1364436 九、發明說明： 【發明所屬之技術領域】 本發明有關乙烯μ -烯烴共聚物之擠製發泡成形品。 【先前技術】 ^由聚乙烯系樹脂所成擠製發泡成形品，由於柔軟性、 衝擊吸收性、輕量性、斷熱性優異，因此，一直二來便使 用裝材料、緩衝材、蕊材、斷熱材、襯墊（Packing)、 建染資材等各種用it。然而，至今廣泛採用的高壓法低密 度聚乙烯之擠製發泡成形品，容易發生所謂波紋 (c〇rrugati0n)之周期性的不均勻厚度外觀之變動等。 a日本專利特開2001-347619號公報中記載一種具有平 句氣泡在度為15個/9mm2以上之表層的高壓法低密度聚乙 烯擠製發泡成形品’惟其外觀並不佳。而且，此種成形品 之機械強度不足而容易破裂。1364436 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to an extruded foamed molded article of an ethylene μ-olefin copolymer. [Prior Art] ^The foamed molded article is extruded from a polyethylene resin, and is excellent in flexibility, impact absorption, light weight, and heat-insulating property. Therefore, the material for use, the cushioning material, and the core material have been used for two purposes. It is used for various materials such as heat-dissipating materials, packing, and dyeing materials. However, the extruded foam molded article of high-pressure method low-density polyethylene which has been widely used hitherto is prone to occurrence of fluctuations in the periodic uneven thickness appearance of the so-called corrugation. Japanese Patent Laid-Open Publication No. 2001-347619 discloses a high-pressure low-density polyethylene extruded foam molded article having a surface layer having a degree of bubble of 15/9 mm 2 or more, but the appearance is not good. Further, such a molded article is insufficient in mechanical strength and is easily broken.
本專利特開2〇〇0-119427號公報中記載一種由乙稀 心烯fe共聚物、芳㈣乙烤化合物聚合物嵌段（bi〇ck)與在 輛二烯聚合物嵌段所成的嵌段共聚物之加氫物、及由稀 糸聚合物所成的聚合物組成物、以及使用熱分解型發泡濟 使該聚合物組成物發泡而得之發泡體，惟該發泡體之氣% 尺寸較大，因此表面平祕較差。而且，由於前述聚合步 組成物之㈣張力較低’因此，在擠製發泡成形時容㈣ 泡’因此，如欲製造發泡倍率較高之發泡成形品時，因母 泡而使表面容易變㈣，所得發泡成形品之外觀並不佳。 此外’因破泡而使氣泡變得粗大之發泡成形品，其編 316749 5 1364436 度亦差。 【發明内容】 本發明之目的在於提供一種由乙稀-α-稀烴共聚物所 成’外觀及機械強度優異的擠製發泡成形品。 本發明提供一種由分子量分佈在5以上，而膨脹比 L 611 at10)在1 15至1 45之乙烯-α烯烴共聚物所成之擠 :成形品。另夕卜本發明中所謂「撥製發泡成形品」 久才曰藉由擠2發泡所製造的成形品。此外，在下述說明中， 除非特別註明，「成形品」乃表示「擠製發泡成形品」之意。 【實施方式】 本卷明之成形品係由乙烯_ α •稀烴共聚物所成。該乙 稀I稀煙共聚物係乙烤與碳數3以上之！種以上α_烯煙 的共聚物’而含有來自乙烯之構成單元50重量％以上。較 佳之α_烯烴係為碳數4至12之^•烯烴。 α -稀烴而言，可列盛· 。了列舉.丙烯'丁烯-1、4-曱基戊烯-1、 己烯-1、辛烯-1、癸烯4等 ^ 罕又仏為丁稀·1及己：fcfjj-l。尤 ”，從成形品之機械強度的觀 ..町咸點來看，以乙烯-己烯-1共聚 物為佳。 構成本發明之成形品的 分伟為5以上，較佳為6以上"7佳T:共聚物之Γ! 分佈過小，則氣泡變大，或 =UJl °如&子里 致成形品外觀變差。分子4八2而在成形品表面穿孔以 π以下，牯私立μ 佈較佳為30以下，更佳為 25以下，特4為2〇以下。如 泡成形品容易發生波紋。刀子里刀佈過大，則擠製發 316749 6 1364436 本發明中之「分子量分佈」係指重量平均分子量（Mw) ·,·相對於數平均分子量（Μη)的比。Mn及Mw可由凝膠滲透 ··色譜法（Gel Permeatl〇n Chr〇matography, GPC)求得。 構成本發明之成形品的乙烯-α -烯烴共聚物之密度， 車义仫為890至94〇kg/m3 ’更佳為895至935kg/m3，更佳為 900至930kg/m3。如密度過低，則成形品之剛性降低。又， 如饴度過尚，則成形品之機械強度降低。 構成本如明之成形品的乙烯-α -婦烴共聚物之膨脹比 •(以下，有時簡記為SR)為！ 15至i 45，較佳為1 15至j 4〇，、) 更佳為1.20至1.35。如SR在1.15以下，則氣泡變大，或 因破泡而在成形品表面穿孔以致成形品之外觀變差。如SR 在1.45以上’則發生波紋以致成形品之外觀變差。 本發明中之膨脹比係在溫度l5(rc、剪切速度6〇 8s-〗 •之下所測定的值，更詳細者係如下所示。測定時，使用具 有直控1 mm、長度40mm、流入角90度之毛細管的毛細管 籲流變計（capillary phe〇meter)(例如，東洋精機（股）製之 CAPIROGRAPH-IB)。依照 JIS K7199，在溫度 150。(：、剪） 切速度60.8s·1之下’連續擠出熔融狀態之乙烯-α-烯烴共 t物。於毛細管出口切斷所撥出之股線（strand)並去除。持 續進行擠出，並當新擠出的股線長度成為2〇ηιηι以上時， 測疋從毛細管之出口 15mm時之位置的股線直徑。於前述 直徑之測定則使用電射位移計（]aser disp]aceixient gauge)。 SR係由下式算出。 SR=D/D〇 7 316749 1364436 在此，D表示股線之直徑（mm)、Dq表示毛細管之直和 (mm)。 構成本發明之成形品之乙烯-α -烯烴共聚物之流動的 活化能（activation energy)較佳為40kJ/莫耳以上，更佳為 50kJ/莫耳以上，最佳為55kJ/莫耳以上，特佳為6〇u/莫耳 以上。如流動之活化能過低，則從成形機所擠出之熔融狀 態的擠製物之冷卻速度增快。因此，氣泡狀態變為不均句， 以致成形品之外觀惡化之同時，機械強度降低。 • 由成形品之外觀及機械強度之觀點來看，乙烯烯 烴共聚物之流動活化能較佳為丨〇〇kJ/莫耳以下，更佳為 ’ 90kJ/莫耳以下。 … [動態黏彈性（dynamic viscoelasticity)之測定] 在動態黏彈性（儲存模量（st〇rage modulus) : 〇，、損失 模量（loss modulus : G”）之測定時，採用黏彈性測定裝置。 動態黏彈性之代表性測定條件係如下所述。 鲁（1)測疋部形狀.平行板（直徑25mm，板間隔：約1 (2) 剪應變（stearing strain) : 50/〇 (3) 角頻率：0.1至l〇〇ra(j/秒範圍内之預定值 (4) 溫度：130°C、15CTC、17〇。(：、190°C(4 點） 在測定之試樣（sample)中，預先調配適量（例如200至 lOOOOppm)抗氧化劑，全在氮氣環境下進行測定。 [位移因素（shift factor)之求算] 位移因素（aT)之求算步驟如下所述。 將1 30°C (403 ^ K)作為基準溫度（T〇)，依照式（I)及（2)， 8 316749 1364436 製作 G (Pa)及 Gn(Pa)之主曲線（master curve)。 〇'(ω ' T)=bTG'(aT〇; > χ〇) ⑴ • <3"(ω、T)=bTG"(aTa)、Τ〇) (2) 在此，ω表示角頻率（ra(j/秒），τ表示各測定溫度（。κ)、 Τ〇表不基準溫度、aT表示角頻率方向之位移量、卜表示 G'、G"軸方向之位移量。 [活化能之求算] 流動之活化能（Ea)係按如下步驟求出。 鲁 繪製對1/T之l〇g(aT)之曲線。就此所繪製之曲線，進 行利用最小平方法之近似直線，以算出直線之斜率。將所 .得斜率視作Ea/2.3〇3R，以算出Ea(kJ/莫耳）（關於流動之活 化旎，可參照例如：聚合物工程及科學Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a hydrogenated product of a block copolymer, a polymer composition obtained from a dilute polymer, and a foam obtained by foaming the polymer composition using a thermally decomposable foam, but the foaming The volume of the body is larger, so the surface is less flat. Further, since the (IV) tension of the above-mentioned polymerization step composition is low, "the foam is formed during the extrusion molding". Therefore, when a foamed molded article having a high expansion ratio is to be produced, the surface is formed by the mother glass. It is easy to change (4), and the appearance of the obtained foamed molded article is not good. In addition, the foamed molded article in which the bubble is coarsened due to the breaking of the bubble is also inferior to the 316749 5 1364436. DISCLOSURE OF THE INVENTION An object of the present invention is to provide an extruded foam molded article which is excellent in appearance and mechanical strength from an ethylene-α-dilute hydrocarbon copolymer. The present invention provides an extruded product of an ethylene-α olefin copolymer having a molecular weight distribution of 5 or more and an expansion ratio of L 611 at 10) of 1 15 to 1 45. Further, in the present invention, the "puffed molded product" is a molded article produced by extrusion 2 foaming for a long time. In addition, in the following description, unless otherwise indicated, "molded article" means "extruded foamed molded article". [Embodiment] The molded article of the present invention is composed of an ethylene_α•dilute hydrocarbon copolymer. The Ethylene I smoke copolymer is B-baked with a carbon number of 3 or more! The above copolymer of α-olefin is contained