TW200530307A

TW200530307A - Polyolefin resin foam and manufacturing method thereof

Info

Publication number: TW200530307A
Application number: TW093140597A
Authority: TW
Inventors: Kazuhiko Morita; Satoshi Iwasaki
Original assignee: Jsp Corp
Priority date: 2004-01-08
Filing date: 2004-12-24
Publication date: 2005-09-16
Also published as: TWI337612B; CN1670069A; KR100860251B1; JP2005194433A; KR20050073557A; CN100513468C

Abstract

The objective of the present invention is to provide a polyolefin resin foam containing 2 to 12 wt% of a polymeric anti-static agent, with an apparent density of 15 to 65 g/L and a surface inherent resistivity of 1x10<SP>8</SP> to 1x10<SP>13</SP> Ω after being subjected to ultrasonic wash with ethanol, and an average bubble size satisfying the following formula: 0.35 ≤ Z/X ≤ 1.2 (1), 0.35 ≤ Z/Y ≤ 1.2 (2), 0.2 ≤ Z ≤ 1.4 (3) (X, Y and Z are respectively the average bubble size in the extrusion direction: X (mm), the average bubble size in the width direction : Y(mm), and the average bubble size in the thickness direction: Z (mm).)

Description

200530307 (1) 九、發明說明【發明所屬之技術領域】本發明係關於具抗靜電性能之聚烯烴樹脂發泡物及其製造方法，特別是關於抗靜電性能優良，表觀密度低之聚烯烴樹脂發泡物及其製造方法。【先前技術】向來，聚烯烴樹脂發泡物富有柔軟性及緩衝性，不易鲁傷及被包裝物，故廣泛適用作緩衝材料、包裝材料等。尤以聚乙烯樹脂發泡物因易於高度發泡，可低價製造故已廣爲使用。但是，這些發泡物因靜電之作用，具有易惹塵埃之不佳性質，而有了使用抗靜電劑提升導電性之具抗靜電性能的聚烯烴樹脂發泡物之開發及使用。作爲上述賦予抗靜電性能之手段，界面活性劑型抗靜電劑因可廉價取得而廣爲所用。界面活性劑型抗靜電劑有例如日本專利特開平9- 1 690 72號公報等記載之甘油脂肪酸 ® 酯、聚氧乙烯烷基胺、烷基二乙醇醯胺等。然而，界面活性劑型抗靜電劑之抗靜電效果係由，抗靜電劑自樹脂滲出表面，吸附空氣中之水分而出現。因而，界面活性劑型抗靜電劑有在濕度較低之環境下不易出現，抗靜電效果之問題。而雖在濕度較高之環境下出現抗靜電，效果，吸收水分之抗靜電劑因遷移至被包裝物，發生被包裝物表面生黏、白化等現象，並有引起被包裝物表面污染之問題。 -4 - 200530307 (2) 【發明內容】發明所欲解決之課題本發明係鑒於上述問題而作，其目的在提供，用作包裝材料時污染所接觸之對方表面的可能性低，外觀優良， +大受溫度影響而安定發揮良好抗靜電性能之聚烯烴樹脂發泡物及其製造方法。用以解決課題之手段本發明人等爲解決上述問題，嘗試以高分子型抗靜電劑及聚烯烴樹脂供給於擠出機製造發泡物。此時，使發泡物之表觀密度爲特定値，使用特定之聚烯烴樹脂及高分子型抗靜電劑，意外得知即使高分子型抗靜電劑之用量少亦可出現抗靜電性能。亦即，根據本發明可提供如下之抗靜電性能優良之聚烯烴樹脂發泡物，及其製造方法。〔1〕其特徵爲含2〜12重量％之高分子型抗靜電劑，表觀密度15〜65 g/ L，用乙醇以超音波洗淨後表面電阻率ΙχΙΟ8〜1χ1〇13(Ω)，平均氣泡徑滿足下述（1) 、（2 )及（3 )式之聚烯烴樹脂發泡物。 0.35^ Ζ/Χ^ 1.2 ...... ( 1 ) 0·35$Ζ/Υ$1.2 ...... ( 2 ) 0.2 ^ Z ^ 1.4 ...... ( 3 ) (X、Y及Z係，擠出方向之平均氣泡徑：X ( mm )，寬度方向之平均氣泡徑：Y ( mm )及厚度方向之平均氣泡徑： -5- 200530307 (3) Z ( mm ) 〇 ) 〔2〕上述〔1〕之聚烯烴樹脂發泡物，其中高分子型抗靜電劑含量爲2〜1 0重量％。〔3〕上述〔1〕之聚烯烴樹脂發泡物，其中高分子型抗靜電劑含量爲2〜8重量％。〔4〕如申請專利範圍第丨項之聚烯烴樹脂發泡物之製造方法’係將聚烯烴樹脂、高分子型抗靜電劑、氣泡調整劑及物理發泡劑於擠出機中混練，形成發泡性聚烯烴樹脂溶體’將該發泡性聚烯烴樹脂溶體擠出發泡之聚烯烴樹脂發泡物之製造方法，其特徵爲上述高分子型抗靜電劑之添加量係對於聚烯烴樹脂 1 0 0重量份2〜14重量份，上述高分子型抗靜電劑之結晶溫度係1 1 〇 t：以下，上述聚烯烴樹脂於測定溫度1 9 0 °C、剪切速度1 0 0 sec—1之熔融黏度：Ma(Pa.s)，及上述高分子型抗靜電劑於測定溫度190 °C、剪切速度100 sec— 1之熔融黏度：Mb (Pa · s )之關係滿足下述（4 )及（5 )式。200530307 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a polyolefin resin foam having antistatic properties and a method for producing the same, especially to a polyolefin having excellent antistatic properties and a low apparent density. Resin foam and its manufacturing method. [Previous technology] Polyolefin resin foams have always been flexible and cushioning, and they are not easy to damage the package. Therefore, they are widely used as cushioning materials and packaging materials. In particular, polyethylene resin foams are widely used because they are easy to be highly foamed and can be manufactured at low cost. However, due to the effect of static electricity, these foams have the poor property of easily causing dust, and the development and use of polyolefin resin foams with antistatic properties that use antistatic agents to improve conductivity have been developed. As a means for imparting the above-mentioned antistatic properties, surfactant-type antistatic agents are widely used because they are available at low cost. Surfactant-type antistatic agents include, for example, glycerol fatty acid ® esters, polyoxyethylene alkylamines, and alkyldiethanolamidamines described in Japanese Patent Laid-Open No. 9-1690690. However, the antistatic effect of the surfactant antistatic agent is caused by the antistatic agent seeping out of the surface from the resin and adsorbing the moisture in the air. Therefore, the surface active agent type antistatic agent has the problems that it is not easy to appear under the environment of low humidity and the antistatic effect. Although the antistatic effect occurs in a high humidity environment, the antistatic agent that absorbs moisture migrates to the package, causing the surface of the package to become sticky, whitening, etc., and causing the problem of surface pollution of the package. . -4-200530307 (2) [Summary of the Invention] Problem to be Solved by the Invention The present invention has been made in view of the above problems, and its purpose is to provide, when used as a packaging material, the possibility of contaminating the surface of the counterpart being touched is low, and the appearance is excellent. + Polyolefin resin foam which is greatly affected by temperature and stably exhibits good antistatic performance, and its manufacturing method. MEANS TO SOLVE THE PROBLEM In order to solve the above-mentioned problems, the present inventors tried to supply a polymer type antistatic agent and a polyolefin resin to an extruder to produce a foam. At this time, by making the apparent density of the foam to a specific ratio and using a specific polyolefin resin and a high-molecular antistatic agent, it is unexpectedly found that even if the amount of the high-molecular antistatic agent is small, antistatic performance may occur. That is, according to the present invention, there can be provided a polyolefin resin foam having excellent antistatic properties as follows, and a method for producing the same. [1] It is characterized by containing 2 to 12% by weight of a polymer-type antistatic agent, with an apparent density of 15 to 65 g / L. The surface resistivity after ultrasonic washing with ethanol is ΙΟΙΟ8 to 1 × 1013 (Ω). A polyolefin resin foam having an average cell diameter satisfying the following formulae (1), (2), and (3). 0.35 ^ ZZ / Χ ^ 1.2 ...... (1) 0.35 $ Z / Υ $ 1.2 ...... (2) 0.2 ^ Z ^ 1.4 ...... (3) (X, Y and Z series, average bubble diameter in the extrusion direction: X (mm), average bubble diameter in the width direction: Y (mm) and average bubble diameter in the thickness direction: -5- 200530307 (3) Z (mm) 〇) [2] The polyolefin resin foam according to the above [1], wherein the content of the polymer-type antistatic agent is 2 to 10% by weight. [3] The polyolefin resin foam according to the above [1], wherein the content of the polymer-type antistatic agent is 2 to 8% by weight. [4] According to the method of manufacturing a polyolefin resin foam according to item 丨 of the patent application, 'the polyolefin resin, a high-molecular antistatic agent, a bubble regulator, and a physical foaming agent are mixed in an extruder to form A method for producing a foamable polyolefin resin solution by extruding the foamable polyolefin resin solution into a foamed polyolefin resin foam, which is characterized in that the amount of the above-mentioned polymer antistatic agent added to the polyolefin is Resin 100 parts by weight 2 to 14 parts by weight, the crystallization temperature of the polymer antistatic agent is 1 10 t: below, the polyolefin resin is measured at a temperature of 190 ° C and a shear rate of 100 sec. —1 melt viscosity: Ma (Pa.s), and the above polymer type antistatic agent at a measurement temperature of 190 ° C and a shear rate of 100 sec — 1 melt viscosity: Mb (Pa · s) relationship satisfies the following (4) and (5).

