201231538 六、發明說明： 【發明戶斤屬之技術領域】 技術領域 本發明係有關於一種適合於射出成形的聚丙烯樹脂組 成物及將該樹脂組成物射出成形而製得之成形品。 本發明係根據2010年12月15日在日本所申請的特願 2010-279656號主張優先權，且在此援用其内容。 C先前技術3 背景技術 將聚丙烯作為主成分的聚丙烯樹脂組成物係廉價且機 械物性優異，因此，被使用在各種用途，且亦廣泛地使用 在衣物箱或食品容器之外殼類等。 . 於衣物箱或外殼類中，為了作成可辨識收納物，會要 求透明性。又，為了防止輸送中或使用時之破損，會要求 高耐衝擊強度。再者，當具有鉸鏈部時，會要求彎折時的 耐白化性。又，由於衣物箱或外殼類係藉由射出成形而成 形，因此，亦會要求射出成形性。 以往，在要求透明性之成形品中，會使用如專利文獻1 所揭示般含有乙烯.丙烯之隨機共聚物作為主成分的樹脂 組成物。又，在要求高耐衝擊強度之成形品中’會使用如 專利文獻2、專利文獻3所揭示般含有嵌段聚丙稀作為主成 分的樹脂組成物。 先行技術文獻 專利文獻 3 201231538 [專利文獻1]日本專利公開公報特表2008-540756號公 報 [專利文獻2]日本特開平7-3087號公報 [專利文獻3]日本特開平9-31264號公報 【發明内容】 發明概要 發明欲解決之課題 然而’自專利文獻1所揭示之樹脂組成物製得之成形品 會有耐衝擊強度，特別是低溫下的耐衝擊強度不足之情 形。自專利文獻2、專利文獻3所揭示之樹脂組成物製得之 成形品會有透明性及耐白化性不足之情形。 本發明之目的係提供一種透明性、耐白化性及低溫衝 擊強度優異之射出成形用聚丙烯樹脂組成物及成形品。 用以欲解決課題之手段 本發明之射出成形用聚丙烯樹脂組成物係含有丙烯系 樹脂材料及結晶化核劑者，其係二曱苯可溶份M135°c之四 氫萘中的極限黏度為〇.8dl/g至1.4dl/g，且依據日本工業規格 JISK7210’於溫度230°C、負載21.6N之條件下所測定的熔 融流率係5g/l〇分至i5g/l〇分，又，前述丙烯系樹脂材料係 於乙烯單元為2.0質量％至4.0質量％之乙烯.丙烯共聚物之 存在下，使乙烯單元為74質量％至86質量％之乙烯.1-丁稀 共聚物聚合者’又’在將射出成形用聚丙烯樹脂組成物作 成100質量。/°時，乙烯.1-丁烯共聚物之含量係10質量％至20 質量％。 4 201231538 本發明之射出成形用聚丙烯樹脂組成物係相對於丙烯 系樹脂材料100質量份，結晶化核劑之含量為0 01質量份至 0.5質量份。 本發明之成形品係將前述射出成形用聚丙烯樹脂組成 物射出成形者。 發明效果 本發明之射出成形用聚丙烯樹脂組成物係透明性、耐 白化性及低溫衝擊強度優異’且適合於射出成形。 E：實施方式：！ 用以實施發明之形態 本發明之射出成形用聚丙稀樹脂組成物（以下，簡稱作 「樹脂組成物」）係含有丙烯系樹脂材料及結晶化核劑。 於本發明之樹脂組成物中，二曱苯可溶份於135°c之四 氫萘中的極限黏度為0.8dl/g至1.4dl/g，且宜為〇 8di/g至 1.2dl/g。若樹脂組成物之極限黏度大於前述上限值，則會 有耐白化性及透明性降低之傾向。樹脂組成物之二曱苯可 溶份之極限黏度係大幅地依存乙烯.丨_丁烯共聚物之黏 度’然而，用以將極限黏度作成小於前述下限值之丙烯系 樹脂材料係製造困難。 又，樹脂組成物之熔融流率（MFR)係5g/l〇分至15g/1〇 分，且宜為8g/l〇分至12g/10分。在此，MFR係依據jiS κ 72丨〇，於溫度230t：、負載21.6Ν之條件下所測定之值。若 樹脂組成物之MFR小於前述下限值，則射出成形性會降 低’若大於前述上限值，則低溫衝擊強度會降低。 201231538 (丙稀系樹脂材料） 丙烯系樹脂材料係以下反應摻合型聚丙烯，即：於聚 合反應器内，在乙烯.丙烯共聚物之存在下使乙烯· 1-丁 烯共聚物聚合而製得者。 另，乙烯· 1-丁烯共聚物係橡膠成分。 藉由於乙烯.丙烯共聚物之存在下使乙烯.1-丁烯共 聚物聚合，可提高生產性。又，由於材料之分散性會提高， 因此，亦會提升物性平衡。 前述丙烯系樹脂材料可藉由多段聚合來製造。舉例言 之，可藉由第一段之聚合反應器，聚合乙烯-丙烯共聚物， 並將所製得之乙烯-丙烯共聚物供給至第二段之聚合反應 器，同時藉由第二段之聚合反應器，聚合乙烯· 1-丁烯共 聚物，藉此，製得丙烯系樹脂材料。於該方法中，藉由第 二段之聚合反應器，混合乙烯-丙烯共聚物與生成的乙烯· 1-丁烯共聚物。 另，多段聚合並不限於前述方法，亦可藉由複數聚合 反應器聚合乙烯-丙烯共聚物，且亦可藉由複數聚合反應器 聚合乙烯.1-丁烯共聚物。 使用在聚合的觸媒可使用公知之烯烴聚合觸媒，其 中，若由可輕易地製造顯現所期望物性之丙烯系樹脂材料 之觀點來看，則宜為戚格勒·納他觸媒。 又，聚合時，為了MFR之調整，亦可依需要添加氫。 乙烯.丙烯共聚物中的乙烯單元含量係2.0質量％至4.0 質量％，且更宜為3.0質量％至4.0質量％。若乙烯.丙烯共 201231538 ==烯單元含量大於前述上限值，則會有丙烯系樹 月曰材枓之製造_之傾向，若小於前訂限值，則會有所 製得之樹脂組成物之透明性與低溫衝擊強度降低之情形。 乙烯.1-丁稀共聚物中的乙稀單元含量係74質量％至86 質量。/。’且宜為79質量％至84質量％。若乙烯.丨_丁烯共聚 物中的乙稀單元含4大於前述上限值，則會有所之 脂組成物之低溫衝擊強度降低之傾向，若小於前述下限 值’則會有丙稀請脂材料之製造困難之傾向，並有樹脂 組成物之剛性、透明性降低之情形。 樹脂組成物中的乙烯·b丁稀共聚物之含量係於將樹 月曰組成物作成100質量％時的1〇質量％至2〇質量％ ,且宜為 12質量％至16質量％。若乙烯.丨丁烯共聚物之含量大於前 述上限值，則會有剛性降低之傾向，若小於前述下限值， 則會有所製得之樹脂組成物之低溫衝擊強度降低之傾向。 (結晶化核劑） 結晶化核劑係促進聚丙烯結晶核之形成，並提升所製 得之樹脂組成物之透明性或剛性。藉由含有結晶化核劑， 可將霾度值(JISK7105，lmm厚）輕易地作成30%以下。 結晶化核劑之具體例可列舉如：山梨醇化合物、羧酸 之金屬鹽、芳香族磷酸酯系化合物、二氧化矽、滑石等。 於臭氣少之觀點中，宜為芳香族磷酸酯系化合物。 舉例言之，山梨醇化合物可列舉如：二亞苄基山梨醇、 1，3,2,4_一-(甲基亞苄基）山梨醇、ι，3,2,4-(乙基亞节基）山梨 醇、1，3,2,4-(甲氧基亞苄基）山梨醇、丨，3,2,4-(乙氧基亞苄基） 201231538 山梨醇、1,2,3-三去氧-4,6-5,7-雙-〇-[(4-丙基苯基）亞甲基] 壬醇等。 舉例言之，羧酸之金屬鹽可列舉如：己二酸鈉、己二 酸鉀、己二酸紹、癸二酸鈉、癸二酸斜、癸二酸铭、安息 香酸鈉、安息香酸鋁、二-對-t-丁基安息香酸鋁、二-對-t-丁基安息香酸鈦、二-對-t-丁基安息香酸鉻、羥基-二-t-丁基 安息香酸鋁等。 又，結晶化核劑可使用三胺苯衍生物。 結晶化核劑之含量係相對於丙稀系樹脂材料100質量 份，宜為0.01質量份至0.5質量份，且更宜為0.1質量份至0.4 質量份。不過，當結晶化核劑為三胺苯衍生物時，宜為0.01 質量份至0.02質量份。若結晶化核劑之含量為前述下限值 以上，則可進一步地提高自樹脂組成物製得之成形品之透 明性，若為前述上限值以下，則可抑制臭氣。 (其他聚合物） 於樹脂組成物中，依需要亦可含有其他聚合物。 其他聚合物可使用公知之熱可塑性樹脂或熱硬化性樹脂。 舉例言之，熱可塑性樹脂可列舉如：乙烯或α-烯烴單 獨聚合物、乙烯或碳數3至10之烯烴之共聚物、該等之 混合物、耐綸、聚碳酸酯、聚氧化二曱苯、石油樹脂等。 舉例言之，乙烯或烯烴單獨聚合物可列舉如：高密 度聚乙烯、低密度聚乙烯、聚丙烯、聚-1-丁烯、聚-1-戊烯、 聚-1-己烯、聚(3-甲基-1-戊烯）、聚(3-曱基-1-丁烯）、聚(4-曱基-1-戊烯）、聚-1-己烯、聚-1-庚烯、聚-1-辛烯、聚-1-癸 8 201231538 烯、聚苯乙烯及該等之組合。於該等中，宜為聚丙烯。 (添加劑） 於本發明之樹脂組成物中，舉例言之，亦可含有抗氧 化劑、鹽酸吸收劑、耐熱安定劑、光安定劑、紫外線吸收 劑、内部滑劑、外部滑劑、抗靜電劑、難燃劑、分散劑、 銅抑制劑、中和劑、可塑劑、發泡劑、抗氣泡劑、交聯劑、 過氧化物等之添加劑作為任意成分。 (製造方法） 前述樹脂組成物可藉由下述來製造，即：在業已摻合 丙烯系樹脂材料、結晶化核劑及依需要之其他聚合物、添 加劑後，使用單軸押出機、雙軸押出機、班布里混合機、 捏揉機、報磨機等公知之混練機而’熔融混練者。 (成形品） 前述樹脂組成物係藉由射出成形而加工為成形品。 射出成形時之條件並無特殊之限制，可按照目標成形 品之形狀或大小、使用的射出成形機之種類或規模而適當 地選擇，然而，成形溫度宜為200°C至260°C。若成形溫度 為前述下限值以上，則可確保充分之成形性，若為前述上 限值以下，則可防止樹脂組成物之熱劣化。 實施例 於以下實施例及比較例中，「％」係指「質量％」，「份」 係指「質量份」。 (實施例1至實施例10、比較例1至比較例10) 使用直列地包含有全部四段之聚合反應器之聚合裝 201231538 置，且藉由前段二段之聚合反應器，聚合乙烯·丙烯共聚 物，並將該等供給至後段二段之聚合反應器，且藉由後段 二段之聚合反應器，聚合乙烯· 1-丁烯共聚物（於表1至表3 中，標示為「C2C4」。），或乙烯.丙烯共聚物(於表1至表3 中，標示為「C2C3」。）。此時，藉由調整乙烯供給量、氫 供給量、聚合溫度、聚合壓力、觸媒之添加量，製得表1至 表3所示之丙稀系樹脂材料。 於該丙烯系樹脂材料10 0份中摻合結晶化核劑（美利肯 (Milliken)公司製美利得(Millad)3988)0.2份，並使用押出 機，以230°C熔融混練而製得樹脂組成物。 (比較例11) 使用於乙烯·丙烯隨機共聚物中摻合有橡膠成分之樹 脂組成物（SunAllomer公司製PM633V)。 10 201231538 [表l] 實施例編號 1 2 3 4 5 6 7 8 9 10 樹脂組成物之主成分 PP PP PP PP PP PP PP PP PP PP PP之乙烯含量(％) 3.5 3.5 3.4 2.0 3.8 3.5 3.5 3.5 3.5 3.5 橡膠成分之種類 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 橡膠成分之含有率(％) 12 13 13 13 13 10 20 13 13 13 橡膠成分中的乙烯 單元含量(％) 81 82 82 82 82 82 82 82 86 74 橡耀成分之混合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 極限黏度(dl/g) 0.8 1.0 1.4 1.1 1.0 1.0 1.0 1.0 1.0 1.0 MFR(g/分） 11 10 10 10 30 10 10 15 10 10 結晶化核劑之含量(份） 0.2 0.2 0.2 0.2 0,2 0.2 0.2 0.2 0.2 0.2 生產性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 霾度(％) 10 10 12 13 10 9 15 11 16 9 财白化性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 彎曲彈性率(MPa) 850 860 890 1030 840 890 800 870 880 800 〇°C下的 耐衝擊性 面衝擊強度(J) 22 23 22 20 23 20 29 21 20 23 破裂狀況 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 [表2]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition suitable for injection molding and a molded article obtained by injection molding the resin composition. The present invention claims priority from Japanese Patent Application No. 2010-279656, filed on Jan. C. Prior art 3 Background Art A polypropylene resin composition containing polypropylene as a main component is inexpensive and excellent in mechanical properties. Therefore, it is used in various applications, and is also widely used in cases of clothes boxes or food containers. In the case of the clothes box or the outer casing, transparency is required in order to create a identifiable storage item. Further, in order to prevent breakage during transportation or use, high impact strength is required. Further, when the hinge portion is provided, whitening resistance at the time of bending is required. Further, since the clothes box or the outer casing is formed by injection molding, injection moldability is also required. Conventionally, a resin composition containing a random copolymer of ethylene and propylene as a main component as disclosed in Patent Document 1 is used in a molded article requiring transparency. Further, in the molded article requiring high impact strength, a resin composition containing block polypropylene as a main component as disclosed in Patent Document 2 and Patent Document 3 is used. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei 9-31264 (Patent Document 3). DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION However, the molded article obtained from the resin composition disclosed in Patent Document 1 has impact strength, and particularly, the impact strength at low temperature is insufficient. The molded article obtained from the resin composition disclosed in Patent Document 2 and Patent Document 3 may have insufficient transparency and whitening resistance. An object of the present invention is to provide a polypropylene resin composition and a molded article for injection molding which are excellent in transparency, whitening resistance and low-temperature impact strength. Means for Solving the Problem The polypropylene resin composition for injection molding of the present invention contains a propylene-based resin material and a crystallization nucleating agent, and is an ultimate viscosity in tetrahydronaphthalene in which diphenylbenzene is soluble in M135 °c. 