in an amount of 50% by weight or more of the constituent unit derived from ethylene. The preferred α-olefin is an olefin having 4 to 12 carbon atoms. For α-dilute hydrocarbons, it can be listed. Listed. propylene 'butene-1, 4-decylpentene-1, hexene-1, octene-1, decene 4, etc. ^ 仏 仏 丁 丁 · 1 and hex: fcfjj-l. In particular, the ethylene-hexene-1 copolymer is preferred from the viewpoint of the mechanical strength of the molded article. The molded article of the present invention has a bifurcation of 5 or more, preferably 6 or more. ; 7 good T: copolymer Γ! If the distribution is too small, the bubble becomes larger, or = UJl ° such as & sub-formation of the molded article is deteriorated. Molecule 4 8 2 and the surface of the molded product is perforated by π or less, 牯 private The μ cloth is preferably 30 or less, more preferably 25 or less, and the specific 4 is 2 or less. If the foamed article is likely to be corrugated, if the knife is too large, the extruded 316749 6 1364436 "Molecular weight distribution" in the present invention It means the ratio of the weight average molecular weight (Mw) ·, · relative to the number average molecular weight (Μη). Mn and Mw can be obtained by gel permeation chromatography (Gel Permeatl〇n Chr〇matography, GPC). The density of the ethylene-α-olefin copolymer constituting the molded article of the present invention is preferably 890 to 94 〇 kg/m 3 ', more preferably 895 to 935 kg/m 3 , still more preferably 900 to 930 kg/m 3 . If the density is too low, the rigidity of the molded article is lowered. Further, if the degree of enthalpy is too high, the mechanical strength of the molded article is lowered. The expansion ratio of the ethylene-α-glycol copolymer constituting the molded article of the present invention (hereinafter, abbreviated as SR) is! 15 to i 45, preferably 1 15 to j 4 〇, and more preferably 1.20 to 1.35. When SR is at most 1.15, the bubble becomes large, or the surface of the molded article is perforated by foaming, so that the appearance of the molded article is deteriorated. If SR is 1.45 or more, waviness occurs and the appearance of the molded article deteriorates. The expansion ratio in the present invention is a value measured at a temperature of l5 (rc, shear rate: 6 〇 8 s -), and is more detailed as follows. For measurement, a straight control of 1 mm and a length of 40 mm are used. Capillary phe〇meter (for example, CAPIROGRAPH-IB manufactured by Toyo Seiki Co., Ltd.) which flows into a capillary of 90 degrees. According to JIS K7199, at a temperature of 150. (:, shear) Cutting speed 60.8s ·1 below' continuous extrusion of molten ethylene-α-olefin co-t material. The strands are cut off at the capillary outlet and removed. The extrusion is continued, and the newly extruded strands When the length is 2 〇ηιηι or more, the diameter of the strand at a position 15 mm from the outlet of the capillary is measured. The above-mentioned diameter is measured using an electro-displacement meter (] aser disp] aceixient gauge. The SR is calculated by the following formula. SR=D/D〇7 316749 1364436 Here, D represents the diameter (mm) of the strand, and Dq represents the sum of the capillary (mm). Activation of the flow of the ethylene-α-olefin copolymer constituting the molded article of the present invention. The activation energy is preferably 40 kJ/mole or more, more preferably 50 kJ/ Above the ear, it is preferably 55kJ/mole or more, especially preferably 6〇u/mole or more. If the activation energy of the flow is too low, the cooling rate of the extruded material extruded from the forming machine is increased. Therefore, the state of the bubble becomes a non-uniform sentence, so that the appearance of the molded article is deteriorated, and the mechanical strength is lowered. • From the viewpoint of the appearance and mechanical strength of the molded article, the flow activation energy of the ethylene olefin copolymer is preferably 丨. 〇〇kJ/mole below, more preferably '90kJ/mole below. ... [Determination of dynamic viscoelasticity] in dynamic viscoelasticity (st〇rage modulus: 〇, loss mode) The measurement of the loss modulus (G" is carried out using a viscoelasticity measuring device. The representative measurement conditions of dynamic viscoelasticity are as follows: Lu (1) Measuring the shape of the jaw. Parallel plate (diameter 25 mm, plate spacing: approx. 1 (2) Stearing strain: 50/〇(3) Angular frequency: 0.1 to l〇〇ra (predetermined value in the range of j/sec (4) Temperature: 130 ° C, 15 CTC, 17 〇. :, 190 ° C (4 points) In the sample (sample), pre-mixed with appropriate amount For example, 200 to 1000 ppm) of antioxidants are all measured under a nitrogen atmosphere. [Measurement of displacement factor] The calculation procedure of the displacement factor (aT) is as follows: 1 30 ° C (403 ^ K) As the reference temperature (T〇), the master curves of G (Pa) and Gn (Pa) were prepared according to the formulas (I) and (2), 8 316749 1364436. 〇'(ω ' T)=bTG'(aT〇; > χ〇) (1) • <3"(ω, T)=bTG"(aTa), Τ〇) (2) Here, ω represents the angular frequency (ra (j/sec), τ represents the measured temperature (.κ), Τ〇 indicates the reference temperature, aT indicates the displacement amount in the angular frequency direction, and Bu indicates the displacement amount in the G' and G" axis directions. The calculation of the activation energy (Ea) of the flow is as follows: The curve of l〇g(aT) of 1/T is plotted. For the curve drawn by this, the approximate line using the least square method is used to Calculate the slope of the straight line. The slope obtained is regarded as Ea/2.3〇3R to calculate Ea(kJ/mole). (For the activation enthalpy of flow, refer to, for example, Polymer Engineering and Science.
