処理の凝集分散相について、その円相
当径を求め、その平均値を平均粒子径とした。The average particle diameter of the elastomer aggregate dispersed phase (domain) in the present invention is determined by taking a transmission electron microscope photograph (magnification ratio × 10000) of the resin by the ultrathin section method. Since the dispersed particles shown in the electron micrograph are not perfectly circular, an image processing apparatus (Asahi Kasei: IP-100
0) was used to determine the equivalent circle diameter of the aggregation-dispersed phase subjected to the prescribed treatment, and the average value was used as the average particle diameter.
【００２８】高結晶性ポリプロピレン樹脂のポリプロピ
レン単独成分の連続相（マトリックス）中に分散するエ
ラストマー凝集分散相が、粒子状で平均粒径が、０．１
〜１μｍの範囲に微細分散させることにより、剛性と衝
撃強度のバランスに優れる。平均粒子径が０．１μｍ以
下及び１μｍ以上では、物性バランスが悪い。好ましく
は、平均粒子径が０．２〜０．８μｍである。The elastomer aggregate dispersed phase dispersed in the continuous phase (matrix) of the polypropylene single component of the highly crystalline polypropylene resin is particulate and has an average particle size of 0.1.
By finely dispersing in the range of up to 1 μm, the balance between rigidity and impact strength is excellent. When the average particle size is 0.1 μm or less and 1 μm or more, the physical property balance is poor. Preferably, the average particle size is 0.2 to 0.8 μm.
【００２９】更に、２相構造を形成するエラストマー凝
集分散相の水素添加ブロック共重合体部分の膜厚は、内
側のポリエチレン相の平均粒子径を上記の方法により求
め、先に求められるエラストマー凝集分散相の平均粒子
径との両者の差をとり１／２倍したものである。本発明
の膜厚比は、エラストマー凝集分散相の平均粒子径と２
相構造を形成するエラストマー凝集分散相の外側の水素
添加ブロック共重合体部分の膜厚との比率である。Furthermore, the thickness of the hydrogenated block copolymer portion of the elastomeric cohesive dispersed phase forming a two-phase structure, an average particle diameter of the inner polyethylene down phase by the method described above, elastomeric cohesive required previously The difference between the average particle size of the dispersed phase and the average particle size is taken and multiplied by 1/2. The film thickness ratio of the present invention is the average particle size of the elastomer aggregate dispersed phase and 2
It is the ratio with the film thickness of the hydrogenated block copolymer portion outside the elastomer aggregate dispersion phase forming the phase structure.
【００３０】本発明のポリプロピレン樹脂複合組成物の
製造方法は、溶融混練法で機械的混練機を用いペレット
化する方法により製造することができる。例えば、本発
明の樹脂組成物を構成する各成分をヘンシェルミキサ
ー、ブレンダー等で予備混合し、次いで高速２軸押出機
にて１８０〜２５０℃の温度にて溶融混練することが好
ましい。また、水素添加ブロック共重合体と高強度ポリ
エチレンから構成されるエラストマー成分を予備混合に
先立って、予め溶融混練して用いても構わない。The polypropylene resin composite composition of the present invention can be manufactured by a method of pelletizing using a mechanical kneader in a melt kneading method. For example, it is preferable that each component constituting the resin composition of the present invention is premixed with a Henschel mixer, a blender or the like, and then melt-kneaded with a high-speed twin-screw extruder at a temperature of 180 to 250 ° C. Further, the hydrogenated block copolymer and the high strength polyethylene <br/> ethylene emission that consists of an elastomer component prior to premixing, may be used in advance melt kneading.
【００３１】そして、必要に応じて酸化防止剤、熱安定
剤、光安定剤、紫外線吸収剤、滑剤、顔料、帯電防止
剤、金属劣化防止剤、結晶造核剤、高級脂肪酸塩、難燃
剤等の各種添加剤を適宜配合することができる。このよ
うにして得られたポリプロピレン樹脂複合組成物は、射
出成形法により種々の大型成形品に用いられる。If necessary, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, pigments, antistatic agents, metal deterioration inhibitors, crystal nucleating agents, higher fatty acid salts, flame retardants, etc. Various additives can be appropriately added. The polypropylene resin composite composition thus obtained is used for various large molded articles by an injection molding method.