〇.8dl/g to 1.4dl/g, and the melt flow rate measured according to Japanese Industrial Standard JIS K7210' at a temperature of 230 ° C and a load of 21.6 N is 5 g / l 至 to i5 g / l ,, Further, the propylene-based resin material is polymerized in an ethylene-butadiene copolymer having an ethylene unit of from 74% by mass to 86% by mass in the presence of an ethylene.propylene copolymer having an ethylene unit of from 2.0% by mass to 4.0% by mass. The 'again' was made into a 100-mass mass of the polypropylene resin composition for injection molding. In the case of /, the content of the ethylene.1-butene copolymer is from 10% by mass to 20% by mass. 4 201231538 The polypropylene resin composition for injection molding of the present invention is contained in an amount of from 0.01 to 0.5 parts by mass based on 100 parts by mass of the propylene resin material. In the molded article of the present invention, the polypropylene resin composition for injection molding is injected into a molded article. EFFECTS OF THE INVENTION The polypropylene resin composition for injection molding of the present invention is excellent in transparency, whitening resistance and low-temperature impact strength, and is suitable for injection molding. E: Implementation:! EMBODIMENT OF THE INVENTION The polypropylene resin composition for injection molding of the present invention (hereinafter, simply referred to as "resin composition") contains a propylene resin material and a crystallization nucleating agent. In the resin composition of the present invention, the intrinsic viscosity of the diphenylbenzene soluble component in tetrahydronaphthalene at 135 ° C is from 0.8 dl / g to 1.4 dl / g, and is preferably from di 8 di / g to 1.2 dl / g . When the ultimate viscosity of the resin composition is more than the above upper limit, whitening resistance and transparency tend to be lowered. The ultimate viscosity of the diphenylbenzene-soluble component of the resin composition is largely dependent on the viscosity of the ethylene-丨-butene copolymer. However, it is difficult to manufacture the propylene-based resin material having an ultimate viscosity of less than the above lower limit. Further, the melt flow rate (MFR) of the resin composition is 5 g/l to 15 g/1 Torr, and preferably 8 g/l 12 to 12 g/10 minutes. Here, the MFR is a value measured under conditions of a temperature of 230 t: and a load of 21.6 Torr according to jiS κ 72 。. When the MFR of the resin composition is less than the above lower limit, the injection moldability is lowered. If it is larger than the above upper limit, the low-temperature impact strength is lowered. 