Engineenng and Science)，第 8 卷，第 235 頁（1968 年出版））。 構成本發明之成形品的乙烯烯烴共聚物，較佳為 在190 C下的炫體流動速率（me】t fi〇w rate)(以下，簡記為 籲MFR)在〇·〇】至5g/1〇分鐘，更佳為〇 〇5至4^1〇分鐘， 再佳為0_1至3g/10分鐘》MFR係依照Jis K6760所求得 之值。如MFR過低，成形品之表面會變為粗糙，有時無 法獲得充分的發泡倍率。如MFR過高，則成形品中之氣 泡變粗大，或成形體表面穿孔。 構成本發明之成形品的乙焊-α -烯煙共聚物之製造方 法，可例舉如：在使下述助觸媒載體（Α)、交聯型雙茚基鍅 錯合物（Β)以及有機鋁化合物（c)接觸所得金烯 (meta]]ocene)系觸媒之存在下，進行乙烯與碳數3以上之 316749 9 1364436 ίϊ -如煙之共聚的方法。 上述助觸媒載體（A)，係使（a)二乙基鋅、（b)氟化酚、 (c)水、（d)二氧化矽以及卜）三甲基二矽胺烷（（（CHASihNH) 接觸所得之載體。 上述成分（a)、（b)以及（c)之使用量並無特別限制，惟 將各成分使用量之莫耳比設為成分（a):成分（b广成分 (c)=l : y : Z時，則較佳為y及z能符合下述式。 I 2-y-2z I ^ 1 上述式中’ y的數值較佳為〇 〇1至丨9 至⑽，再佳為㈣至⑽，最佳為0.30至⑽為010 相對於成分（a)所使用的成分（d)之量而言因成分 (a)、（b)、（c)、（d)以及（e)之接觸所得的粒子中所含之鋅原 =之莫耳數，較佳為在每lg該粒子中為〇1毫莫耳以上之 里’更佳為0.5 20毫莫耳之量。相對於成分⑷所使用 的成分⑷之量而言，較佳為在每lg之成分⑷中為成分 ()〇.1毫莫耳以上之夏，更佳為G 5至2G毫莫耳之量。 父聯型雙印基結錯合物（B)較佳為外；肖旋乙婦雙 基)錯一氣化物及外消旋乙烯雙(1•茚基)錯二苯氧化物。 有機紹化合物（C)較佳為三異丁基缝三正辛基銘。 交橋型雙節基錯錯合物⑻之使用量，在每 媒載體㈧中’較佳為5xl。-6至5><1。.4莫耳。此外，有： 链化。物（C)之使用量較佳為在每丨莫耳之 鍅錯合物（B)的鍅原子中，女h 又印基 至2_莫耳的量。 冑難化合物⑹之紹原子為] 316749 10 ^用在料之t，從經濟性、安全性之觀點而言，較佳 马彳木用二氧化碳或氮氣。 二學侧可例舉如：碳酸錢、碳酸納、碳酸氨錄、 機：：：；亞編安、氫蝴酸納、無水檸檬酸-納等的無 包m酿胺、偶氮二賴鎖、偶氮雙丁腈、 _ 启基五亞甲基四銨、ν，ν，-二甲基 醯车士―亞靖基對m㈣、對^伽肼、對甲苯續 >氧基雙苯磺酿半卡㈣T5偶氣雙異丁猜、p，p，- 干下匕細5-本基四唑、三肼基三畊、伸胼 軸等㈣系發泡劑等。在這些之中，從經濟性、 之f 占而5 ’卓父佳為採用偶氮基二幾酿胺、碳酸氫 〃 、P’P~氧基雙笨^肼。由於成形溫度範圍較大，且可 f微細f包之擦製發泡成形品’因此，特佳為採用含有偶 氮一羧胺及碳醯氫鈉之發泡劑。 。採用化學發泡劑時，通常使用分解溫度在】40至刚 卜C的化學發泡劑。如使用分解溫度在i8〇t>c以上的化學發 泡劑時’較佳為藉由發泡助劑之併用而將分解溫度降至 180。。以下後使用。發泡助劑可例舉如：氧化鋅、氧化妒等 金屬氧化物；碳酸鋅等金屬碳酸鹽；氯化鋅等.金屬氯化二； 尿素；硬脂酸鋅、硬脂酸錯、二鹽基性硬脂酸錯、月桂酸 鋅、2-乙基己酸鋅、二鹽基性鄰苯二甲酸錯等金屬專；二 丁基錫二月桂酸醋、二丁基錫二馬來酸g|等有機錫化合 物；三鹽基性硫酸錯、二鹽基性亞鱗酸船、鹽基性亞硫酸 錯等無機鹽類；二丁基錫二月桂酸鹽系、二丁基錫二馬來 316749 ]2 1364436 _酸鹽系、鈣-鋅系、鋇_鋅系等聚氯化乙烯用複合安定劑等。 :發泡助劑之使用量，係將發泡劑和發泡助劑的總合計為 • 100重量％時，通常為0.1至30重量％、較佳為丄至20重 量％。 採用化本發/包劑時，通常使用由前述化學發泡劑、發 泡助劏以及樹脂所構成之母料（master batch)。母料所用樹 脂^種類，只要是不妨礙本發明之效果，則並無特別限定， 惟較佳為構成發明之成形品的乙烯_α_烯烴共聚物。母料 •中所含有的化學發泡劑以及發泡助劑之總量對樹脂的調配） 比例通常為5至90重量％。 如採用物理發泡劑時，經由併用發泡晶核劑，即可製 得具有更微細氣泡之成形品。發泡晶核劑可例示如：滑石、 一氧化矽、雲母、沸石、碳酸鈣、矽酸鈣、碳酸鎂、氫氧 化鋁、硫酸鋇、鋁矽酸鹽、黏土、石英粉、矽燥土等無機 填充劑’·由聚甲基甲基丙稀酸醋、聚苯乙婦所成粒經_ m以下之珠粒；硬脂酸鈣、硬脂酸鎂、硬脂酸鋅、安息 香酸鈉、安息香酸辦、安息香酸紹、氧化鎮等金屬鹽，此） 等發泡晶核劑可組合二種以上使用。此外，使用物^發泡 劑時，亦可使用前述化學發泡劑作為發泡晶核劑。如使用 化學發泡劑作為發泡晶核劑時，較佳為使用分解溫度較低 之化學發泡劑。較佳為，例如，以偶氮二羧醯胺、ρ，ρ，_氧 基又本讲、Ν，Ν- 一亞石肖基五亞甲基四胺等作為主成八 的化學發泡劑。此外，亦可併用複數種化學發泡劑。刀 發泡劑之添加量係依所使用發泡劑之種類、或所製造 316749 】3 1364436 成形异之發泡倍率而適本# 形品:樹脂，通常為〇二。重量二:。。*量份之構成成 可例舉如：過氧^ 一^衣七/包成升）時添加交聯劑。交聯劑 三丁基)己烧、2,5:異 -3、過氧化二笨曱酿、2 ^二（過乳化第三丁基）己缺 息香酸第三丁醋、過氧化異丁醋' 13 :(:基)丁烧、過安 異丙基）苯等。 ，3-又（過氧化第三丁基 如使用父聯劑時，亦可六 舉如：三聚氰酸三烯丙醋、三稀：丄：劑二聯助劑可例 ^甲基丙細酸縮水甘油醋、聚二甲基丙婦酸乙二醇酿 使用交聯劑時之添加量，對於刚重量份之構成成形 品的樹脂’通常為0.01至L0重 ：成成开/ 各曰a 里物餃佳為0.03至0.5 ，更佳為0.05至0.3重量份。如交聯劑之使用量過Engineenng and Science), Vol. 8, p. 235 (published in 1968)). The ethylene olefin copolymer constituting the molded article of the present invention preferably has a glare flow rate (me) t fi〇w rate at 190 C (hereinafter, abbreviated as MFR) at 〇·〇] to 5 g/1. 〇 minutes, more preferably 〇〇5 to 4^1〇 minutes, and even better 0_1 to 3g/10 minutes. MFR is based on the value obtained by Jis K6760. If the MFR is too low, the surface of the molded article becomes rough, and sometimes sufficient expansion ratio cannot be obtained. If the MFR is too high, the air bubbles in the molded article become coarse, or the surface of the molded body is perforated. The method for producing the ethylene-containing-α-olefin copolymer constituting the molded article of the present invention may, for example, be a carrier-supporting carrier (Α) or a cross-linked bis-indenyl ruthenium complex (Β). And a method in which ethylene and a carbon number of 3 or more 316749 9 1364436 ίϊ-such as a cigarette are copolymerized in the presence of an organoaluminum compound (c) in contact with the obtained gold (meta)] ocene) catalyst. The above-mentioned cocatalyst carrier (A) is obtained by (a) diethylzinc, (b) fluorinated phenol, (c) water, (d) cerium oxide, and trimethyldiamine. CHASihNH) Contact with the obtained carrier. The amounts of the above components (a), (b) and (c) are not particularly limited, but the molar ratio of each component is used as the component (a): component (b broad component) (c) = l : y : Z, preferably y and z can satisfy the following formula: I 2-y-2z I ^ 1 The value of 'y in the above formula is preferably from 〇〇1 to 丨9 to (10), preferably (4) to (10), preferably 0.30 to (10) is 010. The components (a), (b), (c), (d) are related to the amount of the component (d) used in the component (a). And the number of moles of zinc former contained in the particles obtained by the contact of (e) is preferably 〇1 mmol or more per lg of the particles, more preferably 0.5 20 mmol. The amount of the component (4) to be used in the component (4) is preferably in the range of (1) millimolar or more in the component (4) per lg, and more preferably in the range of G 5 to 2 G in the summer. The amount of the parent-type double-printing complex (B) is preferably external; And racemic ethylene bis(1·fluorenyl) stilbene oxide. The organic compound (C) is preferably triisobutyl sulphide tri-n-octylamine. The use of bridge type double-blocked base error complex (8) The amount is preferably 5xl.-6 to 5<1..4 moles per medium carrier (eight). In addition, there is: chaining. The amount of the substance (C) is preferably used in each mole. In the tantalum atom of the complex (B), the female h is printed to the amount of 2_mol. The difficult atom of the compound (6) is 316749 10 ^ used in the t, economic and safety From the viewpoint of view, it is preferable to use carbon dioxide or nitrogen gas for the eucalyptus wood. The second side can be exemplified by: carbonic acid money, sodium carbonate, ammonium carbonate recording, machine:::; sub-coded, sodium hydrogen hydride, anhydrous citric acid -Nano, such as unpackaged m-bristamine, azo-dialog, azobisbutyronitrile, _ keki pentamethyltetraammonium, ν, ν, - dimethyl 醯 Chess - Yajingji pair m (four), right ^Glycerin,p-toluene continued>oxybisbenzenesulfone-branched half-card (4)T5-even gas double-isobutyl, p,p,-dry 匕5-benzazole, triterpene three tillage, stretch axis (4) is a foaming agent, etc. Among these, from the economy , f accounted for 5 'Zhu father Jia is the use of azo bisamine, bicarbonate, P'P ~ oxy double stupid. Because of the large forming temperature range, and can be fine f package rub Therefore, it is particularly preferable to use a foaming agent containing azo-monocarboxylamine and sodium borohydride. When a chemical foaming agent is used, a chemical reaction having a decomposition temperature of 40 to C is usually used. If a chemical foaming agent having a decomposition temperature of i8〇t>c