【００３２】[0032]
【実施例】本発明のポリプロピレン樹脂複合組成物を以
下に実施例及び比較例を挙げて具体的に説明するが、こ
れら実施例に限定されるものではない。なお、実施例及
び比較例で用いた試験方法は、次の方法によった。EXAMPLES The polypropylene resin composite composition of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The test methods used in Examples and Comparative Examples were as follows.
【００３３】メルトフローレート（ＭＦＲ）
ＡＳＴＭ Ｄ１２３８に準拠。温度：２３０℃、荷重：
２．１６ｋｇｆ
曲げ弾性率
ＡＳＴＭ Ｄ７９０に準拠。
アイゾット衝撃値
ＡＳＴＭ Ｄ２５６に準拠。
脆化温度
ＡＳＴＭ Ｄ７４６に準拠。Melt Flow Rate (MFR) According to ASTM D1238. Temperature: 230 ℃, load:
2.16 kgf Flexural Modulus Complies with ASTM D790. Izod impact value Complies with ASTM D256. Brittleness temperature According to ASTM D746.
【００３４】高速面衝撃強度の測定
厚み３ｍｍの射出成形平板を用い、東洋精機（製）落錘
グラフィックインパクトテスターＢ型により、衝撃破壊
時の全吸収エネルギーを測定。
衝撃速度：５ｍ／秒、ストライカーの径：１インチ
射出成形加工性の評価
射出成形機に、断面が幅；１０ｍｍ、厚み：１ｍｍのス
パイラルフロー試験用金型を取り付け、樹脂温度、金型
温度、出射圧力、出射速度、出射成形時間を同一として
樹脂の流動性を比較し、流動距離が大きく薄肉成形品も
容易に成形できる場合を優、悪い場合を不良として評
価。Measurement of high-speed surface impact strength Using an injection-molded flat plate with a thickness of 3 mm, the total absorbed energy at the time of impact destruction was measured by a falling weight graphic impact tester B type manufactured by Toyo Seiki Co., Ltd. Impact speed: 5 m / sec, Striker diameter: 1 inch Evaluation of injection molding workability A mold for spiral flow test with a cross section of width 10 mm and thickness 1 mm was attached to an injection molding machine, and the resin temperature, mold temperature, The resin flowability is compared under the same ejection pressure, ejection velocity, and ejection molding time, and when the flow distance is large and thin-walled molded products can be easily molded, it is rated as bad, and when bad, it is evaluated as defective.
【００３５】エラストマー凝集分散相の分散状態、平均
粒子径及び膜厚の測定
厚み３ｍｍの射出成形平板の中央部分の一部を切出し、
四酸化ルテニウムで染色を施した後、超ミクロトームを
使用して、超薄切片を切出し、透過型電子顕微鏡（日立
製）を用い、平均的な凝集分散相のミクロ構造の電子顕
微鏡像を観察し、拡大倍率１００００倍で撮影して、視
野の大きさ縦２２０×横１８０ｍｍの写真を作成した。Measurement of Dispersion State of Emulsion Coagulation Dispersed Phase, Average Particle Size and Film Thickness A part of the central portion of an injection-molded flat plate having a thickness of 3 mm was cut out,
After staining with ruthenium tetroxide, an ultrathin section was cut out using an ultramicrotome, and a transmission electron microscope (manufactured by Hitachi) was used to observe an electron microscopic image of the microstructure of the average coagulated dispersed phase. Then, the image was taken at a magnification of 10,000 times to prepare a photograph having a field of view of 220 mm in length and 180 mm in width.
【００３６】写真には、無機充填剤（例えばタルク）と
四酸化ルテニウムで染色されたエラストマー成分が、黒
い凝集分散相として写り観察される。タルクは、細長く
燐片状に、そしてエラストマー成分は、粒子状或いは層
状等ににほぼ均一に分散した様子が観察される。更に、
エラストマー凝集分散相は、内側のポリエチレン相が結
晶ラメラ又は薄黒く染色され、それを包み囲む様に外側
に水素添加ブロック共重合体が最も黒く染色された２相
構造が観察される。電子顕微鏡写真に写った分散粒子は
完全な円形でないため、画像処理装置（旭化成製：ＩＰ
−１０００）を用い、凝集分散相の最小除去面積を０．
００５μｍ2 として画像処理し、その円相当径の平均値
を求め、凝集分散相の平均粒子径とした。In the photograph, the inorganic filler (for example, talc) and the elastomer component dyed with ruthenium tetraoxide are shown as a black cohesive dispersed phase. It is observed that talc is elongated and scale-like, and the elastomer component is almost uniformly dispersed in particles or layers. Furthermore,
Elastomeric cohesive dispersed phase, inner polyethylene emission phase is dyed crystal lamellae or darken, the hydrogenated block copolymer outside as surrounding packaging it is most black stained 2 phase structure is observed. Since the dispersed particles shown in the electron micrograph are not perfectly circular, an image processing device (made by Asahi Kasei: IP
-1000) and the minimum removal area of the aggregated dispersed phase is set to 0.