Ma > Mb ( 4 ) 80Pa · s ^ Mb ^ 1 OOOPa · s ( 5 ) 〔5〕上述〔4〕之聚烯烴樹脂發泡物之製造方法，其中聚烯烴樹脂係19(TC之熔融張力爲30〜400 mN之聚乙烯樹脂。〔6〕上述〔4〕之聚烯烴樹脂發泡物之製造方法，其中聚烯烴樹脂係2 3 0 °C之熔融張力爲3 0〜4 0 0 mN之聚丙烯 200530307 (4) 樹脂。發明效果本發明之申請專利範圍第1項有關發明之聚烯烴樹脂發泡物含少量局分子型抗靜電劑，呈低表觀密度及特定氣泡形狀，使用乙醇的超音波洗淨後表面電阻率呈特定値，故係用作包裝材料等時污染接觸對方表面之可能性低，外觀優良’不大受溫度影響而安定發揮良好抗靜電性能，柔鲁軟性、緩衝性優良之聚烯烴樹脂發泡物。上述聚烯烴樹脂發泡物因將發泡物洗淨亦不失抗靜電性能，適於再利用。本發明的申請專利範圍第2、3項之聚烯烴樹脂發泡物、高分子型抗靜電劑之含量更少而亦能發揮充分之抗靜電性能’用作包裝材料時污染接觸對象表面之可能性極低。因昂貴高分子型抗靜電劑之用量更少，生產成本低。依本發明之申請專利範圍第4項有關發明的聚烯烴樹脂發泡物之製造方法，由於具有特定結晶溫度及特定熔融 · 黏度’且經使用熔融黏度上與聚烯烴樹脂滿足特定關係之尚分子型抗靜電劑’以少量的高分子型抗靜電劑添加即可輕易製造如申請專利範圍第i項之聚烯烴樹脂發泡物。依本發明之申請專利範圍第5項有關的發明之製造方，法，易㈡特別是獨立氣泡率高，外觀優良，表觀密度低之聚乙烯樹脂發泡物’依本發明之申請專利範圍第6項有關的發明之製造方法，易得特別是獨立氣泡率高，外觀優良 ’表觀密度低之聚丙烯樹脂發泡物。 200530307 (5) 【實施方式】以下詳細說明本發明之聚烯烴樹脂發泡物（以下或簡稱「發泡物」。）。本發明之發泡物的形狀有例如棒狀、薄片狀、板狀。其中作爲包裝材料基於被包裝物之容易捆包、熱成形容易 ’以薄片狀或板狀爲佳。本發明之發泡物係由聚烯烴樹脂所成。聚烯烴樹脂表面硬度低柔軟性優，被包裝物之表面保護性能優良而適用。上述聚烯烴樹脂有聚乙烯樹脂、聚丙烯樹脂等。本說明書中聚烯烴樹脂指含烯烴成分單元50莫耳％以上，較佳者75莫耳％以上，更佳者85莫耳％以上之樹脂。上述聚乙烯樹脂有例如，乙烯成分單元50莫耳％以上之樹脂，有高密度聚乙烯、低密度聚乙烯、直鏈低密度聚乙烯等乙烯單聚物，乙烯一乙酸乙烯酯共聚物，乙烯-乙酸乙烯酯共聚物與高密度聚乙烯樹脂之混合物，乙烯-丙烯共聚物、乙烯一丙烯一丁烯一丨共聚物、乙烯一丁烯—1 共聚物、乙烯一己烯一 1共聚物、乙烯一4一甲戊烯一 1共聚物、乙烯一辛烯- 1共聚物等乙烯系共聚物、以及該等2 種以上之混合物。這些聚乙烯樹脂中，以密度935 g/L以下之聚乙烯樹脂爲佳。具體而言，以用低密度聚乙烯、直鏈低密度聚乙烯等爲佳，發泡性良好之低密度聚乙烯更佳。聚乙烯樹脂密度之下限爲890 g/L，9]0 g/L更佳。 200530307 (6) 上述聚丙烯樹脂有丙烯共聚物，或與可和丙烯共聚之其它烯烴的共聚物。可與丙烯共聚之其它烯烴有例如乙烯、1— 丁細、異丁細、1 一戊烯、3 —甲一 1 一丁嫌、1—己烯、3，4 —二甲一1 一丁烯、丨—庚烯' 3一甲—丨―己烯等乙烯、碳原子數4〜1〇之“—烯烴。上述共聚物可係隨機共聚物亦可係嵌段共聚物，不只二元共聚物亦可係三元共聚物。這些聚丙烯樹脂可以單獨或混合2種以上使用。上述共聚物用作構成發泡物之樹脂時，共聚物中可與鲁丙烯共聚之其它烯烴以含25重量％以下，尤以15重量％以下之比率爲佳。而下限値係〇 . 3重量％。上述聚丙烯樹脂中適於擠出發泡之樹脂，以較之一般聚丙烯樹脂熔融張力高的高熔體張力型聚丙烯樹脂爲佳。具體而言有例如，特開平7-53797號公報記載之，（1)具有未達1之分枝指數及相當之應變硬化伸長黏度之聚丙烯 ’ （2) (Ο Z平均分子量（Mz)爲Ι.Οχίο6以上，或Z平均分子量（Mz)與重量平均分子量（Mw)之比（Mz/Ma > Mb (4) 80Pa · s ^ Mb ^ 1 OOOPa · s (5) [5] The method for producing a polyolefin resin foam according to the above [4], wherein the polyolefin resin is 19 (the melt tension of TC is Polyethylene resin of 30 to 400 mN. [6] The method for producing a polyolefin resin foam according to the above [4], in which the polyolefin resin is a polymer having a melting tension of 230 ° C at 30 to 400 mN Propylene 200530307 (4) Resin. Effect of the Invention The polyolefin resin foam of the first aspect of the patent application scope of the present invention contains a small amount of local molecular antistatic agent, which has a low apparent density and a specific bubble shape. After sonic cleaning, the surface resistivity is specific. Therefore, when it is used as packaging materials, the possibility of contamination contacting the surface of the other party is low, and the appearance is excellent. It is stable without being affected by temperature. It exhibits good antistatic properties, softness, and cushioning. Excellent polyolefin resin foam. The above polyolefin resin foam is suitable for re-use because it does not lose the antistatic performance after washing the foam. The polyolefin resins of the scope of application for patents No. 2 and 3 of the present invention Foam, polymer antistatic The content of the agent is less and can also exert sufficient antistatic performance. 'The possibility of contaminating the surface of the contact object when used as packaging material is extremely low. Because the amount of expensive polymer antistatic agent is less, the production cost is low. According to the present invention The fourth method of the invention relates to a method for manufacturing a polyolefin resin foam, which has a specific crystallization temperature and a specific melting and viscosity, and is a molecular antistatic that has a specific relationship with the polyolefin resin by using melt viscosity. Adding a small amount of high-molecular-type antistatic agent can easily produce a polyolefin resin foam such as the scope of application for item i. According to the method of manufacturing the invention related to the scope of application for scope of patent application No. 5, Easy to make, especially the polyethylene resin foam with high closed cell ratio, excellent appearance, and low apparent density. According to the manufacturing method of the invention related to item 6 of the patent application scope of the present invention, it is easy to obtain especially high closed cell ratio. Good appearance 'Polypropylene resin foam with low apparent density. 200530307 (5) [Embodiment] The polyolefin resin according to the present invention will be described in detail below. (Hereinafter referred to as "foam"). The shape of the foam of the present invention includes, for example, a rod shape, a sheet shape, and a plate shape. Among them, the packaging material is based on the ease of packaging of the packaged material and the ease of thermoforming. A sheet or plate shape is preferred. The foam of the present invention is made of a polyolefin resin. The polyolefin resin has low surface hardness and excellent flexibility, and is excellent in surface protection performance of a packaged product. The above polyolefin resin is polyethylene Resin, polypropylene resin, etc. The polyolefin resin in the present specification refers to a resin containing olefin component units of 50 mol% or more, preferably 75 mol% or more, and more preferably 85 mol% or more. The above polyethylene resins include, for example, Resins with an ethylene content of 50 mol% or more, such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and other ethylene monopolymers; ethylene-vinyl acetate copolymers; Mixtures with high-density polyethylene resins, ethylene-propylene copolymers, ethylene-propylene-butene-copolymers, ethylene-butene-1 copolymers, ethylene-hexene-1 copolymers, A 4-ene A-1-pentene copolymers, ethylene-octene - 1 copolymer, ethylene copolymer and the like, and mixtures of two or more of these. Among these polyethylene resins, polyethylene resins having a density of 935 g / L or less are preferred. Specifically, low-density polyethylene and linear low-density polyethylene are preferred, and low-density polyethylene having good foamability is more preferred. The lower limit of the density of polyethylene resin is 890 g / L, and more preferably 9 g / L. 200530307 (6) The above polypropylene resins are propylene copolymers, or copolymers with other olefins copolymerizable with propylene. Other olefins that can be copolymerized with propylene are, for example, ethylene, 1-butadiene, isobutylene, 1-pentene, 3-methyl-1, 1-butane, 1-hexene, 3, 4-dimethyl-1, butene , 丨 -heptene '3-methyl— 丨 -hexene and other ethylene, "-olefins with 4 to 10 carbon atoms. The above copolymers can be random copolymers or block copolymers, not only binary copolymers Terpolymers can also be used. These polypropylene resins can be used alone or as a mixture of two or more. When the above copolymers are used as resins constituting foams, other olefins that can be copolymerized with propylene in the copolymer contain 25% by weight In the following, a ratio of 15% by weight or less is particularly preferred. The lower limit is 0.3% by weight. Among the above polypropylene resins, resins suitable for extrusion foaming are high melts having a higher melt tension than ordinary polypropylene resins. Tensile polypropylene resin is preferred. Specifically, for example, it is described in Japanese Patent Application Laid-Open No. 7-53797 (1) Polypropylene having a branch index of less than 1 and equivalent strain-hardening elongation viscosity (2) ( 〇 Z average molecular weight (Mz) is 1.0 or more, or Z average molecular (An Mz) to weight average molecular weight (Mw) ratio (Mz /