or more is used, it is preferred to reduce the decomposition temperature to 180 by the combination of the foaming assistants. For example, metal oxides such as zinc oxide and cerium oxide; metal carbonates such as zinc carbonate; zinc chloride, etc. metal chloride; urea; zinc stearate, stearic acid, dibasic stearic acid Misty, zinc laurate, zinc 2-ethylhexanoate, dibasic phthalic acid, etc.; organotin compounds such as dibutyltin dilaurate, dibutyltin dimaleic acid g; tribasic Inorganic salts such as sulphuric acid sulphate, dibasic sulphite, salt-based sulphite, etc.; dibutyltin dilaurate, dibutyl Base tin two Malay 316749 ] 2 1364436 _ acid salt, zinc-zinc system, 钡_zinc system and other compound stabilizer for polyvinyl chloride. The amount of the foaming aid to be used is usually from 0.1 to 30% by weight, preferably from 丄 to 20% by weight, based on the total of the foaming agent and the foaming aid. When a hair/packaging agent is used, a master batch composed of the above-mentioned chemical foaming agent, foaming aid, and resin is usually used. The type of the resin to be used in the master batch is not particularly limited as long as it does not impair the effects of the present invention, and is preferably an ethylene-α-olefin copolymer constituting the molded article of the invention. The ratio of the total amount of the chemical foaming agent and the foaming aid contained in the masterbatch to the resin is usually from 5 to 90% by weight. When a physical foaming agent is used, a molded article having finer bubbles can be obtained by using a foaming nucleating agent in combination. Examples of the foaming crystal nucleating agent include talc, cerium oxide, mica, zeolite, calcium carbonate, calcium citrate, magnesium carbonate, aluminum hydroxide, barium sulfate, aluminum silicate, clay, quartz powder, dried earth, and the like. Inorganic Filler'·Beads granulated by polymethylmethacrylate vinegar and polystyrene, _ m or less; calcium stearate, magnesium stearate, zinc stearate, sodium benzoate, Azeotropic acid, benzoin acid, oxidized town and other metal salts, this) and other foaming crystal nucleating agents can be used in combination of two or more. Further, when a foaming agent is used, the above chemical foaming agent can also be used as the foaming nucleating agent. When a chemical foaming agent is used as the foaming nucleating agent, it is preferred to use a chemical foaming agent having a lower decomposition temperature. Preferably, for example, a azobiscarboxyxanthamine, ρ, ρ, _ oxy group, a sulfonium, a fluorene-monosuccinylpentamethylenetetramine or the like is used as a chemical foaming agent. In addition, a plurality of chemical blowing agents may be used in combination. The amount of the foaming agent to be added is determined according to the type of the foaming agent used or the foaming ratio of the molded 316749 】 3 1364436. The shape is: resin, usually bismuth. Weight two: . * The composition of the components can be exemplified by the addition of a crosslinking agent such as: peroxyl ^ 1 coat / 7 packs. Cross-linking agent, tributyl), calcined, 2,5:iso-3, peroxide, abbreviated, 2^2 (over-emulsified, tert-butyl), glycerol, third vinegar, isobutyl peroxide Vinegar '13: (: base) butadiene, peroxy isopropyl) benzene and so on. , 3- (peroxidized tributyl group, if using a parent-linked agent, it can also be used as follows: cyanuric acid triacetate, tris: 丄: agent two auxiliary agents can be ^ methyl propyl The amount of addition of the acid glycidol vinegar and the polydimethyl ketoacetate to the cross-linking agent is usually 0.01 to L0 for the resin of the molded product of the original part by weight: The dumplings are preferably from 0.03 to 0.5, more preferably from 0.05 to 0.3 parts by weight.
A，則有氣泡直徑變得不均句、或無法得到微細氣泡之 傾向，而如交聯劑之使用量過多日夺，則有流動性變差而難 以成形之傾向^如使用交聯助劑時，通常約為交聯劑之3 至10倍左右（重量基準）。 本發明之成形體中，在不妨礙本發明之效果之程度 下，可含有前述乙烯-α-烯烴共聚物以外之樹脂或添加劑1 本發明之成形品中可含有乙烯_ α _烯烴共聚物以外之 樹脂，係有·尚密度聚乙稀、中密度聚乙婦、低密度聚乙 烯等乙烯單獨聚合物、或含有源自丙烯酸之構成單元50 316749 14 1364436 重里。/〇以上的乙烤-丙烯酸共聚物、或乙燁-丙烤酸-丁烯-1 共聚物等之共聚物、不符合本發明所使用之乙烯-α -烯烴 •共聚物的共聚合物等。本發明所使用之乙烯-α-烯烴共聚 物以外之樹脂之含量，如將構成該成形品的樹脂重量設為 100%時，通常為 10重量％以下。 添加劑可採用習知之添加劑，可例舉如：玻璃纖維、 碳纖維等無機充填劑；如染料、顏料等著色劑；中和劑、 k氡化劑、熱安定劑、耐候劑、潤滑劑、紫外線吸收劑、 U靜電劑、防黏連劑、防霧劑、分散劑、難燃劑、抗菌劑、） 螢光增白劑等。 在本發明之成形體的製造中，如與乙烯-α-烯烴共聚 物同時使用其他樹脂或添加劑時，則便可預先將此等混合 後以作為樹脂組成物而使用。製造樹脂組成物時，可使用 白知之混合機或混練機。此外，亦可一面使用計量機進行 乙烯烯烴共聚物與其他樹脂或添加劑之計量，一面分 鲁別供給至擠製發泡成形機。 本％明之成形品的製造方法並無特別限定，係將乙稀-, α -烯烴共聚物或含有此種共聚物之樹脂組成物，使用單軸 螺旋擠製機、雙軸螺旋擠製機等習知成形機進行熔融混 練，從經安裝在成形機前端之模頭（die)擠出大氣中的方 法。模頭可依目的而由縫隙式模頭、圓盤條隙式模頭、圓 形模頭、異形模頭等各種型式之模頭中進行選擇。成形機 與杈頭之間，為擠製量穩定化起見，可設置齒輪泵 pump)。此外，以混練樹脂與發泡劑為目的，而可將^態 316749 1364436 攪拌器（static mixer)設置於擠製機與模頭之間。如使用物 理發泡劑時，則在乙烯_α •稀烴共聚物或樹脂組成物炫融 後，從成形機之物理發泡劑供給口注入物理發泡劑。 。在擠製發泡成形中，擠製機之溫度通常在1〇〇至26〇 C，而模頭之溫度通常在％至24(rc。剛從模頭擠製後的 炫融狀態之播製成形品正形成發泡。藉由以冷卻輕輪冷 ，心師。。!】ng ma論el)、冷卻空氣、冷卻水等將“融^ 悲之播製發泡成品冷卻，即可製得作為最終製 泡成形品。 〜表知 本發明之成形品的發泡倍率並無特別限定，通常為^ 至％倍。本發明之成形品，即使發泡倍率高，外觀依然長 好而且’成形品之厚度、形狀亦無特別限定者。 本發明之成形品中，可依需要層合丨層以上之追办 層’以作成多層成形品。此種多層成形品，可藉 製造’而且，亦可將經由擠製發泡成形所得“A, there is a tendency that the bubble diameter becomes uneven, or that fine bubbles are not obtained, and if the amount of the crosslinking agent is too large, the fluidity is deteriorated and it is difficult to form. For example, a crosslinking aid is used. It is usually about 3 to 10 times (by weight) of the crosslinking agent. In the molded article of the present invention, the resin or the additive other than the ethylene-α-olefin copolymer may be contained to the extent that the effect of the present invention is not impaired. The molded article of the present invention may contain an ethylene_α-olefin copolymer. The resin is a vinyl individual polymer such as a polyethylene density, a medium density polyethylene, or a low density polyethylene, or a constituent unit derived from acrylic acid 50 316749 14 1364436. a copolymer of an ethylene-acrylic copolymer or an acetamidine-propane-butene-1 copolymer or the like, a copolymer of ethylene-α-olefin copolymer not used in the present invention, and the like . The content of the resin other than the ethylene-α-olefin copolymer used in the present invention is usually 10% by weight or less when the weight of the resin constituting the molded article is 100%. The additive may be a conventional additive, and may, for example, be an inorganic filler such as glass fiber or carbon fiber; a coloring agent such as a dye or a pigment; a neutralizing agent, a k-tellurizing agent, a heat stabilizer, a weathering agent, a lubricant, and