Image processing was performed with a diameter of 005 μm 2 , and the average value of the equivalent circle diameters was determined and used as the average particle diameter of the aggregated dispersed phase.
【００３７】次に、２相構造を形成するエラストマー凝
集分散相の外側の水素添加ブロック共重合体部分の膜厚
は、内側のポリエチレン相の平均粒子径を上記の方法に
より求め、先に求められるエラストマー凝集分散相の平
均粒子径との両者の差をとり１／２倍したものである。
更に、エラストマー凝集分散相の平均粒子径に対する水
素添加ブロック共重合体部分の膜厚の比率を膜厚比とし
た。Next, the thickness of the outer hydrogenated block copolymer portion of the elastomeric cohesive dispersed phase forming a two-phase structure, the average particle diameter of the inner polyethylene emission phase determined by the above method, obtained previously The difference between the average particle diameter and the average particle diameter of the elastomer-aggregated dispersed phase is multiplied by 1/2.
Further, the ratio of the film thickness of the hydrogenated block copolymer portion to the average particle size of the elastomer aggregate dispersed phase was defined as the film thickness ratio.
【００３８】総合評価
無機充填剤配合量と曲げ弾性率との関係、エラストマー
成分配合量とアイゾット値との関係及び成形加工性のバ
ランスを比較し、バランスの良い場合を◎、悪い場合を
×として評価した。Comprehensive Evaluation The relationship between the blending amount of the inorganic filler and the flexural modulus, the relationship between the blending amount of the elastomer component and the Izod value, and the balance of the molding processability were compared. evaluated.
【００３９】実施例１〜５、比較例１〜１１
高結晶性ポリプロピレン樹脂、水素添加ブロック共重合
体、高密度ポリエチレン／又はエチレン・ブテン−１共
重合体及び無機重点剤を表３，表４に記載する各成分の
配合内容の他に、組成物に対し、ペンタエリスリチル−
テトラキス〔３−（３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフェニル）プロピネート〕０．３ＰＨＲ、トリス
（２，４−ジ−ｔ−ブチルフェニル）ホスファイト０．
２ＰＨＲ、ステアリン酸マグネシウム０．２ＰＨＲ、リ
ン酸２，２’メチレンビス（４，６−ジ−ｔ−ブチルフ
ェニル）ナトリウム０．２ＰＨＲを添加し、ヘンシェル
ミキサーにて１分間の予備混合を行い、該混合物を高速
２軸混練機を用い、混練温度１８０℃〜２００℃で押出
し、ペレット状の樹脂組成物を得た。得られたペレット
を射出成形にて物性試験用試験片に成形し、各種の物性
測定を実施し、その結果を表３、表４にまとめて示す。
表３、表４に記載する各原料は次のものを用い、配合割
合は重量部を示す。Examples 1 to 5 and Comparative Examples 1 to 11 Highly crystalline polypropylene resins, hydrogenated block copolymers, high density polyethylene / or ethylene butene-1 copolymers and inorganic additives are shown in Tables 3 and 4. In addition to the content of each component described in 1., pentaerythrityl-
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.3PHR, tris (2,4-di-t-butylphenyl) phosphite.
2 PHR, 0.2 PHR of magnesium stearate, 0.2 PHR of 2,2'methylenebis (4,6-di-t-butylphenyl) sodium phosphate were added, and premixed for 1 minute with a Henschel mixer to prepare a mixture. Was extruded at a kneading temperature of 180 ° C. to 200 ° C. using a high-speed biaxial kneader to obtain a pellet-shaped resin composition. The obtained pellets were molded into test pieces for physical properties by injection molding, various physical properties were measured, and the results are summarized in Tables 3 and 4.
The following raw materials are used as the raw materials shown in Tables 3 and 4, and the mixing ratios are parts by weight.