201231538 (acrylic resin material) The propylene-based resin material is a reaction-blended polypropylene which is obtained by polymerizing an ethylene·1-butene copolymer in the presence of an ethylene-propylene copolymer in a polymerization reactor. Winner. Further, the ethylene·1-butene copolymer is a rubber component. The productivity can be improved by polymerizing the ethylene.1-butene copolymer in the presence of an ethylene.propylene copolymer. Moreover, since the dispersibility of the material is increased, the physical balance is also enhanced. The aforementioned propylene-based resin material can be produced by multistage polymerization. For example, the ethylene-propylene copolymer can be polymerized by the polymerization reactor of the first stage, and the obtained ethylene-propylene copolymer can be supplied to the polymerization reactor of the second stage while being passed through the second stage. In the polymerization reactor, an ethylene·1-butene copolymer was polymerized, whereby a propylene-based resin material was obtained. In this method, an ethylene-propylene copolymer and a produced ethylene·1-butene copolymer are mixed by a polymerization reactor of the second stage. Further, the multistage polymerization is not limited to the above method, and the ethylene-propylene copolymer may be polymerized by a complex polymerization reactor, and the ethylene.1-butene copolymer may also be polymerized by a plurality of polymerization reactors. A well-known olefin polymerization catalyst can be used as the catalyst to be polymerized, and from the viewpoint of easily producing a propylene-based resin material which exhibits desired physical properties, it is preferably a Zigler Nata catalyst. Further, at the time of polymerization, hydrogen may be added as needed for the adjustment of the MFR. The ethylene unit content in the ethylene.propylene copolymer is from 2.0% by mass to 4.0% by mass, and more preferably from 3.0% by mass to 4.0% by mass. If the ethylene. propylene total 201231538 == olefin content is greater than the above upper limit, there will be a tendency to manufacture propylene-based eucalyptus enamel, and if it is less than the previous limit, the resulting resin composition will be obtained. The transparency and the low-temperature impact strength are reduced. The ethylene unit content in the ethylene.1-butadiene copolymer is from 74% by mass to 86% by mass. /. And it is preferably 79% by mass to 84% by mass. If the ethylene unit content of the ethylene. 丨-butene copolymer is greater than the above upper limit, the low-temperature impact strength of the fat composition tends to decrease, and if it is less than the lower limit, there is propylene. The tendency of the production of the fat material is difficult, and the rigidity and transparency of the resin composition are lowered. The content of the ethylene-b-butylene copolymer in the resin composition is from 1% by mass to 2% by mass, and preferably from 12% by mass to 16% by mass, based on 100% by mass of the composition of the sapphire. When the content of the ethylene oxime copolymer is more than the above upper limit, the rigidity tends to decrease, and if it is less than the lower limit, the low-temperature impact strength of the obtained resin composition tends to decrease. (Crystalizing nucleating agent) The crystallization nucleating agent promotes the formation of a crystalline nucleus of polypropylene and enhances the transparency or rigidity of the obtained resin composition. By containing a crystallization nucleating agent, the twist value (JISK7105, 1 mm thick) can be easily made 30% or less. Specific examples of the crystallization nucleating agent include a sorbitol compound, a metal salt of a carboxylic acid, an aromatic phosphate compound, cerium oxide, and talc. From the viewpoint of low odor, it is preferably an aromatic phosphate compound. For example, the sorbitol compound may, for example, be dibenzylidene sorbitol, 1,3,2,4-mono-(methylbenzylidene) sorbitol, iota, 