an ultraviolet absorbing agent. Agent, U static agent, anti-blocking agent, anti-fogging agent, dispersing agent, flame retardant, antibacterial agent, fluorescent brightener, etc. In the production of the molded article of the present invention, when other resins or additives are used together with the ethylene-α-olefin copolymer, these may be mixed in advance and used as a resin composition. When manufacturing a resin composition, a mixer or a kneading machine of Shichi can be used. Further, it is also possible to measure the ethylene olefin copolymer and other resins or additives while using a measuring machine, and supply them to the extrusion foam molding machine. The method for producing the molded article of the present invention is not particularly limited, and a acetylene-, α-olefin copolymer or a resin composition containing the copolymer is used, and a uniaxial screw extruder, a biaxial screw extruder, or the like is used. The conventional molding machine performs melt kneading and extrudes the atmosphere from a die attached to the front end of the molding machine. The die can be selected from various types of die, such as a slit die, a disk strip die, a circular die, and a profiled die, depending on the purpose. Between the forming machine and the boring head, the gear pump can be set for the purpose of stabilizing the amount of extrusion. In addition, for the purpose of kneading the resin and the foaming agent, a static mixer of 316749 1364436 can be placed between the extruder and the die. When a physical foaming agent is used, the physical foaming agent is injected from the physical foaming agent supply port of the molding machine after the ethylene_α•thin hydrocarbon copolymer or the resin composition is condensed. . In the extrusion foam molding, the temperature of the extruder is usually from 1 〇〇 to 26 〇C, and the temperature of the die is usually from % to 24 (rc. The broadcast state immediately after extrusion from the die) The molded product is forming foaming. By cooling the light wheel, the heart, the singer, the cooling air, the cooling water, etc. The foaming ratio of the molded article of the present invention is not particularly limited, and is usually from 2 to 5%. The molded article of the present invention has a high appearance and a good appearance even when the expansion ratio is high. The thickness and shape of the product are not particularly limited. In the molded article of the present invention, a layer of the above-mentioned layer of the enamel layer or more may be laminated as needed to form a multilayer molded article. Such a multilayer molded article may be manufactured by Can be formed by extrusion foaming
^合以追加層，藉由乾式層合法或熱融合法㈣ :作：追加層而設置乙稀_乙稀醇共聚物、聚酿⑴ I對本H6S§樹脂等氣體阻障層性優異之樹; 猪夕爲層，即可作成氣體阻障層性優異之多層成形品” 二：成形品可適用於食品容器等。此外，可作成具有$ 士、木粉之未發泡樹脂所成最外層的多層成形品。又叫 M t月之&衣發泡成形品經由被覆成形於未發泡輸送/ ⑽’未發泡導管(pipe)外側，即可對輸送管或導管賦」 316749 16 1JM436 試樣溶液注入量：40〇m1 制▲、鄰"I氯笨中添加試樣，在140。〇下加熱2小時，以調 衣式^'展度〇1%之溶液。將此溶液（400 /z 1)注入於GPC裝 置=s = (140 C )中。使用示差折射計檢測從管柱所溶出之 =刀而付到色_。從所得色譜、與由單分散標準聚苯乙稀 :(月又）製’分子量=5〇〇至6 〇〇〇 〇〇〇)所作成的Gpc裝置 之=正曲線，求出試樣之重量平均分子量（Mw)、數平均分 里（Μη)奴所付之Mw與—算出試樣之分子量分佈 (MW/Mn)。（分子量分佈簡記為MWD)。 4.膨脹比（SR) μ使用具有直徑lmm、長度40mm、流入角90度之毛 二的毛細官型點度計（商品名：capir〇gr··出；東 月機（股）製）’依據JIS ，在溫度眞、剪切速 〇.8s之下連續撥製試樣。於毛細管出口切斷所擠製的 ί並t除、。持續進行擠製，並當新擠製的股線長度為2此 :右：f疋攸毛細官之出口 l5mm時之位置的股線之 7 ""錢時，係❹雷純料。將股線之直 除以毛細管之直徑的值以作為膨脹比_。 5.擠製發泡成形品之厚度 播製發泡成形品之原声r罝 制之勃仞白叙I自_ mm)，係採用三i(月] 衣之數位自動顯不式標準外側測微計而測定。 6·擠製發泡成形品之發泡倍率 擠製發泡=形品之發泡倍率係採用密度計㈣·讓 t ’ A&D(股）衣）’依水中取代法在饥下測定。 316749 18 1364436 7.擠製發泡成形品之外觀 揭‘叙/包成形品之表面係依目視，按下述之基準的三 個階段加以評估。 (評估基準） A :未發生波紋且光澤佳。 B:稍微發生波紋。 C:有發生波紋、或表面變成粗糙或穿孔而使外觀變差。 8 ·播製發泡成形品之撕裂強度 瞻依據ASTM D1922-67所規定的方法（A法），測定後述 方去所知·播製發泡片材往捲取方向的愛爾曼多夫撕裂強度 (單位：kgf/cm)。 9.流動之活化能Ea [動態黏彈性之測定] 測定動態黏彈性（儲存模量（G，）、損失模量（G，，)）時，採 用點彈性測定裝置（流變儀（Rheometrics)公司製rMS_800 鲁型）°測定係在氮氣環境下依下述條件進行。 (1) 測疋部形狀：平行板（直徑25mm、板間隔：約1 mm) (2) 剪應變：5% (3) 角頻率：〇」、〇 15849、〇 2512、〇 39812、〇 63〇98、 ^00003、1.58496、2.51202、3.98132、6.31006、10.0007、 ^.8501、25.1206、39.8135、63.1006、l〇〇ra(j/秒^Additional layer, by dry layering or heat fusion method (4): for: additional layer to set up ethylene-ethylene glycol copolymer, polymer (1) I to this H6S § resin and other gas barrier layer properties; When the pig is a layer, it can be used as a multilayer molded article with excellent gas barrier properties. 2: The molded article can be applied to a food container, etc. In addition, it can be made into an outermost layer of an unfoamed resin having a sap and wood powder. Multi-layer molded product. Also known as M t Yue & clothing foam molded product can be formed on the outside of the unexpanded conveying / (10) 'unexpanded pipe by coating, 316749 16 1JM436 test Sample solution injection amount: 40 〇m1 system ▲, adjacent "I chlorine stupid addition sample, at 140. Heat the underarm for 2 hours to adjust the solution to a 1% solution. This solution (400 / z 1) was injected into the GPC unit = s = (140 C ). A differential refractometer is used to detect the squeezing from the column and the color _ is applied. Calculate the weight of the sample from the obtained chromatogram and the positive curve of the Gpc device made from monodisperse standard polystyrene: (molecular weight = 5 〇〇 to 6 制) The average molecular weight (Mw), the number average aliquot (Μη), the Mw paid by the slave and the calculated molecular weight distribution (MW/Mn) of the sample. (Molecular weight distribution is abbreviated as MWD). 4. Expansion ratio (SR) μ Use a capillary official meter with a diameter of 1 mm, a length of 40 mm, and an inflow angle of 90 degrees (trade name: capir〇gr··出; Dongyueji (share)) According to JIS, samples were continuously drawn under temperature 眞 and shear speed 〇8s. Cut off the squeezed ί and remove by the capillary outlet. Continue to squeeze, and when the length of the newly extruded strand is 2: Right: f疋攸 毛细官's exit l5mm when the position of the strand of 7 "" money, is the pure material. The straight line is divided by the value of the diameter of the capillary as the expansion ratio _. 5. The thickness of the extruded foamed molded article is the original sound of the foamed molded product. The 仞 仞 仞 叙 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自6. The expansion ratio of the extruded foamed product is extruded. The foaming ratio of the molded product is determined by the density meter (4) · Let t ' A & D (stock) clothing) Determination of hunger. 