【００４０】ポリプロピレン樹脂
特開平５−６５３２１号公報に記載される立体規則性の
高い高活性触媒、重合条件を応用して表１に示すＡ−１
〜Ａ−６の高結晶性ポリプロピレン樹脂を重合して用い
た。Polypropylene resin A-1 shown in Table 1 by applying the high stereoregular highly active catalyst and polymerization conditions described in JP-A-5-65321.
The highly crystalline polypropylene resins of ~ A-6 were polymerized and used.
【００４１】[0041]
【表１】 [Table 1]
【００４２】水素添加ブロック共重合体
ｎ−ブチルリチウムを重合触媒とし、シクロヘキサン液
中でテトラヒドロフランをビニル含有量調節剤として、
スチレンとブタジエンをアニオンブロック共重合するこ
とにより、表２に示すブロック共重合体を合成した。な
お、ポリマー構造はモノマーの仕込み、分子量は触媒量
を変化させることによりコントロールした。スチレン含
量は、紫外線分光光度計を、ビニル含量は、核磁気共鳴
装置を用いて測定した。Hydrogenated block copolymer n-butyllithium was used as a polymerization catalyst, and tetrahydrofuran was used as a vinyl content modifier in cyclohexane solution.
The block copolymers shown in Table 2 were synthesized by anion block copolymerizing styrene and butadiene. The polymer structure was controlled by charging a monomer, and the molecular weight was controlled by changing the catalyst amount. The styrene content was measured with an ultraviolet spectrophotometer, and the vinyl content was measured with a nuclear magnetic resonance apparatus.
【００４３】次に各ブロック共重合体をジ−ｐ−トリル
ビス（１−シクロペンタジエン）チタニウムとｎ−ブチ
ルリチウムを水添触媒として、水素圧５ｋｇ／ｃｍ3 、
温度５０℃で２時間水素添加を行った。ブタジエンブロ
ック部分の二重結合の９０％以上は水素添加され、スチ
レンブロック部分のベンゼン環は殆ど水添されないで残
った。水素添加率は、核磁気共鳴装置を用いて測定し
た。Next, each block copolymer was treated with di-p-tolylbis (1-cyclopentadiene) titanium and n-butyllithium as a hydrogenation catalyst to obtain a hydrogen pressure of 5 kg / cm 3 ,
Hydrogenation was carried out at a temperature of 50 ° C. for 2 hours. 90% or more of the double bonds in the butadiene block portion were hydrogenated, and the benzene ring in the styrene block portion remained almost unhydrogenated. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus.
【００４４】[0044]
【表２】 [Table 2]
【００４５】高密度ポリエチレン
Ｃ−１：密度＝０．９６ｇ／ｃｍ3 ，ＭＦＲ＝ ２ｇ／
１０分
Ｃ−２：密度＝０．９７ｇ／ｃｍ3 ，ＭＦＲ＝２０ｇ／
１０分
Ｃ−３：密度＝０．９７ｇ／ｃｍ3 ，ＭＦＲ＝５５ｇ／
１０分
Ｃ−４：密度＝０．９４ｇ／ｃｍ3 ，ＭＦＲ＝１５ｇ／
１０分
エチレン・ブテン−１共重合体
Ｅ−１：ブテン−１含量＝２０％，ＭＦＲ＝ ７ｇ／１
０分
Ｅ−２：ブテン−１含量＝１７％，ＭＦＲ＝３５ｇ／１
０分
無機充填剤
Ｄ−１：浅田製粉（製）ＭＭＲ、平均粒径１μｍのタル
ク。High-density polyethylene C-1: Density = 0.96 g / cm 3 , MFR = 2 g /
10 minutes C-2: density = 0.97 g / cm 3 , MFR = 20 g /
10 minutes C-3: density = 0.97 g / cm 3 , MFR = 55 g /
10 minutes C-4: Density = 0.94 g / cm 3 , MFR = 15 g /
10 minutes Ethylene / butene-1 copolymer E-1: butene-1 content = 20%, MFR = 7 g / 1
0 minutes E-2: butene-1 content = 17%, MFR = 35 g / 1
0 minutes Inorganic filler D-1: Asada Milling (manufactured) MMR, talc having an average particle size of 1 μm.