Mw)在3.0以上，（b )而且平衡柔量^在ux〗（T 3Pa 一1 以上’且每單位應力之剪切應變恢復Sr/ S在1 sec— 1爲5 X 1(T 4Pa~ 1以上之聚丙烯樹脂。本發明中，亦可係（3 )聚丙烯樹脂、自由基聚合引，發劑及苯乙烯單體熔融混練得之改質聚丙烯樹脂，（4 ) β 聚丙儲樹脂、異平單體及自由基聚合啓始劑熔融混練得之改質聚丙綠樹脂。上述聚烯烴樹脂係所用不溶成分比率低者。不熔成分 -9- 200530307 (7) 比率指以發泡物爲試樣，將試樣放入1 4 5 t之二甲苯中煮沸8小時後，以1 〇〇目之金屬網快速過濾，然後將殘留在金屬網上之沸騰二甲苯不溶成分於2 〇之烘箱中乾燥2 4小時後’測定不溶成分之重量G ( g )，依下述式（6 )求出之不溶成分之比率爲0〜1〇重量％之結合，較佳者〇〜5重量 % ’更佳者0〜2重量％。不溶成分比率愈低回收性愈優，並於成本之降低較佳。乾燥後不溶成分之比率（重量％) = [ G (g) /試樣重量（g) ] X 1 0 0 ......(6 ) 本發明中’在無妨於其目的及效果之範圍內，可於聚烯烴樹脂添加聚苯乙烯等苯乙烯樹脂、乙烯丙烯橡膠等彈性體。此時之添加量以40重量％以下爲佳，25重量％以下更佳，1 0重量％以下尤佳。本發明之發泡物含高分子型抗靜電劑。用於本發明之高分子型抗靜電劑詳敘於後。本發明之發泡物含2〜12重量％之高分子型抗靜電劑，表觀密度爲1 5〜6 5 g / L。表觀密度在此範圍則聚烯烴樹脂於發泡時被拉伸，同時，均勻含於聚烯烴樹脂中之高分子型抗靜電劑定向，形成抗靜電劑網路，故高分子型抗靜電劑含量1 2重量％以下之少量添加，本發明之發泡物亦可發揮表面電阻率1 X 1 0 8〜1 X 1 0 1 3 ( Ω )之優良抗靜電性能。又因高分子型抗靜電劑之添加量少，本發明之發泡物引起被包裝物表面污染之可能性低。高分子型抗靜電劑含量超過1 2重量％，則氣泡徑粗大 -10- 200530307 (8) 、外觀差，並有獨立氣泡率低之虞。因此高分子型抗靜電劑含量以10重量％以下爲佳，8重量％以下更佳，7重量％以下又更佳，6.5重量％以下尤佳。而高分子型抗靜電劑含量未達2重量％則有不能發揮表面電阻率1 χ 1 〇 8〜i χ 1 0 1 3 ( Ω )之抗靜電性能之虞。因此，3 · 5重量％以上爲較佳，4重量％以上更佳。發泡物中高分子型抗靜電劑含量可由紅外線分光分析求出。高分子型抗靜電齊彳若不於擠出發泡時分解，可從高分子型抗靜電劑添加量求出。發泡物之表觀密度若超過6 5 g / L，則無發泡時隨氣泡成長的含高分子型抗靜電劑聚烯烴樹脂之拉伸效果，有抗靜電性能差之虞。因此以6 1 g / L以下爲佳，5 1 g / L以下又更佳，44 g/L以下再更佳。而表觀密度未達15 g/L ，則發泡倍率過大，有包裝材料所要求之物理強度低之虞。因此’以15 g/L以上爲佳’ 18 g/L以上又更佳，21 g / L以上再更佳。本說明書中發泡物之表觀密度測定方法如下。發泡物爲薄片狀或板狀時，首先如下測定發泡物厚度〇將發泡物於沿擠出方向的垂直方向切斷，用顯微鏡以等間隔於寬度方向作上述切斷面厚度之][〇點攝影，於攝影之各點測定發泡物厚度，以所得値之算術平均爲發泡物厚度。其次，測定發泡物之基重（g / m2 )。發泡物之基重係’切出縱2 5 m m X橫2 5 m m X發泡物厚度之試片，測定試 -11 - 200530307 (9) 片重量（g)後，由該重量之1600倍得之。上述發泡物之基重（g/ m2 )除以發泡物之厚度（mm )予以單位換算，得發泡物之表觀密度（g / L )。於發泡物層合有聚烯烴樹脂層時，發泡物之基重係從層合發泡物之基重扣除聚烯烴樹脂層之基重求出。聚烯烴樹脂層之基重（g / πι2 )係如同上述發泡物厚度之測定方法，以顯微鏡作層合發泡物切斷面之攝影，求出之聚烯烴樹脂層厚度乘以構成聚烯烴樹脂層之樹脂的密度，換算單 ® 位而求出。唯聚烯烴樹脂層含大量無機物時，係採用自層合發泡物去除聚烯烴樹脂層，如同上述發泡物之基重求出發泡物之基重等方法。依上述方法不能測定表觀密度時，表觀密度可將該發泡物試片重量除以發泡物試片沈入水中從水位上升求出之體積計算求出。本發明之發泡物，使用乙醇作超音波洗淨後表面電阻率爲 lxio8〜lxio13 ( Ω ) 。 · 上述表面電阻率超過1 . 0 X 1 0 1 3 ( Ω )時，抗靜電性能不足’靜電蓄積於發泡體表面，容易惹塵埃。爲使不易惹塵埃，上述表面電阻率以5 X 1 0] 2 ( Ω )以下爲佳，1 x 1 0 12 ( Ω )以下更佳。，而發泡物表面電阻率未達1 X 1 0 8 ( Ω )時，包裝材料曹要求之ί几靜電性能過高，有高成本之虞。本發明之發泡物以乙醇作超音波洗淨後，亦不失抗靜電性能。相對於此，於發泡物添加甘油-硬酸酯等界面活 -12- 200530307 (10) 性劑型抗靜電劑時，以乙醇作超音波洗淨則抗靜電特性消失。亦即，使用界面活性劑型抗靜電劑時，抗靜電劑滲出成形品表面吸收空氣中之水分，出現抗靜電特性。因此，通常狀態下即使出現抗靜電性能，以乙醇作超音波洗淨後抗靜電劑從樹脂表面洗除，失去抗靜電性能。故，樹脂層的抗靜電性能其持續性之有效判別手段，即以乙醇作超音波洗淨後之表面電阻率。本說明書中「用乙醇作超音波洗淨」係，燒杯中注入 2 3 °C之乙醇，其中沈入切自發泡物之試片（縱1 〇〇 m m X橫 100mm X厚度：試片厚度）以超音波洗淨24小時後，將該試片於溫度3 0 °C、相對濕度3 0 %之環境下放置3 6小時乾燥之洗淨操作。乙醇之超音波洗淨後的表面電阻率係將上述超音波洗淨操作後之試片隨即調整狀態後，依JIS K 691 1 (1 9 7 9 )測定。本發明之發泡物，擠出方向之平均氣泡徑：x ( mm ) ，寬方向之平均氣泡徑：Y ( m m )及厚度方向之平均氣泡徑：Z ( mm )之間，下示關係成立。 0.35^ Z/ 1.2 ......(1 ) 0.35^ Z/ Y ^ 1.2 ......(2 ) Z / X、Z / Y之値在上述（1 ) 、（ 2 )式之範圍，則高分子型抗靜電劑量少亦可降低表面電阻率，z / X、z / Y之値愈接近1 . 0，即氣泡愈近乎球狀發泡物之壓縮強度愈佳。Z / X、Z / Y値未達0.3 5則壓縮強度有惡化之虞。因之Z/X、Z/Y之範圍以0.4以上爲佳，0.45以上更佳。而 -13 - 200530307 (11) z/ X、z/ Y値超過1·2時，發泡物可見所謂瓦楞之厚度參差有外觀惡化之虞。故Ζ/Χ、Ζ/Υ之範圍以1.1以下爲佳，1 . 0以下更佳。厚度方向之平均氣泡徑：z ( mm )滿足下式關係。 0.2 ^ Z ^ 1.4 ...... ( 3 ) Z値在上述（3 )式範圍，則發泡物表面平滑性優，發泡物外觀良好。Z値未達0·2則發泡物有連續氣泡率升高之傾向，壓縮強度等剛性有降低之虞。因之Ζ的範圍以0 · 3以 ® 上爲佳，0.4以上更佳。而超過1.4則發生所謂瓦愣之厚度參差有外觀惡化之虞。因而Ζ之範圍係以1 · 3以下爲佳， 1.2以下更佳。本發明之發泡物厚度1〜2 mm時多用作包裝用緩衝材料。此時，上述Z/ X、Z/ Y及Z値之範圍以如下爲佳。 0.5^ Z/X^ 0.85 ...... ( 7 ) 0.5 S Ζ/ Y S 0.85 ...... ( 8 ) 0.3^ Z ^ 0.6 ...... ( 9 ) · Z/X、Z/Y及Z値在上述（7) 、（8)及（9)式範圍，則可得外觀優良且緩衝性優良之發泡物。本發明之發泡物係厚度3 mm以上之厚片時，多係作熱成形，以樹脂層層合等二次加工。此時，Z / X、Z / Y . 及Z値以下示範圍更佳。 0 · 7 S Ζ/ X s 1 · 〇 5 ...... (10) 0.7^ Ζ/ 1.05 ……(11) 0.6 ^ Ζ ^ 1.2 ......(12) -14 - 200530307 (12) Z/X、z/Y及Z値在上述（10) 、（11)及（12)範圍內，則以熱恢復之恢復力小，熱成形時發泡物不易發生龜裂，二次加工時發泡物與樹脂層之層合面不易有皺紋之二次加工性不良。本說明書中，擠出方向之平均氣泡徑、寬度方向平均氣泡徑、厚度方向平均氣泡徑，各係如下測定。擠出方向平均氣泡徑：於發泡物寬度方向中心部，沿擠出方向垂直切斷，於其斷面中央部附近沿擠出方向畫出長3 0 mm之線段，測定該線上之氣泡，採用線段長度除以氣泡數之値作爲擠出方向之平均氣泡徑：X ( mm )。寬度方向之平均氣泡徑：正交於發泡物之擠出方向的垂直斷面中央附近沿寬度方向畫出長度30 mm之線段，測定該線段上之氣泡數，採用線段長度除以氣泡數之値作爲厚度方向之平均氣泡徑：Y ( mm )。厚度方向之平均氣泡徑··於發泡物厚度方向之垂直斷面，於發泡物的厚度方向於全厚度畫出線段，測定該線段上之氣泡數，採用線段長度除以氣泡數之値作爲厚度方向平均氣泡徑·· Z ( mm )。這些線段係自起點氣泡壁外側端畫出，與線段部份相交之氣泡亦計入氣泡數。本發明之發泡物，連續氣泡率係以65 %以下爲佳。連續氣泡率在該範圍內則發泡物薄，於包裝用途之緩衝性亦優良。熱成形時，模具重現性優良，可成形爲與模具相同之形狀。故連續氣泡率以6 0 %以下爲佳，5 0 %以下 200530307 (13) 更佳，4 0 %以下又更佳，2 5 %以下最佳。發泡物之連續氣泡率：S ( % )係依a S T M D 2 8 5 6 - 7 0之順序C，使用東芝BECkMAN (股）製空氣比較式比重計 93 0型測定發泡物試片之實容積（獨立氣泡之容積及樹脂部分容積之和）：VX(L)，依下述（13)式算出之値。 S(%) = (Va-Vx)xl〇〇(va_W///〇) ...... (13) 上述（13)式中Va、W、p如下。Mw) above 3.0, (b) and equilibrium compliance ^ at ux (T 3Pa-1 or more 'and shear strain recovery per unit stress Sr / S at 1 sec — 1 is 5 X 1 (T 4Pa ~ 1 The above polypropylene resin. In the present invention, it can also be (3) a polypropylene resin, a radical polymerization initiator, a modified polypropylene resin obtained by melting and mixing styrene monomer, (4) a beta polypropylene storage resin, Modified polypropylene green resin obtained by melt-kneading isoflat monomers and radical polymerization initiators. The polyolefin resins mentioned above have a low insoluble content ratio. Insoluble content-9-200530307 (7) The ratio refers to the foam as After the sample is boiled in 145 t of xylene for 8 hours, it is quickly filtered through a 1000-mesh metal mesh, and then the boiling xylene insoluble content remaining on the metal mesh is placed in an oven of 200. After 2 to 4 hours of intermediate drying, 'Measure the weight G (g) of the insoluble component, and the ratio of the insoluble component calculated according to the following formula (6) is a combination of 0 to 10% by weight, preferably 0 to 5% by weight' More preferably, it is 0 to 2% by weight. The lower the insoluble content ratio, the better the recoverability, and the better the cost reduction. Drying The ratio (% by weight) of the following insoluble components = [G (g) / weight of the sample (g)] X 1 0 0 ...... (6) In the present invention, 'within the scope of its purpose and effect It is possible to add elastomers such as styrene resins such as polystyrene and ethylene propylene rubber to polyolefin resins. At this time, the added amount is preferably 40% by weight or less, more preferably 25% by weight or less, and even more preferably 10% by weight or less. The foamed material of the present invention contains a polymer-type antistatic agent. The polymer-type antistatic agent used in the present invention is described in detail later. The foamed material of the present invention contains 2 to 12% by weight of a polymer-type antistatic agent. The apparent density is 15 to 65 g / L. When the apparent density is in this range, the polyolefin resin is stretched when foamed, and at the same time, the polymer-type antistatic agent uniformly contained in the polyolefin resin is oriented to form Antistatic agent network, so the polymer type antistatic agent is added in a small amount of 12% by weight or less. The foam of the present invention can also exhibit surface resistivity 1 X 1 0 8 ~ 1 X 1 0 1 3 (Ω) Excellent antistatic performance. Because the added amount of polymer antistatic agent is small, the foamed product of the present invention causes the surface of the packaged object The possibility of dyeing is low. If the content of the polymer antistatic agent exceeds 12% by weight, the bubble diameter is large -10- 200530307 (8), the appearance is poor, and there may be a low rate of independent air bubbles. Therefore, the polymer antistatic agent may be low. The content is preferably 10% by weight or less, 8% by weight or less, 7% by weight or less, and 6.5% by weight or less. However, if the content of the polymer antistatic agent is less than 2% by weight, the surface resistance cannot be exhibited. The ratio 1 χ 1 〇8 ~ i χ 1 0 1 3 (Ω) may cause antistatic performance. Therefore, it is more preferable that it is 3.5% by weight or more, and it is more preferable that it is 4% by weight or more. The content of the polymeric antistatic agent in the foam can be determined by infrared spectroscopic analysis. If the polymer type antistatic compound does not decompose during extrusion and foaming, it can be determined from the amount of the polymer type antistatic agent added. If the apparent density of the foam exceeds 65 g / L, there is no stretching effect of the polymer-type antistatic agent-containing polyolefin resin that grows with the air bubbles during foaming, and there is a possibility that the antistatic performance is poor. Therefore, it is preferably less than 61 g / L, more preferably less than 51 g / L, and more preferably less than 44 g / L. When the apparent density is less than 15 g / L, the expansion ratio is too large, and there is a risk that the physical strength required by the packaging material is low. Therefore, '15 g / L or more is preferable 'and 18 g / L or more is more preferable, and 21 g / L or more is more preferable. The method for measuring the apparent density of the foam in this specification is as follows. When the foam is in the form of a sheet or a plate, first determine the thickness of the foam as follows: Cut the foam in the vertical direction along the extrusion direction, and use a microscope to make the thickness of the cut surface at equal intervals in the width direction.] [0 point photography, the foam thickness was measured at each point of the photography, and the arithmetic average of the obtained 値 was the foam thickness. Next, the basis weight (g / m2) of the foam was measured. The basis weight of the foam