3,2,4-(ethyl amide) Succinyl) sorbitol, 1,3,2,4-(methoxybenzylidene) sorbitol, hydrazine, 3,2,4-(ethoxybenzylidene) 201231538 Sorbitol, 1,2,3 -Trideoxy-4,6-5,7-bis-indole-[(4-propylphenyl)methylene] decyl alcohol and the like. For example, the metal salt of a carboxylic acid may, for example, be sodium adipic acid, potassium adipate, adipic acid, sodium azelate, azelaic acid, azelaic acid, sodium benzoate, aluminum benzoate. , di-p-butyl-butyl benzoate, titanium di-p-butyl-benzoate, chromium di-p-butyl-benzoate, hydroxy-di-t-butyl benzoate, and the like. Further, as the crystallization nucleating agent, a triamine benzene derivative can be used. The content of the crystallization nucleating agent is preferably from 0.01 part by mass to 0.5 part by mass, and more preferably from 0.1 part by mass to 0.4 part by mass, per 100 parts by mass of the acryl-based resin material. However, when the nucleating agent is a triamine benzene derivative, it is preferably from 0.01 part by mass to 0.02 part by mass. When the content of the crystallization nucleating agent is at least the above lower limit value, the transparency of the molded article obtained from the resin composition can be further improved, and if it is at most the above upper limit value, the odor can be suppressed. (Other polymer) In the resin composition, other polymers may be contained as needed. As the other polymer, a known thermoplastic resin or thermosetting resin can be used. For example, the thermoplastic resin may, for example, be an ethylene or an α-olefin individual polymer, a copolymer of ethylene or a carbon number of 3 to 10, a mixture of the same, a nylon, a polycarbonate, or a poly(fluorene oxide). , petroleum resin, etc. For example, examples of the ethylene or olefin alone polymer include high density polyethylene, low density polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly( 3-methyl-1-pentene), poly(3-mercapto-1-butene), poly(4-mercapto-1-pentene), poly-1-hexene, poly-1-heptene , poly-1-octene, poly-1-癸8 201231538 Arene, polystyrene and combinations thereof. Among these, it is preferably polypropylene. (Additive) In the resin composition of the present invention, for example, it may contain an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an internal lubricant, an external lubricant, an antistatic agent, An additive such as a flame retardant, a dispersant, a copper inhibitor, a neutralizing agent, a plasticizer, a foaming agent, an anti-bubble agent, a crosslinking agent, a peroxide, or the like is optional. (Manufacturing Method) The resin composition can be produced by blending a propylene-based resin material, a crystallization nucleating agent, and other polymers and additives as needed, and then using a uniaxial extruder and a double shaft. A known kneading machine such as an extruder, a Bamburi mixer, a kneading machine, and a refiner, and a 'melt kneader. (Molded product) The resin composition is processed into a molded article by injection molding. The conditions at the time of injection molding are not particularly limited, and may be appropriately selected depending on the shape or size of the target molded article, the type or scale of the injection molding machine to be used, and the molding temperature is preferably 200 ° C to 260 ° C. When the molding temperature is at least the above lower limit value, sufficient moldability can be ensured, and if it is at most the above upper limit value, thermal deterioration of the resin composition can be prevented. EXAMPLES In