【００４６】比較例１
実施例４の組成で、ポリプロピレン樹脂にエチレン含有
量が７％品を用いると凝集散相が大きくなり、剛性と耐
衝撃性が低い。Comparative Example 1 When a polypropylene resin having a composition of 7% and an ethylene content of 7% is used, the aggregated and dispersed phase becomes large, and the rigidity and impact resistance are low.
【００４７】比較例２
実施例４の組成で、ポリプロピレン樹脂をＭＦＲの高い
ものを用い、更に水素添加ブロック共重合体、高密度ポ
リエチレンも高流動性に変えた場合、成形性に優れるが
脆化温度は高く、耐衝撃性に劣るものである。Comparative Example 2 When a polypropylene resin having a high MFR was used in the composition of Example 4 and the hydrogenated block copolymer and the high-density polyethylene were changed to have high fluidity, the moldability was excellent but the embrittlement was caused. The temperature is high and the impact resistance is poor.
【００４８】比較例３
実施例４の組成で、ポリプロピレン樹脂をＭＦＲの低い
ものを用い、更に水素添加ブロック共重合体、高密度ポ
リエチレンも低流動性に変えた場合、剛性や耐衝撃性の
物性に優れるものの、出射成形加工性が悪く、出射成形
温度、圧力を高くする必要があり、大型薄肉成形に適さ
ない。Comparative Example 3 When a polypropylene resin having a low MFR was used in the composition of Example 4 and the hydrogenated block copolymer and high-density polyethylene were changed to have low fluidity, the physical properties of rigidity and impact resistance were improved. However, it is not suitable for large-scale thin-wall molding because it has poor workability for extrusion molding and requires high extrusion molding temperature and pressure.
【００４９】比較例４
実施例４の組成で、水素添加ブロック共重合体のスチレ
ン含量が４０％になると凝集分散相が大きくなり２相構
造に成りにくく、物性バランスに劣る。Comparative Example 4 With the composition of Example 4, when the styrene content of the hydrogenated block copolymer was 40%, the coagulated dispersed phase became large and it was difficult to form a two-phase structure, resulting in poor physical property balance.
【００５０】比較例５
実施例４の組成で、水素添加ブロック共重合体のＭＦＲ
がポリプロピレン樹脂より高いものを用いると、凝集分
散相が層状となり、物性バランスに劣る。Comparative Example 5 MFR of hydrogenated block copolymer having the composition of Example 4
However, when a resin having a higher value than that of polypropylene resin is used, the coagulation-dispersed phase becomes layered, resulting in poor physical property balance.
【００５１】比較例６
実施例４の組成で、水素添加ブロック共重合体とポリプ
ロピレン樹脂のＭＦＲ比が大きい場合、凝集分散相が２
相構造でなく、物性バランスに劣る。Comparative Example 6 In the composition of Example 4, when the MFR ratio of the hydrogenated block copolymer and the polypropylene resin was large, the coagulated dispersed phase was 2
It does not have a phase structure and has poor physical property balance.
【００５２】比較例７
実施例４の組成で、水素添加ブロック共重合体と高密度
ポリエチレンの配合比率が約２８／７２となると水素添
加ブロック共重合体の膜厚が薄く、脆化温度は高く、耐
衝撃性に劣るものである。Comparative Example 7 In the composition of Example 4, when the blending ratio of the hydrogenated block copolymer and the high density polyethylene was about 28/72, the hydrogenated block copolymer was thin and the embrittlement temperature was high. , Inferior in impact resistance.
【００５３】比較例８
実施例４の組成で、水素添加ブロック共重合体と高密度
ポリエチレンの配合比率が約８９／１１となると水素添
加ブロック共重合体の膜厚が厚くなり、剛性に劣る。Comparative Example 8 In the composition of Example 4, when the blending ratio of the hydrogenated block copolymer and the high density polyethylene was about 89/11, the film thickness of the hydrogenated block copolymer was large and the rigidity was poor.
【００５４】比較例９
実施例４の組成で、高密度ポリエチレンのＭＦＲがポリ
プロピレン樹脂より低い場合、凝集分散相の平均粒子径
が大きくなり、物性バランスに劣る。Comparative Example 9 With the composition of Example 4, when the MFR of the high-density polyethylene is lower than that of the polypropylene resin, the average particle size of the coagulation-dispersed phase becomes large and the balance of physical properties is poor.