316749 18 1364436 7. Appearance of extruded foamed molded articles The surface of the finished or coated molded articles was evaluated according to the three stages of the following basis. (Evaluation criteria) A: No ripples occurred and the gloss was good. B: There is a slight ripple. C: There is a ripple, or the surface becomes rough or perforated to deteriorate the appearance. 8 · The tear strength of the molded foamed product is in accordance with the method specified in ASTM D1922-67 (method A), and the measurement is described later. The foamed sheet is taken to the direction of winding. Tear strength (unit: kgf/cm). 9. Activation energy of flow Ea [Determination of dynamic viscoelasticity] When measuring dynamic viscoelasticity (storage modulus (G,), loss modulus (G,,)), a point elasticity measuring device (Rheometrics) is used. The company's rMS_800 Lu type) was measured under the following conditions in a nitrogen atmosphere. (1) Shape of the measuring part: parallel plate (diameter 25mm, plate spacing: about 1 mm) (2) Shear strain: 5% (3) angular frequency: 〇", 〇15849, 〇2512, 〇39812, 〇63〇 98, ^00003, 1.58496, 2.51202, 3.98132, 6.301006, 10.0007, ^.8501, 25.1206, 39.8135, 63.1006, l〇〇ra (j/sec
(4) 溫度：130°C、150t、170。(：、190°C 19 316749 丄允4436 [位移因素之求算] • 位移因素（aT)之求算步驟係如下所述。 將U〇<t(403。κ)作為基準溫度（To)，依照式（1)及（2)， 作成G，(Pa)及G，，(Pa)之主曲線。 - °'(ω > T)=bTG'(aT6； ' T〇) (1) G"(6j ^ T)=bTG"(aT6j ' T〇) (2) 在此，ω表示角頻率（^…秒）、T表示各測定溫度 K) T〇表示基準溫度、打表示角頻率方向之位移量、卜表 W示G’、G”轴方向之位移量。 [活化能之求算] 流動之活化能（Ea)係按以下步驟求出。 繪製對1/T的l0g(aT)之曲線。就此所繪製的曲線，進 行以最小平方法之近似直線，算出直線之斜率。將所得斜 率視作Ea/2.303R ’以算出Ea(kJ/莫耳）。 在實施例及比較例中所採用的聚合物如下所述。各聚 I合物之物性示於表1。 1. 乙烯-1-己烯共聚物 溶體流動速率（職)為Ug/10分鐘，密度⑷為923kg /m3之乙烯-1-己稀共聚物。 2. 乙烯-1-辛烯共聚物 熔體流動速率_)為lg/1〇分鐘，密度⑷為_ /1Ώ3之市售的乙烯-1-辛烯共聚物。 3. 高壓法低密度聚乙烯 住友化學（股）製之商品名Λ ςττΛ/ττΡΛ 马 SUMJK^SEN F]02-0 的高 316749 20 1364436 壓法低密度聚乙烯。該聚乙烯之熔體流動速率（MFR)為 0.3g/10 分鐘，密度（d)為 922kg/m3。 4.苯乙烯-異戊二烯-苯乙烯嵌段共聚物 克萊雷（股）製之商品名為SEPTON 2104的苯乙烯-異 戊二烯-苯乙烯嵌段共聚物。該共聚物之熔體流動速率為 0.8g/10 分鐘，密度（d)為 970kg/m3。 [實施例1] [乙烯-1-己烯共聚物之製造] 依下述方法實施乙烯與1-己烯之共聚合，製得乙烯-1- ) 己稀共聚物。 [觸媒成分之調製] 助觸媒載體（A)之調製 於具備有經氮氣取代的攪拌機之反應器中，其中放入 2.8kg之於氮氣流通下經300°C加熱處理之二氧化矽（商品 名：Sy]οροί 948 ;德比遜公司製；平均粒徑=5 // m ;微孔 容量=1.67ml/g ;比表面積=325m2/g)與24kg之甲苯，並攪 > 拌。冷卻至5°C後，將反應器溫度維持在5°C，並同時在 / 33分鐘内滴入0.91kg之1,1,1,3,3,3-六曱基二矽胺烷與 1.43kg之曱苯的混合溶液。點滴結束後，在5°C下攪拌1 小時，在95°C下攪拌3小時之後進行過濾。使用21kg之 曱苯清洗所得之固體生成物6次。然後，添加6.9kg之曱 苯作成漿液，並靜置一晚。 於上述所得之漿液中，投入2.05kg之二乙基鋅的己烷 溶液（二乙基鋅濃度：50wt%)與1.3kg之己烷，並攪拌。接 316749 1364436 著，冷卻至5。(：後，將反應器溫度維持在5。〇，並同時在 61分鐘内滴入〇 77kg之五氟酚與丨l7kg之甲苯的混合溶 液。點滴結束後，在5 C下攪拌1小時，在4〇它下授拌工 小4。然後，將反應态溫度維持在5 〇C，並同時在1 5小 h内滴入0.11 kg之水。點滴結束後，在5 〇c下授拌】5小 時，在55°C下攪拌2小時。然後，在室溫下投入}沁“之 一乙基鋅之己烷溶液（二乙基鋅濃度：5〇wt%)與〇 8kg之己 烷。冷卻至5〇C後，將反應器溫度維持在5«>c，並同時在 60刀益里内滴入〇 42kg之3,4,5-三氟酚與〇 77kg之甲苯的 混合溶液。點滴結束後，在下攪拌！小時，在4〇艺下 搜掉1小時。然後，將反應器溫度維持在5t，並同時在 1.5小蚪内滴入〇.〇77kg之水。點滴結束後，在5艺下攪拌 I/ .小時，在4(rc下攪拌2小時並在8〇。〇下攪拌2小時。 停止攪拌後抽出上清液至餘量為16公升為止，並投入 11·㈣之甲苯並授拌。升溫至95t並㈣4小時。靜置而 使固體成分沈澱，當出現沈澱之固體成分之層（下層）與漿 液部分（上層）之間的界面時，去除漿液部分（上層），接著， 過濾所剩餘的液體成分（下層p將所得之固體0生成物以 2〇.8kg之甲苯清洗4次，以及24公升之己燒清洗卜大。 然後，加以乾燥，#此製得固體成分(以下，簡稱為 載體（A))。 〃 [預聚觸媒成分之調製] ^先，氮氣取代的内容積2】〇公升之附有授掉機的 问壓奎中，投入〇.53kg之上述助觸媒載體（A)，在25七之 316749 22 1364436 • 大氣壓下的高壓爸中放入3公升之氫氣、20g之丁烯-1以 ··. 及80公升之丁烷後，將高壓爸升溫至30°C。再將乙烯按 . 高壓蒼内之氣相壓力計送入0.03MPa之相當量，待系内安 定後，投入159毫莫耳之三異丁基鋁與53毫莫耳之外消旋 乙烯雙（1-茚基）錯二苯氧化物，並開始聚合。升溫至31 °C 之同時，在連續供給乙烯與氫氣之下再升溫至51°C，共實 施4小時之預聚。聚合結束後，實施乙烯、丁烷、氫氣等 之沖洗（purge)，並將殘留固體在室溫下真空乾燥。如此， 籲製得於每lg之上述助觸媒載體（A)中有15g之乙烯經預聚 ' 的預聚觸媒成分。 '[聚合] 使用上述所得之預聚觸媒成分，於連續式流化床氣相 聚合裝置中實施乙烯與1-己烯之共聚合，製得乙烯-1-己烯 - 共聚物粉體。聚合條件而言，作成聚合溫度為75°C，聚合 壓力為2MPa，對乙烯之氫莫耳比為0.9%，相對於乙烯之 1-己烯莫耳比為0.9%。在聚合中，為了維持固定之氣體組 成，便連續性地供給乙稀、1 -己烤以及氫氣。此外，連續 性地供給上述預聚觸媒成分與三異丁基鋁，以維持流化床 中之總粉體重量為一定（80kg)。平均聚合時間為4小時。 [混練] 在所得之乙烯-1-己烯共聚物粉體中添加抗氧化劑（商 品名：SUMIRIZER GP，住友化學（股）製），使濃度成為 7 5 0ppm，並加以混合。採用擠製機（商品名：LCM50 ;神 戶製鋼所公司製），經由在進給速度50kg/小時，螺旋旋轉 23 316749 1364436 •數 450ppm，生料口（gate)開度 50%，吸取（sucti〇n)壓力 ·*· 0.lMPa ’樹脂溫度200至230Ϊ之條件下實施所得混合物 ..的造粒，而製得乙焊-1 -己烯共聚物顆粒（peiie〇。 [擠製發泡成形品之製造] 使用滾桶混合機（tumble mixer) ’將1 〇〇重量份之乙稀 -1 -己烯共聚物顆粒，與1重量份之偶氮基二羧酸系化學發 泡劑（商品名：色爾邁克MB2043 ;三協化成（股）製）混合j 分鐘。將此混合原料供給至直徑為5〇inm、長度為2.lm之 鲁具備3處具有混合段的螺旋之片材成形機，依螺旋旋轉數 為60rpm、混練部之溫度為15〇至21(rc、模頭部之溫度 為1 50°C之條件擠製。擠製量為工8kg/小時。在擠製機之中 間部設有注入閥，而從該閥，將經加壓為〗〇MPa之碳酸氣 體連續注入並以成為0.4重量份的方式調節注入量。擠製 '機前端設有外徑為8〇mm、内徑為79.2mm、模唇（lip)之間 隙（clearance)為〇.4mm之圓盤模頭，而從該圓盤模頭以圓 籲盤形狀擠製熔融狀態之發泡樹脂。藉由使溫度乃艽之冷卻 水循ί辰的冷卻模蕊將該熔融狀態之發泡樹脂冷卻並使其固 化，且使用夾膜輥（pinch r〇n)加以捲取，製得厚度〇 8mm、 發泡倍率2.1倍之擠製發泡成形片材。在該擠製發泡成形 片材上並未發生波紋，片材之外觀良好。而且，此種片材 之撕裂強度為38kgf/cm，機械強度亦優異。該結果如表2 所示。 [實施例2] 除了連續注入碳酸氣體使注入量調整成0_5重量份以 316749 24 1364436 -外，其餘則與實施例！同樣方法製造播製發泡成形片材。 ••所得結果如表2所示。在該擦製發泡成形片材上並未發生 ‘·波乡文，片材之外觀良好。而且，此種片材之撕裂強度為W kgf/cm，機械強度亦優異。 [比較例1] 除了採用高壓法低密度聚乙稀（SUMikasen fi〇2 〇) 以取代乙稀小己烯共聚物以外，其餘則與實施例丨同樣方 法製造播製發泡成形片材。所得結果如表2所示。在此種 ♦擠製發泡成形片材上有產生波紋，並非外觀優良之片材。 而且，撕裂強度為20kgf/cm，且機械強度不佳。 [比較例2] 除了採用市售之乙烯辛烯共聚物以取代乙烯-己 •烯共聚物以外，其餘則與實施例丨同樣方法製造擠製發泡 -成形片材。所得結果如表2所示。此種擠製發泡成形片材 上有產生鯊皮紋（shark skin)’而非外觀優良之片材。而且， 籲此種片材之撕裂強度為22kgf/cm ’機械強度亦差。 [比較例3] 使用滾桶混合機，將市售之6〇重量份的乙烯辛烯 共聚物，與30重量份之苯乙烯·異戊二烯·苯乙烯嵌段共聚 物加氫物（SEPTON 2104)，與10重量份之高壓法低密度聚 乙稀（SUMIKASEN F1G2-G)，以及1重量份之化學發泡劑 (/商品名··色爾邁克MB2〇43 ;三協化成（股）製）偶氮二羧酸 系混合1分鐘。將該混合原料供給至與實施例]同樣的片 材成形機，依螺旋旋轉數為6〇rpm，混練部之溫度為】 3J6749 25 U64436 18k _頭部之溫度為18(rc之條件播製。播製量為 kg/小卜依圓盤模頭的模唇（iip)之間隙⑷⑽㈣為 之條件，按圓盤形狀擠製熔融狀態之發泡樹脂。藉 2溫度25t之冷卻水循環的冷卻模蕊而將該熔融狀態 ^泡樹脂冷卻並使其固化，且使用夾膜輥加以捲取，而 ^旱厚度〇.4mm之擠製發泡成形片材。此種播製發泡成形 片材之發泡倍率低至M倍’且片材表面有產生紫皮紋， 仏外親差劣者。而且，撕裂強度為14kgf/cm，機械強度不 [比較例4] 擦製發泡成形中，除了由注入閥連續注入經加壓為 l〇MPa的碳酸氣體而使注入量成為〇4重量份者以外豆 餘則與比較例3同樣方式製造擠製發泡成形片材。此種擠 製發泡成形片材之厚度為〇.72mm，發泡倍率為！ 6倍，惟 片材表面穿孔係外觀差劣者。而且，片材之撕裂強度為13(4) Temperature: 130 ° C, 150 t, 170. (:, 190 ° C 19 316749 丄 4436 [calculation of the displacement factor] • The calculation of the displacement factor (aT) is as follows. U〇<t(403.κ) is used as the reference temperature (To) According to equations (1) and (2), create the main curve of G, (Pa) and G, (Pa). - °'(ω >T)=bTG'(aT6; ' T〇) (1) G"(6j ^ T)=bTG"(aT6j ' T〇) (2) Here, ω represents an angular frequency (^...second), and T represents each measured temperature K) T〇 represents a reference temperature, and represents an angular frequency direction. The displacement amount and the table W indicate the displacement amount in the G' and G" axis directions. [Evaluation of activation energy] The activation energy (Ea) of the flow is obtained by the following procedure. Draw l0g(aT) for 1/T For the curve drawn here, the approximate straight line of the least squares method is used to calculate the slope of the straight line. The obtained slope is regarded as Ea/2.303R ' to calculate Ea (kJ/mole). In the examples and comparative examples The polymers used were as follows. The physical properties of the respective poly-I compounds are shown in Table 1. 