is' cut out 25 mm in length X 25 mm in width X the thickness of the foam test piece, determine the test-11-200530307 (9) After the weight (g) of the piece, 1600 times the weight Got it. The basis weight (g / m2) of the above foamed material is divided by the thickness (mm) of the foamed material and converted into a unit to obtain the apparent density (g / L) of the foamed material. When the polyolefin resin layer is laminated on the foam, the basis weight of the foam is obtained by subtracting the basis weight of the polyolefin resin layer from the basis weight of the laminated foam. The basis weight (g / π2) of the polyolefin resin layer is the same as the above-mentioned method for measuring the thickness of a foamed product, and the cross section of the laminated foamed product is photographed with a microscope. The density of the resin in the resin layer is obtained by converting the unit ® position. When the polyolefin resin layer contains a large amount of inorganic matter, the polyolefin resin layer is removed from the laminated foam, and the basis weight of the foam is obtained in the same manner as the basis weight of the foam. When the apparent density cannot be determined by the above method, the apparent density can be calculated by dividing the weight of the foam test piece by the volume obtained by sinking the foam test piece into the water and rising from the water level. The foamed product of the present invention has a surface resistivity of lxio8 to lxio13 (Ω) after washing with ultrasonic waves using ethanol. · When the above surface resistivity exceeds 1.0 X 1 0 1 3 (Ω), the antistatic performance is insufficient, and static electricity is accumulated on the surface of the foam, which is liable to cause dust. In order to prevent dust easily, the above surface resistivity is preferably 5 X 1 0] 2 (Ω) or less, and more preferably 1 x 10 12 (Ω) or less. When the surface resistivity of the foam does not reach 1 X 108 (Ω), the static electricity performance required by the packaging material is too high, which may cause high costs. After the foam of the present invention is washed with ultrasonic waves using ethanol, the antistatic performance is not lost. On the other hand, when interfacial activities such as glycerol-stearate are added to the foam -12- 200530307 (10) Antistatic agent in the form of an antistatic agent, the antistatic property will be lost when ultrasonic cleaning is performed with ethanol. That is, when a surfactant-type antistatic agent is used, the antistatic agent oozes out, and the surface of the molded product absorbs moisture in the air, and exhibits antistatic properties. Therefore, even if the antistatic performance occurs under normal conditions, the antistatic agent is washed off the surface of the resin after ultrasonic cleaning with ethanol, and the antistatic performance is lost. Therefore, the effective method for judging the durability of the antistatic performance of the resin layer is to use ethanol as the surface resistivity after ultrasonic cleaning. In this manual, "Using ethanol for ultrasonic cleaning" means that ethanol at 23 ° C is poured into the beaker, and the test piece cut from the foam is sunk (100 mm in length X 100 mm in width X thickness: thickness of the test piece) After 24 hours of ultrasonic cleaning, the test piece was placed in an environment with a temperature of 30 ° C and a relative humidity of 30% for 36 hours to dry and clean. The surface resistivity after ultrasonic cleaning of ethanol is determined after adjusting the state of the test piece after the ultrasonic cleaning operation described above, in accordance with JIS K 691 1 (1 9 7 9). In the foam of the present invention, the average bubble diameter in the extrusion direction: x (mm), the average bubble diameter in the width direction: Y (mm), and the average bubble diameter in the thickness direction: Z (mm). The relationship shown below holds. . 0.35 ^ Z / 1.2 ...... (1) 0.35 ^ Z / Y ^ 1.2 ...... (2) The difference between Z / X and Z / Y is in the above formulas (1) and (2) Range, the smaller the polymer type antistatic dose is, the lower the surface resistivity can be. The closer the z / X and z / Y ratios are to 1.0, the closer the bubbles are, the better the compressive strength of the spherical foam. If Z / X and Z / Y 値 are less than 0.35, the compressive strength may deteriorate. Therefore, the range of Z / X and Z / Y is preferably 0.4 or more, and more preferably 0.45 or more. However, when -13-200530307 (11) z / X and z / Y 値 exceed 1.2, it can be seen that the thickness of the so-called corrugated sheet may vary in appearance, which may deteriorate the appearance. Therefore, the range of Z / X and Z / Υ is preferably 1.1 or less, and more preferably 1.0 or less. The average bubble diameter in the thickness direction: z (mm) satisfies the following relationship. 0.2 ^ Z ^ 1.4 ...... (3) Z 値 is in the range of the formula (3), the surface of the foam is excellent in smoothness, and the appearance of the foam is good. If Z 値 is less than 0.2, the foam tends to have an increased continuous cell ratio, and the rigidity such as compressive strength may decrease. Therefore, the range of Z is preferably 0.3 or more, and more preferably 0.4 or more. If the thickness exceeds 1.4, the thickness of the so-called tile may vary, and the appearance may deteriorate. Therefore, the range of Z is preferably 1.3 or less, and more preferably 1.2 or less. When the foam of the present invention has a thickness of 1 to 2 mm, it is often used as a cushioning material for packaging. In this case, the ranges of the Z / X, Z / Y, and Z 及 are preferably as follows. 0.5 ^ Z / X ^ 0.85 ...... (7) 0.5 S Z / YS 0.85 ...... (8) 0.3 ^ Z ^ 0.6 ...... (9) Z / X, When Z / Y and Z 値 are within the ranges of the formulas (7), (8), and (9), foams having excellent appearance and excellent cushioning properties can be obtained. When the foamed material of the present invention is a thick sheet having a thickness of 3 mm or more, it is mostly subjected to secondary processing such as thermoforming and resin layer lamination. In this case, Z / X, Z / Y. And Z 値 are more preferable as shown below. 0 · 7 S Zn / X s 1 · 〇5 ...... (10) 0.7 ^ Zn / 1.05 …… (11) 0.6 ^ Zn ^ 1.2 ...... (12) -14-200530307 ( 12) Z / X, z / Y, and Z 値 are in the range of (10), (11), and (12) above, the recovery force by heat recovery is small, and the foam is not easy to crack during hot forming. During processing, the laminated surface of the foam and the resin layer is less prone to wrinkles and the secondary processability is poor. In this specification, the average cell diameter in the extrusion direction, the average cell diameter in the width direction, and the average cell diameter in the thickness direction are measured as follows. Average bubble diameter in the extrusion direction: at the center of the width direction of the foam, cut vertically in the extrusion direction, draw a line segment of 30 mm in the extrusion direction near the center of the section, and measure the bubbles on the line. Divide the length of the line segment by the number of bubbles as the average bubble diameter in the extrusion direction: X (mm). Average bubble diameter in the width direction: Draw a line segment with a length of 30 mm in the width direction near the center of the vertical section orthogonal to the extrusion direction of the foam. Measure the number of bubbles on the line segment and divide the length of the line segment by the number of bubbles.値 As the average bubble diameter in the thickness direction: Y (mm). Average bubble diameter in the thickness direction ·· A vertical section in the thickness direction of the foam. Draw a line segment in the thickness direction of the foam at the full thickness. Measure the number of bubbles on the line segment. Divide the length of the line segment by the number of bubbles. The average bubble diameter in the thickness direction is Z (mm). These line segments are drawn from the outer end of the bubble wall of the starting point, and the bubbles that intersect the line segment are also counted as the number of bubbles. The foam of the present invention preferably has a continuous cell ratio of 65% or less. When the continuous cell ratio is within this range, the foam is thin, and the cushioning property is excellent in packaging applications. During thermoforming, the mold has excellent reproducibility and can be formed into the same shape as the mold. Therefore, the continuous bubble ratio is preferably 60% or less, 50% or less 200530307 (13) is more preferable, 40% or less is more preferable, and 25% or less is most preferable. Continuous foaming rate of foam: S (%) is in the order C of a STMD 2 8 5 6-70, using Toshiba BECkMAN (Company) Air Comparative Hydrometer 930 to determine the actual test results of foam test pieces. Volume (the sum of the volume of the independent bubble and the volume of the resin part): VX (L), which is calculated by the following formula (13). S (%) = (Va-Vx) x100 (va_W /// 〇) (13) In the above formula (13), Va, W, and p are as follows.