【００５５】比較例１０
実施例４の組成で、高密度ポリエチレンの密度か低い場
合、剛性に劣る。Comparative Example 10 With the composition of Example 4, when the density of the high-density polyethylene is low, the rigidity is poor.
【００５６】比較例１１表４に示す
組成で、エチレン・ブテン−１共重合体のＭ
ＦＲがポリプロピレン樹脂より高いものを用いると、凝
集分散相が層状となり、物性バランスに劣るものであっ
た。Comparative Example 11 M of ethylene / butene-1 copolymer having the composition shown in Table 4 was used.
When the FR having a higher FR than that of the polypropylene resin was used, the coagulation-dispersed phase was layered and the physical property balance was poor.
【００５７】[0057]
【表３】 [Table 3]
【００５８】[0058]
【表４】 [Table 4]
【００５９】[0059]
【発明の効果】本発明は、高流動性の高結晶性ポリプロ
ピレン樹脂に特定のＭＦＲをもつ水素添加ブロック共重
合体と高密度ポリエチレンを特定の配合比率で併用配合
したエラストマー成分と無機充填剤を配合することによ
り、ポリプロピレン樹脂のポリプロピレン単独成分の連
続相中に分散するエラストマー凝集分散相が２相構造を
形成し、且つ粒子状で微細に分散させることができ、高
い物性バランスを達成し、大型薄肉成形品に好適に用い
られる。According to the present invention, high fluidity of the high crystalline polypropylene in a specific hydrogenated block copolymer having a MFR of high-density polyethylene down the specific combination blended at a ratio elastomeric component and an inorganic filler By blending, the elastomer aggregate dispersion phase dispersed in the continuous phase of the polypropylene single component of the polypropylene resin can form a two-phase structure, and can be finely dispersed in the form of particles, achieving a high physical property balance, Suitable for large-sized thin-walled molded products.
【図１】実施例４の樹脂複合組成物のエラストマーの分
散状態を表す粒子構造の電子顕微鏡写真である。FIG. 1 is an electron micrograph of a particle structure showing a dispersed state of an elastomer of a resin composite composition of Example 4.
【図２】図１のエラストマーの分散粒子構造の一部拡大
写真である。2 is a partially enlarged photograph of a structure of dispersed particles of the elastomer of FIG.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 23:04） (56)参考文献 特開 昭57−73034（ＪＰ，Ａ) 特開 平２−51551（ＪＰ，Ａ) 特開 昭61−152752（ＪＰ，Ａ) 特開 平６−172593（ＪＰ，Ａ) 特開 平７−48485（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 23/00 - 23/36 C08L 53/00 - 53/02 Continuation of front page (51) Int.Cl. 7 identification code FI C08L 23:04) (56) Reference JP-A-57-73034 (JP, A) JP-A-2-51551 (JP, A) JP-A-SHO 61-152752 (JP, A) JP-A-6-172593 (JP, A) JP-A-7-48485 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08L 23/00 -23/36 C08L 53/00-53/02
Claims (2)
０ｇ／１０分、１２０℃における１，２，４−トリクロ
ロベンゼン不溶分の重量割合が５０％以上の高結晶性ポ
リプロピレン単独重合体もしくはエチレン含有量４重量
％未満のエチレン−プロピレンブロック共重合体を５０
〜９０重量部、〔ロ〕（ａ）と（ｂ）成分から構成され
るエラストマーで、（ａ）成分は、少なくとも１個のビ
ニル芳香族化合物を主体とする重合体ブロックＡと共役
ジエン化合物部分の不飽和が２０％を越えない程度にま
で水素添加された少なくとも１個のオレフィン化合物を
主体とする重合体ブロックＢとからなりビニル芳香族化
合物の含有量が１０％以上３０％未満、メルトフローレ
ートが使用する〔イ〕成分の０．３〜０．６倍の水素添
加ブロック共重合体、（ｂ）成分は、密度が０．９６ｇ
／ｃｍ3 以上、メルトフローレートが使用する〔イ〕成
分の０．５〜０．８倍の高密度ポリエチレン、これら
（ａ）と（ｂ）の配合比率は４０／６０〜８０／２０重
量％の範囲のエラストマーを５〜２５重量部、〔ハ〕粒
状又は板状の無機充填剤を５〜２５重量部からなり、高
結晶性ポリプロピレン樹脂のポリプロピレン単独成分の
連続相中に分散するエラストマー凝集分散相は、内側に
ポリエチレン又はポリエチレンとエチレン・ポリプロピ
レン共重合体の混和状態で、外側に上記（ａ）成分であ
る水素添加ブロック共重合体となる２相構造を形成する
ことを特徴とするポリプロピレン樹脂複合組成物。1. A melt flow rate of 10 to 15
A highly crystalline polypropylene homopolymer having a weight ratio of 1,2,4-trichlorobenzene insoluble matter at 0 ° C / 10 minutes and 120 ° C of 50% or more or an ethylene-propylene block copolymer having an ethylene content of less than 4% by weight. Fifty
90 parts by weight, with [B] (a) and (b) formed know configured elastomer, (a) component, the polymer block A and a conjugated diene compound portion consisting mainly of at least one vinyl aromatic compound A polymer block B mainly composed of at least one olefin compound hydrogenated to such an extent that the unsaturation of the vinyl aromatic compound does not exceed 20%, and the content of the vinyl aromatic compound is 10% or more and less than 30%. Rate is 0.3 to 0.6 times the hydrogenated block copolymer of the component (a), and the component (b) has a density of 0.96 g.