1. The flow rate of the ethylene-1-hexene copolymer solution was Ug/10 min, and the density (4) was 923 kg/m3. Ethylene-1-hexadiene copolymer. 2. Ethylene-1-octyl The copolymer melt flow rate _) is lg / 1 〇 min, and the density (4) is _ / 1 Ώ 3 of the commercially available ethylene-1-octene copolymer. 3. High pressure method low density polyethylene Sumitomo Chemical Co., Ltd. Name ςττΛ/ττΡΛ Horse SUMJK^SEN F]02-0 high 316749 20 1364436 Pressurized low density polyethylene. The polyethylene has a melt flow rate (MFR) of 0.3 g/10 min and a density (d) of 922 kg /m3 4. Styrene-isoprene-styrene block copolymer styrene-isoprene-styrene block copolymer manufactured by Clayley Co., Ltd. under the trade name SEPTON 2104. The melt flow rate of the material was 0.8 g/10 min, and the density (d) was 970 kg/m3. [Example 1] [Production of ethylene-1-hexene copolymer] Ethylene and 1-hexene were carried out by the following method. Copolymerization to obtain ethylene-1-) hexane copolymer. [Modulation of catalyst component] The catalyst carrier (A) was prepared in a reactor equipped with a nitrogen-substituted mixer, in which 2.8 kg was placed. Cerium dioxide heat-treated at 300 ° C under a nitrogen gas flow (trade name: Sy] οροί 948; manufactured by Derbyson; average particle size = 5 // m; micropore volume Amount = 1.67 ml / g; specific surface area = 325 m2 / g) and 24 kg of toluene, and stirred > After cooling to 5 ° C, the reactor temperature was maintained at 5 ° C, while dropping in / 33 minutes A mixed solution of 0.91 kg of 1,1,1,3,3,3-hexamethylenediamine and 1.43 kg of terpene was introduced. After completion of the dropwise addition, the mixture was stirred at 5 ° C for 1 hour, and at 95 ° C for 3 hours, and then filtered. The obtained solid product was washed 6 times with 21 kg of hydrazine. Then, 6.9 kg of hydrazine was added as a slurry and allowed to stand overnight. To the slurry obtained above, 2.05 kg of a diethylzinc hexane solution (diethylzinc concentration: 50% by weight) and 1.3 kg of hexane were charged and stirred. Connect to 316749 1364436 and cool to 5. (: After that, the reactor temperature was maintained at 5. 〇, and a mixed solution of 77 kg of pentafluorophenol and 7l7 kg of toluene was added dropwise over 61 minutes. After the end of the drip, the mixture was stirred at 5 C for 1 hour. 4 〇 It is taught to mix the small 4. Then, the reaction temperature is maintained at 5 〇C, and 0.11 kg of water is dropped into the water at the same time. After the end of the drip, the mixture is mixed at 5 〇c. After an hour, it was stirred at 55 ° C for 2 hours. Then, at room temperature, one of ethyl hexyl hexane solution (diethylzinc concentration: 5 〇 wt%) and 〇 8 kg of hexane were charged. After 5 〇C, the reactor temperature was maintained at 5«>c, and at the same time, a mixture of kg42 kg of 3,4,5-trifluorophenol and 〇77 kg of toluene was added dropwise to 60 knives. After the end, stir under the hour!, and search for 1 hour under 4〇. Then, maintain the reactor temperature at 5t, and simultaneously add 〇.〇77kg of water into the 1.5 蚪. After the end of the drop, at 5 Stir the mixture for 1 hour, stir at 2 (rc for 2 hours and at 8 Torr. Stir for 2 hours under stirring. After stopping the stirring, extract the supernatant until the balance is 16 liters, and put in 11 (4) Toluene and stir-mix. Warm up to 95t and (4) for 4 hours. Allow to stand to precipitate solid components. When the interface between the precipitated solid component (lower layer) and the slurry portion (upper layer) occurs, the slurry portion (upper layer) is removed. Next, the remaining liquid component is filtered (the lower layer p is washed 4 times with 2 〇.8 kg of toluene, and 24 liters of hexane is washed and washed. Then, it is dried, and this produces a solid component. (Hereinafter, it is abbreviated as carrier (A)). 〃 [Preparation of pre-polymerization component] ^ First, the internal volume of nitrogen substitution 2] 〇 升 之 附 附 附 附 附 附 附The above-mentioned auxiliary catalyst carrier (A), after placing 3 liters of hydrogen, 20 g of butene-1 to ···. and 80 liters of butane in a high pressure dad at 25 VII 316749 22 1364436 Dad warmed up to 30 ° C. Then the ethylene was pressed into the gas pressure gauge in the high pressure Cang, and the equivalent amount was 0.03 MPa. After the system was settled, 159 mmol of triisobutyl aluminum and 53 mmol were put. Racemic ethylene bis(1-indenyl) stilbene diphenyl oxide and start polymerization. At 31 ° C, the mixture was further heated to 51 ° C under continuous supply of ethylene and hydrogen for a total of 4 hours of prepolymerization. After the completion of the polymerization, a purge of ethylene, butane, hydrogen, etc. was carried out, and the residue was retained. The solid was dried under vacuum at room temperature. Thus, 15 g of ethylene prepolymerized prepolymerized component was added per lg of the above-mentioned supporter carrier (A). '[Polymerization] The polymerizable component is subjected to copolymerization of ethylene and 1-hexene in a continuous fluidized bed gas phase polymerization apparatus to obtain an ethylene-1-hexene-copolymer powder. In terms of polymerization conditions, the polymerization temperature was 75 ° C, the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.9%, and the 1-hexene molar ratio to ethylene was 0.9%. In the polymerization, in order to maintain a fixed gas composition, ethylene, 1-hexane and hydrogen are continuously supplied. Further, the above prepolymerizable catalyst component and triisobutylaluminum were continuously supplied to maintain a constant total powder weight (80 kg) in the fluidized bed. The average polymerization time was 4 hours. [Kneading] An antioxidant (trade name: SUMIRIZER GP, manufactured by Sumitomo Chemical Co., Ltd.) was added to the obtained ethylene-1-hexene copolymer powder to adjust the concentration to 750 ppm. Using an extruder (trade name: LCM50; manufactured by Kobe Steel Co., Ltd.), through a feed speed of 50 kg / hour, a spiral rotation of 23 316749 1364436 • a number of 450 ppm, a raw meal opening (50%), suction (sucti〇 n) Pressure·*·0.lMPa 'The granulation of the obtained mixture was carried out under the conditions of a resin temperature of 200 to 230 Torr, and the ethylene-containing 1-hexene copolymer particles (peiie〇) were obtained. [Extrusion foam molding Manufacture of the product] Using a tumble mixer '1 〇〇 part by weight of ethylene-1 -hexene copolymer particles, and 1 part by weight of