Va :從發泡物試片外部尺寸計算之表觀容積（L) W :發泡物試片之重疊（g ) P :構成發泡物試片之樹脂密度（g / L ) 構成發泡物試片之樹脂密度p ( g / L )及發泡物試片之重量W ( g )可將發泡物熱壓脫泡後冷卻，從所得樹脂求出。發泡物試片因須於非壓縮狀態納入空氣比較式比重計附屬之樣本杯，係縱25 mm、橫40 mm試片之表觀體積約25 cm3的最小限片數。本發明之發泡物的厚度從緩衝性優之觀點係以〇 . 3 mm 〜30 mm爲佳，0.3 mm〜20 mm更佳，0.3 mm〜10 mm又更佳。尤以被覆被包裝物表面而捆包時，厚度以0 · 3〜1 0 m m爲佳。厚度未達0.3 m m時，發泡物之剛性、緩衝性恐不足。故發泡物之厚度以0.5 mm以上爲佳，0.8 mm以上更佳。而發泡物過厚時，包裝被包裝物時有取用困難之虞，熱成形之際恐難得與模具相同之形狀，故發泡物之厚度以 8 m m以下爲佳，6 m m以下更佳。爲製成厚度超過3 0 mm之發泡物，可接著2層以上之 -16- 200530307 (14) 發泡物成爲層合發泡物。厚度未達3 0 mm之發泡物者。亦可係接著2層以上而成之層合發泡物。製成2層以上之層合發泡物時，可層合相同之發泡物，亦可層合厚度、氣泡徑、表觀密度不同之發泡物，以至於顏色、基材樹脂、功能性添加劑等配方相異之不同發泡物。發泡物厚度係依上述表觀密度測定方法中所述之使用顯微鏡的方法求出。本說明書中發泡物之厚度，如後敘層合有聚烯烴樹脂 ® 層時’係指不含樹脂層之厚度。因此，於發泡物層合有聚 Μ烴樹脂層時，於如上攝影之各點，各測定發泡物之厚度及樹脂層厚度，以所得測定値之算術平均値爲發泡物厚度、樹脂層厚度。. 本發明之發泡物，爲其不易破損，以於一面設厚度5 β m以上之聚烯烴樹脂層（以下或簡稱樹脂層。）爲佳，上述樹脂層之厚度以8 // m以上爲較佳，厚度丨2 // m以上更佳。而樹脂層之厚度過大則重量增加有輕量性差之虞，故鲁樹S曰層厚度以150// m以下爲佳，100# πί以下又更佳。聚烯烴樹脂層可於發泡物將聚烯烴樹脂薄膜經熱接著等習知層合方法形成。上述構成樹脂層之聚稀烴樹脂有聚乙嫌樹脂、聚丙燒 · 樹脂等。上述聚乙烯樹脂其乙烯成分單元在50莫耳％以上，有例如高密度聚乙烯、低密度聚乙烯、直鏈低密度聚乙烯、乙細一乙酸乙細醋共聚物、乙燒-丙燒共聚物、乙燒一丙 ~ 17- 200530307 (15) 烯一丁烯一 1共聚物、乙烯一丁烯一 1共聚物、乙儲一己稀一 1共聚物、乙M — 4 —甲戊;1¾ 一 1共聚物、乙烯一辛烯一^ 共聚物等，以及這些之2種以上的混合物。又，上述聚丙嫌樹脂有，構成上述發泡物之聚丙嫌樹脂以外的泛用聚丙烯樹脂。構成聚烯烴樹脂層之聚烯烴樹脂，在無妨於本發明發泡物之目的及效果之範圍，可含有乙烯两燦橡膠等彈性體等。此時含量以40重量％以下爲佳，25重量％以下更佳，鲁 10重量％以下尤佳。上述樹脂層亦可含例如，造核劑、抗氧化劑、熱安定劑、耐候劑、紫外線吸收劑、阻燃劑等功能性添加劑，金屬離子含選自鉀、，鉚及絶所成群之鹼金屬的離子體樹脂，用於上述發泡物之高分子型抗靜電劑，無機塡料等各種添加劑。其次詳敘本發明之發泡物含有的高分子型抗靜電劑。該高分子型抗靜電劑，係由表面電阻率未達1 X 102Ω，較 β 佳者未達1 X 1 〇 1 ^ ( Ω )之聚合物所成。本發明中高分子型抗靜電劑之數平均分子量以2000以上爲佳，2000〜10000更佳，5000〜60000又更佳，8000〜 40000尤佳，有別於界面活性劑型抗靜電劑。上述高分子 . 型抗靜電劑數平均分子量之上限約1 000000。高分子型抗 _ 靜電劑之數平均分子量在上述範圍，抗靜電性能不受環境影響而更安定出現，幾無抗靜電劑往被包裝物遷移而污染被包裝物表面。 -18 - 200530307 (16) 上述數平均分子量係用高濕凝膠滲透層析儀求出。例如，高分子型抗靜電劑係以聚醚聚酯醯胺、聚醚爲主要成分之親水性樹脂時，數平均分子量係以鄰氯苯爲溶劑，試樣濃度3 mg / mi，以聚苯乙烯爲標準物質，於管柱溫度 1 3 5 °C之條件測定的値。上述溶劑之種類、管柱溫度係隨高分子型抗靜電劑之種類適當變更。高分子型抗靜電劑之熔點以70〜2 70 C爲佳，80〜230 °C更佳’ 80〜2 00 °C又更佳，於抗靜電功能之出現較佳。高分子型抗靜電劑之熔點可依以下之Π S K 7 ；[ 2 ]( 1 9 8 7 )之方法測定。亦即依j ][ s κ 7 1 2 1 ( 1 9 8 7 )中試片狀態調節（2 )之條件（唯冷卻速度爲〗〇它/分鐘）作前處理^以1 0 °C /分鐘升溫得熔化尖峰。以所得熔化尖峰之頂點溫度爲熔點。出現2以上熔化尖峰時，以最大面積之熔化尖峰的頂點溫度爲熔點。唯最大面積熔化尖峰有多數存在日寺’以該等熔化尖峰內最高溫側之熔化尖峰的頂點溫度爲熔點。用於本發明之高分子型抗靜電劑，係以金屬離子含選自ί如及鉋所成群之鹼金屬的乙烯一不飽和羧酸共聚物等離子體、聚醚爲主要成分之親水性樹脂爲佳。更以於上述離子體、親水性樹脂，以與上述聚烯烴樹脂同種或相溶性高之樹脂嵌段共聚者爲佳，經嵌段共聚，聚嫌烴樹脂與高分子型抗靜電劑之相溶性提升，可發揮優良抗靜電性能，同時，添加高分子型抗靜電劑可抑制物性之下降。用於本發明之高分子型抗靜電劑的具體例有特開 -19- 200530307 (17) 2 0 0 1 - 2 7 8 9 8 5號公報所述之組成物。特開2 0 0卜2 7 8 9 8 5號公報記載之組成物具有聚烯烴（a )之嵌段，及體積電阻率1 0 5〜1 0 1 1 Ώ · c m之親水性聚合物（b)之嵌段重複交替結合之構造’數平均分子量（Μη )2000〜60000之嵌段共聚物（Α)。具有上述（a)之嵌段及（b )之嵌段介著選自酯結合、醯胺結合、醚結合、氨酯結合、醯亞胺結合之至少1種結合重複交替結合之構造。用作高分子型抗靜電劑之上述嵌段聚合物（A)之聚烯烴（a )的嵌段可以使用聚合物二末端有羰基（較佳者爲羧基。以下例示之全部羰基的較佳樣態係羧基。）之聚烯烴（a 1 ) ·，:聚合物二末端有羥基之聚烯烴（&2)，聚合物二末端有胺基之聚烯烴（a3)。並可用聚合物一末端有羰基之聚烯烴（a4 )，聚合物一末端有羥基之聚烯烴（a5 )，聚合物一末端有胺基之聚燃烴（a6)。其中因易於改質以具有羰基之聚烯烴（al )及（a4 )爲佳。構成嵌段聚合物（A )之親水性聚合物（b )之嵌段可以使用聚醚（b ])、含聚醚之親水性聚合物（b2 )、陽離子性聚合物（b3 )及陰離子性聚合物（b4 ) 。（ b 1 )可用聚醚二醇（b 1 — 1 )、聚醚二胺（b 1 — 2 )及這些之改質物（bl— 3) 。（b2)可用具有聚醚嵌段形成成分聚醚二醇（bl— 1)段之聚醚酯醯胺（b2— 1)，具有同（bl— 1 )段的聚醚醯胺醯亞胺（b2—2)，具有同（bl — 1)段之聚醆酯（b 2 — 3 )，具有同（b 1 — 2 )段之聚醚醯胺（b 2 — -20- 200530307 (18) 4)及具有同（bl— 1)或（bl — 2)段之聚醚氨酯（b2— 5 )。（b 3 )可用分子內有經非離子性分子鏈（c 1 )隔開之 2〜80個，較佳者3〜60個陽離子性基（c2 )之陽離子性聚合物。（b4 )可用，以具磺醯基之二羧酸（el )、及二醇 (bO)或聚醚（bl)爲必要構成單元，且分子內有2〜80 個，較佳者3〜60個磺醯基之陰離子性聚合物。上述嵌段聚合物（A )之具體例有以下之嵌段聚合物 (A 1 )〜（A4 ) 〇〔嵌段聚合物（A 1 )〕嵌段聚合物（A1 )係，具有（a 1 )嵌段及（b 1 )嵌段重複交替結合構造之嵌段聚合物，含具有下表1之一般式 (1)之重複單元之聚合物。一般式（1)中η係2〜50之整數’ R1及R2之一係氫原子而另一係氫原子或碳原子數1〜 i 〇之烷基，y係〗5〜800之整數，Ε1係自二醇（bO )去除羥基之餘基，A1係碳原子數2〜4之脂烯基，m及表1〜 3 00之整數，X及χ -係選自下表1之一般式（2)〜（8) 之基及選自對應之（2 / )〜（8 / )之基。亦即，X係一般式（2 )之基時，X -係一般式（2 / )之基，一般式（ 3 )〜（8 )及（3 / )〜（8 / )亦具相同關係。 -21 - 200530307 9) 表【w) ώ s JVJVJO—xo8 麵 —olctllo丨 B·? X u)丨c【<Eo<)l01UJlolE<<0)) xomJJ?x/0Va: Apparent volume (L) calculated from the external dimensions of the foam test piece W: Overlap of the foam test piece (g) P: Resin density (g / L) constituting the foam test piece Composition foam The resin density p (g / L) of the test piece and the weight W (g) of the foam test piece can be decompressed by hot-pressing the foam, and then cooled, and can be obtained from the obtained resin. Because the foam test piece must be included in the sample cup attached to the air comparison hydrometer in an uncompressed state, it is the minimum number of pieces with an apparent volume of about 25 cm3 for a test piece with a length of 25 mm and a width of 40 mm. From the viewpoint of excellent cushioning properties, the thickness of the foam of the present invention is preferably 0.3 mm to 30 mm, more preferably 0.3 mm to 20 mm, and even more preferably 0.3 mm to 10 mm. In particular, when the surface of the package is covered and packed, the thickness is preferably from 0.3 to 10 mm. If the thickness is less than 0.3 m, the rigidity and cushioning properties of the foam may be insufficient. Therefore, the thickness of the foam is preferably 0.5 mm or more, and more preferably 0.8 mm or more. When the foam is too thick, it may be difficult to handle the package. When thermoforming, it may be difficult to obtain the same shape as the mold. Therefore, the thickness of the foam is preferably 8 mm or less, and more preferably 6 mm or less. . In order to make a foam with a thickness of more than 30 mm, more than two layers of -16- 200530307 (14) foam can be used to form a laminated foam. Those whose thickness is less than 30 mm. It may also be a laminated foam formed by two or more layers. When two or more laminated foams are made, the same foams can be laminated, or foams with different thicknesses, cell diameters, and apparent densities can be laminated, such as color, substrate resin, and functionality. Different foams with different formulations such as additives. The foam thickness was determined by the method using a microscope described in the apparent density measurement method. In this specification, the thickness of the foam, as described later when a polyolefin resin ® layer is laminated, means the thickness without the resin layer. Therefore, when a foamed polymer resin layer is laminated, the thickness of the foamed material and the thickness of the resin layer are measured at each point of the photography as described above, and the arithmetic mean of the obtained measurement (値) is the foamed material thickness and resin. Layer thickness. For the foam of the present invention, it is not easy to break. It is preferable to provide a polyolefin resin layer (hereinafter referred to as a resin layer) with a thickness of 5 β m or more on one side. The thickness of the resin layer is 8 // m or more. Better, thickness 丨 2 // m is better. However, if the thickness of the resin layer is too large, the weight increase may result in poor lightness. Therefore, the thickness of the Lu Shu S layer is preferably below 150 // m, and more preferably below 100 # πί. The polyolefin resin layer can be formed by a conventional lamination method such as heat-bonding a polyolefin resin film on a foam. Examples of the polyethylene resins constituting the resin layer include polyethylene resins and polypropylene resins. The polyethylene resin has an ethylene component unit of 50 mol% or more, and includes, for example, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-acetic acid ethyl acetate copolymer, and ethylene-propylene copolymerization Material, ethylene-propane-propane ~ 17- 200530307 (15) olefin-butene-1 copolymer, ethylene-butene-1 copolymer, ethylene storage-hexane di-1 copolymer, ethylene M-4-methylpentane; 1¾- 1 copolymers, ethylene-octene copolymers, etc., and mixtures of two or more of these. The polypropylene resin may be a general-purpose polypropylene resin other than the polypropylene resin constituting the foam. The polyolefin resin constituting the polyolefin resin layer may contain elastomers such as ethylene bibram and the like within the scope of the object and effect of the foam of the present invention. In this case, the content is preferably 40% by weight or less, more preferably 25% by weight or less, and more preferably 10% by weight or less. The resin layer may contain functional additives such as a nucleating agent, an antioxidant, a heat stabilizer, a weathering agent, an ultraviolet absorber, and a flame retardant, and the metal ion may contain a base selected from potassium, rivet, and an extreme group Metal ion resins, polymer antistatic agents for foams, inorganic additives and other additives. Next, the polymer antistatic agent contained in the foam of the present invention will be described in detail. The polymer-type antistatic agent is formed of a polymer having a surface resistivity of less than 1 X 102Ω and a better than β of less than 1 X 1 0 1 ^ (Ω). The number average molecular weight of the polymeric antistatic agent in the present invention is preferably 2,000 or more, more preferably 2000 to 10,000, more preferably 5,000 to 60,000, and even more preferably 8000 to 40,000, which is different from the surfactant antistatic agent. The upper limit of the number average molecular weight of the above polymer .type antistatic agent is about 1,000,000. The number average molecular weight of the polymer type anti-static agent is in the above range, and the antistatic performance appears more stable without being affected by the environment. Few antistatic agents migrate to the package and contaminate the surface of the package. -18-200530307 (16) The number average molecular weight is determined by a high-humidity gel permeation chromatography. For example, when the polymer type antistatic agent is a hydrophilic resin containing polyether polyester ammonium amine and polyether as the main components, the number average molecular weight is based on o-chlorobenzene as the solvent, and the sample concentration is 3 mg / mi. Ethylene is a standard substance. It is measured at a column temperature of 1 3 5 ° C. The type of the solvent and the column temperature are appropriately changed depending on the type of the polymer type antistatic agent. The melting point of the polymer antistatic agent is preferably 70 ~ 2 70 C, and more preferably 80 ~ 230 ° C. 80 ~ 2 00 ° C is more preferable, and it is better in the appearance of antistatic function. The melting point of the polymer-type antistatic agent can be measured according to the following method: Π S K 7; [2] (1 9 8 7). That is to say, according to the conditions of j] [s κ 7 1 2 1 (1 9 8 7) condition adjustment (2) (only the cooling rate is 〖〇 / minutes) as pretreatment ^ at 10 ° C / minutes The temperature rises to melt the spikes. The melting point was taken as the apex temperature of the obtained melting spike. When two or more melting peaks occur, the peak temperature of the melting peak with the largest area is taken as the melting point. Most of the largest area melting peaks exist in Nichi's. The apex temperature of the melting peak at the highest temperature side of these melting peaks is taken as the melting point. The polymer type antistatic agent used in the present invention is a hydrophilic resin whose main components are metal ion containing an ethylene-unsaturated carboxylic acid copolymer plasma selected from the group consisting of alkali metals and polyethers. Better. More preferably, the above-mentioned ionomer and hydrophilic resin are preferably copolymerized with the same kind of resin as the polyolefin resin or highly compatible with the above-mentioned resin. After the block copolymerization, the compatibility between the polyhydrocarbon resin and the polymer antistatic agent is compatible. Improved, can display excellent antistatic performance, at the same time, the addition of polymer antistatic agents can suppress the decline in physical properties. Specific examples of the polymer-type antistatic agent used in the present invention include the compositions described in JP-A-19-200530307 (17) 2 0 0 1-2 7 8 9 8 5. The composition described in Japanese Patent Application Laid-Open No. 2 0 2 2 7 8 9 8 5 has a block of polyolefin (a), and a hydrophilic polymer having a volume resistivity of 1 5 to 1 0 1 1 Ώ · cm (b A block copolymer (A) having a structure having a number-average molecular weight (Mη) of 2000 to 60,000 in which blocks are repeatedly and alternately combined. The block having the above-mentioned (a) block and (b) has a structure in which at least one kind of bond selected from the group consisting of ester bond, amidine bond, ether bond, urethane bond, and imine bond is repeatedly alternately bonded. As the block of the polyolefin (a) of the above-mentioned block polymer (A) used as a high-molecular antistatic agent, a carbonyl group (preferably a carboxyl group) at the both ends of the polymer can be used. Polyolefin (a 1) of the carboxyl group.): Polyolefin (& 2) having a hydroxyl group at both ends of the polymer and polyolefin (a3) having an amine group at the both ends of the polymer. Polyolefins (a4) having a carbonyl group at one end of the polymer, polyolefins (a5) having a hydroxyl group at one end of the polymer, and poly-flammable hydrocarbons (a6) having an amine group at the end of the polymer can be used. Among them, polyolefins (al) and (a4) having a carbonyl group are preferred because they are easily modified. As the block of the hydrophilic polymer (b) constituting the block polymer (A), polyether (b), polyether-containing hydrophilic polymer (b2), cationic polymer (b3), and anionic can be used. Polymer (b4). (B 1) Polyether glycol (b 1-1), polyether diamine (b 1-2) and modified products (bl-3) can be used. (B2) Polyetheresteramide (b2-1) having a polyether block-forming component, polyetherdiol (bl-1), and polyetheramide (imide) having the same (bl-1) segment can be used. b2-2), polyfluorenyl ester (b 2-3) with the same (bl -1) segment, polyetheramide (b 2--20- 200530307 (18) 4 with the same (b 1-2) segment ) And a polyether urethane (b2-5) having the same (bl-1) or (bl-2) segment. (B 3) A cationic polymer having 2 to 80, preferably 3 to 60 cationic groups (c2), separated by a nonionic molecular chain (c 1) in the molecule. (B4) Available, using dicarboxylic acid (el) with sulfofluorenyl group and glycol (bO) or polyether (bl) as necessary constituent units, and there are 2 to 80 in the molecule, preferably 3 to 60 Sulfofluorenyl anionic polymer. Specific examples of the block polymer (A) include the following block polymers (A 1) to (A4). [Block polymer (A 1)] The block polymer (A1) is a type having (a 1 A block polymer having a repeating alternating combination of a block and a (b 1) block, and a polymer having a repeating unit of the general formula (1) in Table 1 below. In the general formula (1), η is an integer of 2 to 50, and one of R1 and R2 is a hydrogen atom and the other is a hydrogen atom or an alkyl group having 1 to i carbon number, and y is an integer of 5 to 800, and E1. Residual group removed from diol (bO), A1 is an aliphatic alkenyl group having 2 to 4 carbon atoms, m and integers shown in Table 1 to 300, and X and χ-are selected from the general formula of Table 1 below ( 2) A base selected from (8) and a base selected from the corresponding (2 /) to (8 /). That is, when X is the basis of the general formula (2), X- is the basis of the general formula (2 /), and the general formulae (3) to (8) and (3 /) to (8 /) also have the same relationship. -21-200530307 9) Table 【w) FREE S s JVJVJO—xo8 surface —olctllo 丨 B ·? X u) 丨 c [< Eo <) l01UJlolE < < 0)) xomJJ? X / 0