the following examples and comparative examples, "%" means "% by mass" and "parts" means "parts by mass". (Example 1 to Example 10, Comparative Example 1 to Comparative Example 10) Polymerization pack 201231538 containing a polymerization reactor in which all four stages were contained in series was used, and ethylene/propylene was polymerized by a polymerization reactor of the first two stages. The copolymer is supplied to the polymerization reactor of the second stage of the second stage, and the ethylene·1-butene copolymer is polymerized by the polymerization reactor of the second stage (in Tables 1 to 3, designated as “C2C4”. . . . , or ethylene. propylene copolymer (in Tables 1 to 3, labeled "C2C3".). At this time, the acrylic resin materials shown in Tables 1 to 3 were obtained by adjusting the ethylene supply amount, the hydrogen supply amount, the polymerization temperature, the polymerization pressure, and the amount of the catalyst added. 0.2 parts of a crystallization-based nucleating agent (Millad 3988, manufactured by Milliken Co., Ltd.) was blended in 10 parts of the propylene-based resin material, and a resin was obtained by melt-kneading at 230 ° C using an extruder. Composition. (Comparative Example 11) A resin composition (PM633V manufactured by Sun Allomer Co., Ltd.) in which a rubber component was blended in an ethylene/propylene random copolymer was used. 10 201231538 [Table 1] Example No. 1 2 3 4 5 6 7 8 9 10 Principal component of the resin composition PP PP PP PP PP PP PP PP PP PP PP ethylene content (%) 3.5 3.5 3.4 2.0 3.8 3.5 3.5 3.5 3.5 3.5 Types of rubber components C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 C2C4 Content of rubber components (%) 12 13 13 13 13 10 20 13 13 13 Ethylene unit content (%) in rubber composition 81 82 82 82 82 82 82 82 86 74 Mixed Polymerization Polymerization Polymerization Polymerization Polymerization Polymerization Polymerization Polymerization Ultimate Viscosity (dl/g) 0.8 1.0 1.4 1.1 1.0 1.0 1.0 1.0 1.0 1.0 MFR (g/min) 11 10 10 10 30 10 10 15 10 10 Content of crystallization nucleating agent (parts) 0.2 0.2 0.2 0.2 0,2 0.2 0.2 0.2 0.2 0.2 Productivity (%) 10 10 12 13 10 9 15 11 16 9 Whitening elastic bending elastic modulus (MPa) 850 860 890 1030 840 890 800 870 880 800 Impact-resistant surface impact strength at 〇 ° C (J) 22 23 22 20 23 20 29 21 20 23 rupture condition 〇〇〇〇〇〇〇〇〇〇[ 2]
比較例編號 1 2 3 4 5 樹脂組成物之主成分 PP PP PP PP PP PP之乙烯含量(％) 3.4 3.3 4.2 3.5 3.5 橡膠成分之種類 C2C4 C2C4 C2C4 C2C4 C2C4 橡膠成分之含有率(％) 12 12 13 9 13 橡膠成分中的乙烯單元含量(％) 83 82 82 82 82 橡膠成分之混合 聚合 聚合 聚合 聚合 聚合 極限黏度(dl/g) 0.7 1.7 1.0 1.0 1.0 MFR(g/分） 11 10 10 10 20 結晶化核劑之含量(份） 0.2 0.2 0.2 0.2 0.2 生產性 X 〇 X 〇 〇 霾度(％) 10 18 10 9 13 耐白化性 〇 X 〇 〇 〇 彎曲彈性率(MPa) 830 930 780 900 880 〇°C下的 而十掛擊性 面衝擊強度(J) 23 21 25 10 13 破裂狀況 〇 〇 〇 X X 201231538Comparative Example No. 1 2 3 4 5 Principal component of the resin composition PP PP PP PP PP PP ethylene content (%) 3.4 3.3 4.2 3.5 3.5 Type of rubber component C2C4 C2C4 C2C4 C2C4 C2C4 Content of rubber component (%) 12 12 13 9 13 Ethylene unit content in rubber composition (%) 83 82 82 82 82 Mixed polymerization of rubber components Polymerization polymerization ultimate viscosity (dl/g) 0.7 1.7 1.0 1.0 1.0 MFR(g/min) 11 10 10 10 20 Content of crystallization nucleating agent (parts) 0.2 0.2 0.2 0.2 0.2 Productivity X 〇X 〇〇霾 degree (%) 10 18 10 9 13 Whitening resistance 〇X 〇〇〇Flexural modulus (MPa) 830 930 780 900 880 Ten impact surface impact strength at 〇°C (J) 23 21 25 10 13 rupture condition 〇〇〇 XX 201231538