azodicarboxylic acid-based chemical foaming agent (commodity) Name: Seymeike MB2043; Sanxiehuacheng (share) system) Mixing j minutes. This mixed raw material is supplied to a sheet having a diameter of 5〇inm and a length of 2.lm and having three spiral sections with mixing sections. The machine is extruded at a screw rotation number of 60 rpm, and the temperature of the kneading part is 15 to 21 (rc, and the temperature of the die head is 150 ° C. The extrusion amount is 8 kg / hour. In the extrusion machine The middle portion is provided with an injection valve, and from the valve, the carbonic acid gas pressurized to 〇 MPa is continuously injected and becomes 0.4. The amount of injection was adjusted in parts by weight. The front end of the extrusion machine was provided with a disk die having an outer diameter of 8 mm, an inner diameter of 79.2 mm, and a lip clearance of 〇.4 mm. The disk die is extruded in a molten disk shape in a molten disk shape, and the molten resin in the molten state is cooled and solidified by cooling the mold core at a temperature of a cooling water. The film was taken up by a pinch roller to obtain an extruded foamed sheet having a thickness of 8 mm and a foaming ratio of 2.1 times. No corrugation occurred on the extruded foamed sheet. The appearance of the material was good, and the tear strength of the sheet was 38 kgf/cm, and the mechanical strength was also excellent. The results are shown in Table 2. [Example 2] The injection amount was adjusted to 0-5 weight in addition to continuous injection of carbonic acid gas. The parts were produced in the same manner as in the examples! The foamed formed sheets were produced in the same manner as in the examples! The results obtained are shown in Table 2. No occurrence occurred on the rubbed foamed formed sheet. Bo Xiangwen, the appearance of the sheet is good. Moreover, the tear strength of the sheet is W kgf/cm, machine The strength was also excellent. [Comparative Example 1] In the same manner as in Example 制造, a broadcast foam molding was produced except that a high-pressure method low-density polyethylene (SUMikasen fi〇2 〇) was used instead of the ethylene small hexene copolymer. The obtained results are shown in Table 2. The pulverized formed sheet was corrugated and was not excellent in appearance. Further, the tear strength was 20 kgf/cm, and the mechanical strength was poor. [Comparative Example 2] An extruded foamed-formed sheet was produced in the same manner as in Example except that a commercially available ethylene octene copolymer was used instead of the ethylene-hexene copolymer. The results obtained are shown in Table 2. Such an extruded foamed sheet has a shark skin which is not a sheet having an excellent appearance. Further, the sheet has a tear strength of 22 kgf/cm' which is also inferior in mechanical strength. [Comparative Example 3] Using a drum mixer, a commercially available 6 parts by weight of an ethylene octene copolymer, and 30 parts by weight of a styrene-isoprene-styrene block copolymer hydrogenated product (SEPTON) 2104), with 10 parts by weight of high-pressure process low-density polyethylene (SUMIKASEN F1G2-G), and 1 part by weight of chemical foaming agent (/trade name·································· The azodicarboxylic acid was mixed for 1 minute. The mixed raw material was supplied to a sheet forming machine similar to that of the example, and the number of spiral rotations was 6 rpm, and the temperature of the kneading section was 3 J6749 25 U64436 18 k _ head temperature was 18 (rc conditions). The amount of the filming is in the gap (4) (10) (4) of the lip (iip) of the disc/head of the disc die, and the foamed resin in the molten state is extruded in the shape of a disk. The cooling mold core of the cooling water circulating at a temperature of 25t is used. The melted state of the foamed resin is cooled and solidified, and is taken up by a nip roll, and the extruded foamed formed sheet having a dry thickness of 44 mm is produced. The bubble ratio is as low as M times' and the surface of the sheet has a purple skin texture, which is inferior to the outside. Moreover, the tear strength is 14 kgf/cm, and the mechanical strength is not [Comparative Example 4] An extruded foamed formed sheet was produced in the same manner as in Comparative Example 3, except that the carbon dioxide gas pressurized to 1 MPa was continuously injected from the injection valve to make the amount of the injection into 4 parts by weight. The thickness of the formed sheet is 〇.72mm, and the expansion ratio is 6 times, but the surface perforation of the sheet is Views are poor. Also, the tear strength of the sheet was 13
kgf/cm，機械強度不佳。 [表1] ΓMFR(g/l〇 分鐘） D(kg/m3) MWD 乙烯-1-己烯共聚物 1.1 923 17.8 1.28 72 高壓法低密度聚乙烯 0.3 923 4.4 1.53 70 乙稀-1-辛稀共聚物 1.0 870 1.7 1.13 41 苯乙烯-異戊二烯-笨乙烯 嵌段聚合物 0.8 970 — — 316749 26 1364436 •[表 2]Kgf/cm, poor mechanical strength. [Table 1] ΓMFR (g/l〇min) D(kg/m3) MWD Ethylene-1-hexene copolymer 1.1 923 17.8 1.28 72 High-pressure process low-density polyethylene 0.3 923 4.4 1.53 70 Ethylene-1-octyl Copolymer 1.0 870 1.7 1.13 41 Styrene-isoprene-stupid ethylene block polymer 0.8 970 — — 316749 26 1364436 • [Table 2]
[產業上之可利用性] 本發明之成形品，係外觀及機械強度優異，適人 於如地板塾材、斷熱材料、斷熱防水材料、緩衝材二吏用 邊屋頂板、熱化劑、接縫材料、榻榻米蕊材等之筮捲 用途；如車内傷砉般、門戶 工μ t 系材料 早内儀表』門扇、天化板等之斷熱緩衝 座墊之蕊材、水管之斷熱緩衝材料等的汽車料；如“ 機器包裝材料、玩具、墊子、座藝、保冷箱、保溫μ :: 套、膠帶基材、盘帽緩衝姑粗、氣D 相 曰 ^目後衝材7^運動益材用保護蕊材、章 板（驗mg Plate)等之雜貨用途；如托盤、購物網 /、 襯墊寺之食品包裝用途；如褥塾㈣）、護具等之 衣 等各種用途。 ’面療用途 316749 27[Industrial Applicability] The molded article of the present invention is excellent in appearance and mechanical strength, and is suitable for use in such as floor slabs, heat-insulating materials, heat-dissipating waterproof materials, cushioning materials for roofing sheets, and heating agents. , seam materials, tatami ruthenium and other roll applications; such as car shackles, portal workers, t t materials, early instrumentation, door fan, Tianhua board, etc. Automobile materials such as cushioning materials; such as "machine packaging materials, toys, mats, seat art, cold storage box, insulation μ :: sets, tape substrates, disk cap buffers, rough gas, gas D phase 曰 ^ after the punching material 7 ^ Sports products are used for the protection of the core material, the chapter board (check mg plate) and other miscellaneous uses; such as trays, shopping nets, food packaging purposes of the padded temple; such as 褥塾 (4)), protective clothing and other clothing. 'Therapeutic use 316749 27