ttlrTr JirHV n 01 5125101 ^ TrJ十r 了 J—ΓΟ,ίιο· V H/o=K Ho= 4x.in4. •ο—βα:—Ν--Κ01Ηυ」ΗΟ-^σ- z-/o=% * f 丨 XI x《Ho-J Ho-)丨 X I* s s £ sttlrTr JirHV n 01 5125101 ^ TrJ Jr Γο, VH / o = K Ho = 4x.in4. • ο—βα: —Ν--Κ01Ηυ 」ΗΟ- ^ σ- z- / o =% * f 丨 XI x 《Ho-J Ho-) 丨 XI * ss £ s

IolH—^:— s—OLXOJXO— 1 ¾IolH — ^: — s—OLXOJXO— 1 ¾

X —oi K— o! —olljv — —0— cIQ1N4^<1 4^1¾^ 0 \xoj ?£?x-?=ow-2l*a:—ο—^Ί3ι4ι=ο-^^<γ IOIHI ec— ο— ο— 02) ox-x-o=\H jX —oi K— o! —Olljv — —0— cIQ1N4 ^ < 1 4 ^ 1¾ ^ 0 \ xoj? £? X-? = Ow-2l * a: —ο— ^ Ί3ι4ι = ο-^^ < γ IOIHI ec— ο— ο— 02) ox-xo = \ H j