[表3] 比較例編號 6 7 8 9 10 11 樹脂組成物之主成分 PP PP PP PP PP PP PP之乙烯含量(％) 3.5 3.5 3.5 3.5 3.5 3.7 橡膠成分之種類 C2C4 C2C4 C2C4 C2C3 C2C3 C2C4 橡膠成分之含有率(％) 13 13 13 13 13 10 橡膠成分中的乙烯單元含量(％) 88 72 82 82 74 80 橡膠成分之混合 聚合 聚合 聚合 聚合 聚合 混練 極限黏度(dl/g) 1.0 1.0 1.0 1.1 2.0 1.2 MFR(g/分） 10 10 10 10 10 8 結晶化核劑之含量(份） 0.2 0.2 0 0.2 0.2 0.2 生產性 〇 X 〇 〇 △ X 霾度(％) 18 - 20 15 87 10 而才白化性 〇 - 〇 X X 〇 彎曲彈性率(MPa) 890 - 740 910 800 860 〇°C下的耐 衝擊性 面衝擊強度(J) 11 - 27 25 11 10 破裂狀況 X - 〇 〇 X X 如下述般評價各樹脂組成物之熔融流率（MFR)、生產 性、透明性、耐白化性、彎曲彈性率、低溫下的耐衝擊性。 表1至表3係顯示評價結果。 [MFR] MFR係依據JIS K 7210，於溫度230°C、負載21.6N之條 件下所測定之值。 [生產性] 错由以下基準’§平價樹脂組成物之生產性。 ◎:可藉由聚合反應器連續生產，且生產速度高。 〇：可藉由聚合反應器連續生產，且生產速度中等。 △:可藉由聚合反應器連續生產，但必須降低生產速度。 X.無法藉由聚合反應器連續生產。 12 201231538 [透明性] 將各樹脂組成物以成形溫度230。(：射出成形，並製作 1mm厚之板狀試驗片。使用該試驗片，依循JJSK7105，藉 由霾度測定裝置（村上色彩技術研究所（股）製HMd5〇型）測 定霾度。霾度之值越小，透明性越優異。 [低溫下的耐衝擊性、耐白化性] 將各樹脂組成物以成形溫度230。(：射出成形，並製作 2mm厚之板狀試驗片。使用該試驗片，於〇。匚之環境下，藉 由面衝擊強度測定裝置（島津製作所公司製Hydroshot)測定 面衝擊強度。 又，將各樹脂組成物以成形溫度230°C射出成形，並製 作有底半球狀之容器。於(TC之環境下，藉由面衝擊強度測 . 定裝置（島津製作所公司製Hydroshot)，使該容器受到破 . 壞。藉由目視，觀察此時的破裂狀況，並藉由以下基準來 評價。 〇：未破裂而壓壞，且未產生碎片。 X :破裂而產生碎片。 又，除了將溫度作成〇°c外，作成與前述面衝擊強度之 測定相同而對試驗片賦予衝擊，並藉由以下基準來評價财 白化性。 〇：未看見白化。 χ :可看見白化。 [彎曲彈性率] 依循JIS K6758來測定。 13 201231538 實施例1至實施例10之樹脂組成物係透明性、耐白化性 及低溫衝擊強度皆優異。 極限黏度為0.7dl/g的比較例1之樹脂組成物係利用聚 合的丙烯系樹脂材料之製造困難。 極限黏度為1.7dl/g的比較例2之樹脂組成物係耐白化 性低。 含有乙烯單元為4.2%之乙烯.1-丁烯共聚物的比較例3 之樹脂組成物係利用聚合的丙烯系樹脂材料之連續製造困難。 將乙烯.1-丁烯共聚物之含量作成9%的比較例4之樹脂 組成物係低溫衝擊強度低。 MFR為20g/l〇分的比較例5之樹脂組成物係低溫衝擊 強度低。 將乙烯.1-丁烯共聚物之乙烯單元作成88%的比較例6 之樹脂組成物係低溫衝擊強度低。 將乙烯.1-丁烯共聚物之乙烯單元作成72%的比較例7 之樹脂組成物係利用聚合的丙烯系樹脂材料之連續製造困難。 未含結晶化核劑的比較例8之樹脂組成物係透明性及 剛性低。 橡膠成分為乙稀.丙稀共聚物的比較例9 、比較例10之 樹脂組成物係耐白化性低。 於乙稀·丙歸隨機共聚物中掺合有橡膠成分的比較例 11之樹脂組成物係低溫衝擊強度低。 產業之可利用性 本發明之射出成形用聚丙烯樹脂組成物可適當地利用 14 201231538 在透明衣物箱、食品用容器、化妝品容器等各種包裝容器， 或是具有鉸鏈之容器蓋等。 r：圖式簡單說明】 (無） 【主要元件符號說明】 (無） 15[Table 3] Comparative Example No. 6 7 8 9 10 11 Principal component of the resin composition PP PP PP PP PP PP PP ethylene content (%) 3.5 3.5 3.5 3.5 3.5 3.7 Type of rubber component C2C4 C2C4 C2C4 C2C3 C2C3 C2C4 Rubber component Content (%) 13 13 13 13 13 10 Ethylene unit content (%) in rubber composition 88 72 82 82 74 80 Mixed polymerization polymerization polymerization polymerization polymerization kneading ultimate viscosity (dl/g) 1.0 1.0 1.0 1.1 2.0 1.2 MFR (g/min) 10 10 10 10 10 8 Content of nucleating agent (parts) 0.2 0.2 0 0.2 0.2 0.2 Productivity 〇X 〇〇△ X 霾 degree (%) 18 - 20 15 87 10 Properties - 〇XX 〇Flexural modulus (MPa) 890 - 740 910 800 860 Impact-resistant surface impact strength at 〇°C (J) 11 - 27 25 11 10 Rupture condition X - 〇〇XX Each evaluation is as follows Melt flow rate (MFR), productivity, transparency, whitening resistance, flexural modulus, and impact resistance at low temperatures of the resin composition. Tables 1 to 3 show the evaluation results. [MFR] MFR is a value measured in accordance with JIS K 7210 at a temperature of 230 ° C and a load of 21.6 N. [Productivity] The following is the basis for the productivity of the equivalent resin composition. ◎: It can be continuously produced by a polymerization reactor, and the production speed is high. 〇: It can be continuously produced by a polymerization reactor, and the production speed is medium. △: It can be continuously produced by a polymerization reactor, but the production speed must be lowered. X. Cannot be continuously produced by a polymerization reactor. 