/ Cm 3 or more, melt flow rate used [a]
Min 0.5-0.8 times the high-density polyethylene, these <br/> (a) and the scope of the elastomeric ratio of 40 / 60-80 / 20% by weight of (b) 5 to 25 Parts by weight, 5 to 25 parts by weight of [c] granular or plate-like inorganic filler, and dispersed in the continuous phase of the polypropylene single component of the highly crystalline polypropylene resin, the elastomer-aggregated dispersed phase has polyethylene or polyethylene inside. and in admixture state of an ethylene-polypropylene copolymer, the outer side to the (a) that the polypropylene resin composite composition characterized to form a two-phase structure comprising a hydrogenated block copolymer as the component.
均粒子径を０．１〜１μｍに微細分散し、更にその平均
粒子径と２相構造を形成する外側の水素添加ブロック共
重合体の厚みとの比率（膜厚比）が１０〜３０％である
ことを特徴とする請求項１記載のポリプロピレン樹脂複
合組成物。2. The elastomer coagulated dispersed phase is finely dispersed in the form of particles having an average particle size of 0.1 to 1 μm, and further the thickness of the outer hydrogenated block copolymer forming a two-phase structure with the average particle size. The polypropylene resin composite composition according to claim 1, wherein the ratio (film thickness ratio) is 10 to 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33093394A JP3525531B2 (en) | 1994-05-06 | 1994-12-09 | Polypropylene resin composite composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-116031 | 1994-05-06 | ||
| JP11603194 | 1994-05-06 | ||
| JP33093394A JP3525531B2 (en) | 1994-05-06 | 1994-12-09 | Polypropylene resin composite composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0820690A JPH0820690A (en) | 1996-01-23 |
| JP3525531B2 true JP3525531B2 (en) | 2004-05-10 |
Family
ID=26454421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33093394A Expired - Fee Related JP3525531B2 (en) | 1994-05-06 | 1994-12-09 | Polypropylene resin composite composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3525531B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3683409B2 (en) * | 1997-05-28 | 2005-08-17 | 三井化学株式会社 | Polypropylene resin composition for automobile interior and exterior |
| US6214934B1 (en) | 1997-05-28 | 2001-04-10 | Mitsui Chemicals Inc | Polypropylene resin composition for use in automotive inner and outer trims |
| EP0926195A1 (en) * | 1997-12-26 | 1999-06-30 | Japan Polychem Corporation | Polypropylene resin composition |
| JP2001181473A (en) * | 1999-12-27 | 2001-07-03 | Japan Polychem Corp | Polypropylene-based resin composition excellent in moldability and physical property |
| JP2006194318A (en) * | 2005-01-12 | 2006-07-27 | Asahi Kasei Chemicals Corp | Polypropylene resin composition pipe |
| JP4931224B2 (en) * | 2007-04-12 | 2012-05-16 | 旭化成ケミカルズ株式会社 | Resin composition molded into secondary battery case |
| US10106663B2 (en) | 2016-08-03 | 2018-10-23 | Toyoda Gosei Co., Ltd. | Foamable polypropylene resin composition and molded body |
-
1994
- 1994-12-09 JP JP33093394A patent/JP3525531B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0820690A (en) | 1996-01-23 |
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