E -22 - 200530307 (20) 表1之一般式（2)〜（8)及（2> )〜（8 / )中， R3、R3 '係碳原子數2〜3之三價烴基，R4係碳原子數】〜 11之2價烴基，R5係氫原子或碳原子數}〜；!〇之烷基，r6係碳原子數2〜2 2之烴基，E2表有機二異氰酸酯餘基，r係1 〜10，u及v係〇或1。Q、Q 、丁及丁 /係下表2之基。表2E -22-200530307 (20) In the general formulae (2) to (8) and (2>) to (8 /) in Table 1, R3 and R3 'are trivalent hydrocarbon groups having 2 to 3 carbon atoms, and R4 is Number of carbon atoms] ~ 11 bivalent hydrocarbon group, R5 is hydrogen atom or carbon number} ~; alkyl group, r6 is a hydrocarbon group with 2 to 22 carbon atoms, E2 is an organic diisocyanate residual group, r is 1 to 10, u and v are 0 or 1. Q, Q, Ding and Ding are the basis of Table 2 below. Table 2

其中R5係氫原子或碳原子數1〜10之烷基，R7係氫原子或甲基，t在R7係甲基時爲0，氫原子時爲1。一般式（1 )之重複單元中{}內之聚醚段 · {OA1) m— Ο— E1 — 0— (Ah) )係由上述聚醚（bl )之聚酸部分構成，式中E 1、A 1、m及m —同上。一般式 (1 )中E 1係自脂肪族二元醇、二元酚或含三級胺基之二醇去除羥基之餘基爲佳。’ . 一般式（1 )中，X係一般式（2 )之基，X /係一般式（2/)之基的嵌段聚合物（A1)，可使上述具羰基之聚烯烴（a 1 )與聚醚二醇（b 1 - 1 )直接反應而得。一般式（2 )及（2 / )中R。及R3 '如表3。R4係氫原子或甲基 -23- 200530307 (21) ，丈在R4係氫原子時爲1，R4係甲基時爲〇。例如聚烯烴之羰基改質係用順丁烯二酸或延胡索酸時，R 3係—c Η 2 — c Η < ，R3 '係 > CH — CH2 -。表3Among them, R5 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R7 is a hydrogen atom or a methyl group, t is 0 when R7 is a methyl group, and 1 is a hydrogen atom. The polyether segment within {} in the repeating unit of general formula (1). {OA1) m— Ο— E1 — 0— (Ah)) is composed of the polyacid portion of the above polyether (bl), where E 1 , A 1, m and m — same as above. In the general formula (1), E 1 is preferably a residue of a hydroxyl group removed from an aliphatic diol, a dihydric phenol or a tertiary amino group-containing glycol. '. In the general formula (1), X is a base of the general formula (2), and X / is a block polymer (A1) of the general formula (2 /), which can make the polyolefin having a carbonyl group (a 1 ) And polyether glycol (b 1-1) directly obtained. R in general formulae (2) and (2 /). And R3 'are shown in Table 3. R4 is a hydrogen atom or methyl -23-200530307 (21), which is 1 when R4 is a hydrogen atom, and 0 when R4 is a methyl group. For example, when the carbonyl modification of polyolefins uses maleic acid or fumaric acid, R 3 is —c Η 2 — c Η <, R3 'is > CH — CH2-. table 3

R 3 -CH-CH-(CH2)t^R4R 3 -CH-CH- (CH2) t ^ R4

構成嵌段聚合物（A 1 )之聚醚（b 1 )之量，基於（a i )及（bl)之合計重量通常係20〜90重量％，25〜90重量 %爲佳，30〜70重量％尤佳。（A1)之Μη通常係2000〜 60000，5000 〜40000較佳，8000 〜30000尤佳。砍段聚合物（Α1)之構造中，聚烯烴（a)之嵌段及親水性聚合物（b )之嵌段之重複單元的平均重複數（Nn )’通常係2〜50’ 2.3〜30爲佳，2.7〜20更佳，3〜10尤The amount of the polyether (b 1) constituting the block polymer (A 1) is usually 20 to 90% by weight, preferably 25 to 90% by weight, and 30 to 70% by weight based on the total weight of (ai) and (bl). % Is better. The Mn of (A1) is usually 2000 to 60,000, preferably 5000 to 40,000, and particularly preferably 8000 to 30,000. In the structure of the chopped polymer (A1), the average repeating number (Nn) of the repeating units of the block of the polyolefin (a) and the block of the hydrophilic polymer (b) is usually 2 to 50 '2.3 to 30 Better, 2.7 ~ 20, especially 3 ~ 10

佳。〔嵌段聚合物（A 2 )〕嵌段聚合物（A2 )係聚烯烴（a )之嵌段與親水性聚合物（b)之嵌段以（a) 一（b)型或（a) 一（b) 一 )型結合而成之嵌段聚合物。（A2 )可由（b2 )與表4之一般式（9)〜（]1)中任一之聚合物一末端有羰基之聚燒烴（a4 )反應而得。 -24- (10)200530307 (22) 表4good. [Block polymer (A 2)] The block polymer (A 2) is a block of polyolefin (a) and a block of hydrophilic polymer (b) is (a)-(b) type or (a) A (b) a) type block polymer. (A2) can be obtained by reacting (b2) with a polymer (a4) having a carbonyl group at one end of any one of the general formulae (9) to () 1) in Table 4. -24- (10) 200530307 (22) Table 4

Re—Q，~Chr\ R>/Re—Q, ~ Chr \ R > /

Fi10Fi10

Re_Q，-CH2一CH-COOH (1 1) (12〉Re_Q, -CH2-CH-COOH (1 1) (12>

R8—Q’-f^-COO_ COOHR8—Q’-f ^ -COO_ COOH

FI10 R»—Q，--COO - (1 3)FI10 R »—Q, --COO-(1 3)

R8-Q'-CI J H 一 COO—R8-Q'-CI J H a COO—

,CH—COOH (14〉 (1 5) r9-q-fi9-conh—, CH—COOH (14〉 (1 5) r9-q-fi9-conh—

COOHCOOH

Fji10Fji10

Re—Q’-CH2—CH—CONH— (I 6) RB — Q’-CH—CONH—Re_Q’-CH2—CH_CONH— (I 6) RB — Q’-CH_CONH—

R yCH-COOH 11 (I 7)R yCH-COOH 11 (I 7)

O R o (l 8) -25- 200530307 (23) 表 —（NH — A2〉P —〇一它3—〇一（AJ — NH) p — R1， 19) (£’“D — Z〕w—〈D_E，）u (2 0) -喟- (2 1) 言 H_E7 N - Ο Η 〇 T Ο Η 〇 (22) -(C-E^-OV-C Ο ο (23) -AMjI— (jj-— (24) -A3—Ν —{C—E*-NJV一 C—E6 * II 1 II Η 〇 Η 〇OR o (l 8) -25- 200530307 (23) Table — (NH — A2> P —〇—It 3—〇1 (AJ — NH) p — R1, 19) (£ '“D — Z] w— <D_E,) u (2 0)-喟-(2 1) H_E7 N-〇 Η 〇T Ο Η 〇 (22)-(CE ^ -OV-C Ο ο (23) -AMjI— (jj-— (24) -A3—N — {C—E * -NJV—C—E6 * II 1 II Η 〇 Η 〇