12 201231538 [Transparency] Each resin composition was formed at a molding temperature of 230. (: Injection molding was carried out, and a 1 mm-thick plate-shaped test piece was produced. Using this test piece, according to JJSK7105, the twist was measured by a measurement apparatus (HMd5 type manufactured by Murakami Color Research Laboratory Co., Ltd.). The smaller the value, the more excellent the transparency. [Impact resistance at low temperature and whitening resistance] The resin composition was formed at a molding temperature of 230. (: Injection molding, and a plate-shaped test piece having a thickness of 2 mm was produced. The test piece was used. The surface impact strength was measured by a surface impact strength measuring device (Hydroshot manufactured by Shimadzu Corporation) under the environment of 〇. In addition, each resin composition was injection-molded at a molding temperature of 230 ° C to produce a bottomed hemisphere. In the environment of TC, the container was damaged by the surface impact strength measuring device (Hydroshot manufactured by Shimadzu Corporation). By visual observation, the rupture at this time was observed, and by the following Evaluation: 〇: not broken and crushed, and no fragments are produced. X: rupture and fragmentation. In addition, the temperature is made 〇°c, and the test is the same as the above-mentioned surface impact strength. The impact was imparted, and the whitening property was evaluated by the following criteria: 〇: whitening was not observed. 白: whitening was observed. [Bending elastic modulus] Measured in accordance with JIS K6758. 13 201231538 Resin compositions of Examples 1 to 10 It is excellent in transparency, whitening resistance, and low-temperature impact strength. The resin composition of Comparative Example 1 having an ultimate viscosity of 0.7 dl/g is difficult to manufacture by using a polymerized propylene-based resin material. The ultimate viscosity is 1.7 dl/g. The resin composition of Example 2 was low in whitening resistance. The resin composition of Comparative Example 3 containing an ethylene.1-butene copolymer having an ethylene unit of 4.2% was difficult to continuously produce by using a polymerized propylene-based resin material. The resin composition of Comparative Example 4 in which the content of the .1-butene copolymer was 9% was low in low-temperature impact strength. The resin composition of Comparative Example 5 having an MFR of 20 g/l was low in low-temperature impact strength. The ethylene unit of the 1-butene copolymer was made 88%. The resin composition of Comparative Example 6 had a low low-temperature impact strength. The ethylene unit of the ethylene.1-butene copolymer was made 72% of the resin composition of Comparative Example 7. Use of poly The continuous production of the propylene-based resin material is difficult. The resin composition of Comparative Example 8 which does not contain the crystallization nucleating agent has low transparency and rigidity. The rubber component is Comparative Example 9 of ethylene propylene copolymer, and Comparative Example 10 The resin composition was low in whitening resistance. The resin composition of Comparative Example 11 in which the rubber component was blended in the ethylene-propylene-based random copolymer was low in low-temperature impact strength. INDUSTRIAL APPLICABILITY The injection molding polymerization of the present invention As the acryl resin composition, various packaging containers such as a transparent clothes box, a food container, and a cosmetic container, or a container lid having a hinge, etc., can be suitably used. r: Simple description of the schema] (none) [Explanation of main component symbols] (none) 15