^^-Ee-C)s-NI Μ—Α3- (2 5) (2 6) —C^N^-E3-N-(E10)q-C-Ο Η Η Ο -Α3~Ν -C-N—Ε3 ~N-(E10)q-C--N 一 Α3_ (2 7) Η Ο Η Ο Η -26- 200530307 (24) 式中R8係聚烯烴餘基，q -係式一 c Η ( R 1G ) — c Η = C(R1G) — CH2 —示之基，R9係碳原子數2、3之三價烴基，R1Q係氫原子或碳原子數1〜iO之烷基，係氫原子或甲基，（b2 )係以表5一般式（19 )者爲佳。式（19 )中，E 3係含聚醚基親水性聚合物餘基，R I 2及R 13係氫原子、式一C〇一NH— E2— NHCOO— R14— NH2、式一CO— NH — E2— NCO、式—G或式—Ch2CH(OH) CH2—〇— E4— 0-G之基，P係0或1，a2係碳原子數2〜4之脂烯基或式—（_ R15 — CO) r -之基，R】6係碳原子數1〜n之2價烴基（以下亦含飽和烴基、不飽和烴基之任一），r係1〜1 〇之整數，R] 4係碳原子數2〜12之2價烴基，E2係有機二異氰酸酯之餘基，G係環氧丙基，Έ4表自二環氧丙醚（G — 0- E4-0—G)去除環氧丙氧基之餘基。R12及R13係以氫原子及/ 或式一 CO — NH—E2— NCO之基爲佳。一般式（19)中E3 係以表5之一般式（2 0 )之基爲佳。一般式（20)中，E5係聚醚（bl)之餘基，D係氧原 ® 子及/或亞胺基，Z係選自聚酯醯胺、聚醯胺醯亞胺、聚酯、聚醯胺及聚氨酯所成群之聚合物段’以表5中一般式 (21)〜（27)之任一的段爲佳。u係0或1，w通常係2〜 5，3〜30爲較佳。Z以一般式（21)之聚醋酸肢段爲佳。 . 一般式（21)〜（27)中，E6係自碳原子數4〜20之二羧 · 酸去除羧基之餘基，E7係自三價或四價之芳香族殘酸去除 3個殘基之餘基，E 8係自與碳原子數4〜1 2之一殘酸及碳原子數2〜1 2之二胺之一醯胺及碳原子數6〜1 2之胺羧酸所成 -27- 200530307 (25) 群之聚醯胺形成成分去除末端之胺基及羧基之餘基，E9係從選自碳原子數4〜12之二羧酸與前敘二醇（b0)之酯及碳原子數6〜12之羥羧酸所成群之聚酯形成成分去除末端羥基及羧基之餘基，S、S#、S〃係0或1〜50之整數，（ S+S —)至少係1，A3係碳原子數2〜4之脂烯基或式—R16 —CO —之基，R16示碳原子數1〜11之2價烴基，q係0或1 〜10 之整數，E1G 係式一 CO— D— E]1 - D-CO— NH— E2 — NH —之基，E2係有機二異氰酸酯之餘基，D係氧原子及/ # 或亞胺基，E 11係鏈延伸劑之餘基。嵌段聚合物（A2 )有，親水性聚合物（b2 )末端之一或二者係以表4中一般式（12)〜（14)之基{ (b2) 末端係羥基或環氧基時}取代的構造者（介著酯結合而結合）；以表4中一般式（15)〜（17)之基{ (b2)末端係胺基或異氰酸酯基時}取代之構造者（介著醯胺結合之結合）；及以表4中一般式（1 8 )之基{ ( b2 )之末端係胺基時丨取代之構造者（介著醯胺結合而結合）。 · 上述表4之聚烯烴餘基係以式ri7—丨（ch(R18) —CH(R19)丨y —之基爲佳（式中R17係氫原子或H2C = CH—之基，R18及R1 9之一係氫原子另一係氫原子或碳原子數1〜10之院基，y表15〜800之整數。）。^^-Ee-C) s-NI Μ-Α3- (2 5) (2 6) —C ^ N ^ -E3-N- (E10) qC-〇 Η Ο Ο -Α3 ~ Ν -CN-Ε3 ~ N- (E10) qC--N-Α3_ (2 7) Η Ο Η Ο Η -26- 200530307 (24) where R8 is a polyolefin residue and q-is a formula c c (R 1G) — c Η = C (R1G) — CH2 — radicals shown, R9 is a trivalent hydrocarbon group having 2 or 3 carbon atoms, R1Q is a hydrogen atom or an alkyl group having 1 to iO carbon atoms, is a hydrogen atom or a methyl group, (b2) It is better to use the general formula (19) in Table 5. In formula (19), E 3 is a polyether group-containing hydrophilic polymer residue group, RI 2 and R 13 are hydrogen atoms, Formula 1 C0—NH— E2— NHCOO— R14— NH2, Formula 1 CO— NH — E2—NCO, formula—G or formula—Ch2CH (OH) CH2—〇— E4— 0-G group, P is 0 or 1, a2 is aliphatic alkenyl or formula of 2 to 4 carbon atoms — (_ R15 — CO) r —, R] 6 is a bivalent hydrocarbon group having 1 to n carbon atoms (hereinafter also containing any of saturated hydrocarbon group and unsaturated hydrocarbon group), r is an integer of 1 to 10, R] 4 series Divalent hydrocarbon group with 2 to 12 carbon atoms, residual group of E2 series organic diisocyanate, G series epoxy group, Έ4 Table shows the removal of propylene oxide from diglycidyl ether (G-0-E4-0-G) Residual group of oxy. R12 and R13 are preferably based on a hydrogen atom and / or a formula of CO—NH—E2—NCO. E3 in the general formula (19) is preferably based on the general formula (20) of Table 5. In the general formula (20), E5 is a residual group of polyether (bl), D is an oxygen atom and / or an imine group, and Z is selected from the group consisting of polyester amide, polyamine imimine, polyester, The polymer segments 'grouped by polyamide and polyurethane' are preferably any of the general formulae (21) to (27) in Table 5. u is 0 or 1, w is usually 2 to 5, 3 to 30 is preferred. Z is preferably the polyacetic acid limb of general formula (21). In the general formulae (21) to (27), E6 is a residue of a carboxyl group from a dicarboxylic acid having 4 to 20 carbon atoms, and E7 is a residue of 3 or 4 valences from an aromatic residual acid. Residual group, E 8 is formed from a residual acid having 4 to 12 carbon atoms, amidamine, a diamine having 2 to 12 carbon atoms, and an amine carboxylic acid having 6 to 12 carbon atoms. 27- 200530307 (25) Group of polyamines forming components Remove the amine and carboxyl residues at the terminal. E9 is selected from the esters of dicarboxylic acids with 4 to 12 carbon atoms and the aforementioned diol (b0) and Polyester-forming components formed from hydroxycarboxylic acids having 6 to 12 carbon atoms. The remaining hydroxyl and carboxyl groups are removed. S, S #, and S〃 are integers of 0 or 1 to 50. (S + S —) is at least System 1, A3 is an aliphatic alkenyl group having 2 to 4 carbon atoms or a group of the formula —R16 —CO —, R16 represents a divalent hydrocarbon group having 1 to 11 carbon atoms, q is an integer of 0 or 1 to 10, and E1G is Formula 1 CO— D— E] 1-D-CO— NH— E2 — NH —, E2 is the remaining group of organic diisocyanate, D is an oxygen atom and / # or imine group, E 11 is a chain extender Yu base. For the block polymer (A2), one or both ends of the hydrophilic polymer (b2) are based on the general formulae (12) to (14) in Table 4. {b2) When the terminal is a hydroxyl group or an epoxy group } Substituted constructors (combined via ester bonding); those substituted by the bases of general formulae (15) to (17) in Table 4 {(b2) when the terminal is an amine or isocyanate group} (via 醯A combination of amine binding); and a structure substituted with a base {(b2) of the general formula (1 8) in Table 4 when the terminal is an amine group (bonding via hydrazine binding). · The polyolefin residues in Table 4 above are preferably based on the formula ri7— 丨 (ch (R18) —CH (R19) 丨 y— (where R17 is a hydrogen atom or H2C = CH—, R18 and R1 One of 9 is a hydrogen atom or the other is a hydrogen atom or a radical with 1 to 10 carbon atoms, and y is an integer of 15 to 800.).

P 構成嵌段聚合物（A2 )之親水性聚合物（b2 )之量，基於（A2)之重量，通常係2〇〜8〇重量％，以3〇〜7〇重量％爲佳。（A2)之Μη通常係2000〜60000，5000〜 4 0 0 0 〇爲較佳。嵌段聚合物（a 2 )之構造中，聚烯烴（a ) -28- 200530307 (26) 之嵌段’及親水性聚合物（b )之嵌段之重複單元的平均重複數（Nn)通常係0.4〜2.1，0.5〜2.0爲佳，〇.6〜1·9 更佳，0 · 7〜1 . 8尤佳。〔嵌段聚合物（A3 )〕嵌段聚合物（A3 )，親水性聚合物（b )係分子內有以非離子性分子鏈（cl )隔開之2〜80個，較佳者3〜60個之陽離子性基（c2 )之陽離子性聚合物（b3 )嵌段者，具有聚烯烴（a )與（b3 )重複交替結合之構造。（A3 )之 Μη通常係 2000 〜60000，5000 〜40000 較佳，8000 〜30000 尤佳。（A3 )中陽離子性基（C2 )含量係（A3 )每1分子 2〜5 0 0個，1 〇〜3 0 0個較佳，1 5〜2 5 0個尤佳。每1個陽離子性基（c2)之（A3)的Μη通常係120〜30000，以200〜 6000爲佳，300〜4000尤佳。嵌段聚合物（A 3 )之構造中，聚烯烴（a )之嵌段’ 及親水性聚合物（b )之嵌段的重複單元之平均重複數（ Nn)通常係2〜50，以2.3〜30爲佳，2.7〜20更佳，3〜1〇尤佳。〔嵌段聚合物（A4)〕嵌段聚合物（A4 )係親水性聚合物（b )以具擴醯基之二羧酸（el )及二醇（b0 )或聚醚（bl )爲必要構成單元，且分子內具有2〜80個，較佳者3〜60個磺醯基之陰離子性聚合物（b4 )之嵌段者，具有（a )及（b4 )重複父 -29- 200530307 (27) 替結合之構造。（A4)之Μη通常係2000〜60000，5000〜 40000爲佳，8000〜30000尤佳。（Α4)中磺醯基之含量係每1 (Α4)分子2〜500個，10〜300個較佳，15〜250個尤佳。每1個磺醯基的（Α4)之Μη通常係120〜30000, 200〜6000較佳，300〜4000尤佳〇嵌段聚合物（Α4 )之構造中，聚烯烴（a )之嵌段，及親水性聚合物（b )之嵌段的重複單元之平均重複數（ Nn)通常係2〜50，2.3〜30較佳，2.7〜20更佳，3〜1〇尤佳。上述高分子型抗靜電劑可各單獨使用，亦可組合使用〇 ^本發明之發泡物獨立於濕度等環境條件出現抗靜電性能’不易附著麈埃故適於緩衝材料、建築絕熱材料、食品容器等’不污染被包裝物表面故適用作包裝物之緩衝材料。本發明之發泡物，將發泡物洗淨亦不失抗靜電性能，故亦適於再利用。以下詳細說明本發明之聚烯烴樹脂發泡物之製造方法〇本發明之製造方法有例如，於擠出機先端安裝τ模、圓模等使用之擠出發泡法。其中爲寬〗000 mm以上之發泡薄片或發泡板之易於製得，以使用發泡性聚烯烴樹脂溶體均勻延伸’以此出現抗靜電性能之安裝圓模的擠出機之擠出發泡法爲佳。具體而言係將上述聚烯烴樹脂、高分子开^ 扒靜電劑及氣泡調整劑由擠出機原料供給口供給於擠出機 -30 - 200530307 (28) ’將之加熱混練，繼之供給物理發泡劑於擠出機中連同聚烯烴樹脂熔體更予混練形成發泡性聚烯烴樹脂熔體，將上述發泡性聚烯烴樹脂熔體調整爲發泡溫度後，自圓模擠出發泡形成筒狀發泡物’切開其一端，得聚烯烴樹脂發泡物〇上述發泡性聚烯烴樹脂熔體在擠出機內之發泡溫度，因可得低表觀密度之發泡物係具充分黏彈性之樹脂溫度。具體而言，發泡溫度以聚烯烴樹脂之〔結晶溫度+ 5 t〕鲁以上’〔結晶溫度+ 30C〕以下爲佳。本發明方法中進行擠出發泡，以得表面電阻率1 X 1 0 8 〜1 X 1 0 13 ( Ω )之發泡物。爲之，:對於聚烯烴樹脂1 0 0重量份添加2〜1 4重量份之高分子型抗靜電劑。高分子型抗靜電劑添加量過多，則發泡受阻，連續氣泡率低，不得低表觀密度之發泡物。連續氣泡率高之發泡物緩衝性差，並因氣泡粗大用途有限。爲此，高分子型抗 · 靜電劑之添加量以1 1重量份以下爲佳，9重量份以下更佳，8重量份以下又更佳，7重量份以下再更佳，6.5重量份以下尤佳。高分子型抗靜電劑添加量過少，則發泡物表面電阻率蓽不達ΙχΙΟ13 ( Ω )以下。故高分子型抗靜電劑之添加量以 3重量份以上爲佳，3 . 8重量份以上更佳。高分子型抗靜電劑係用上述者。本發明方法係以擠出發泡形成發泡物，使所得發泡物 -31 - 200530307 (29) 之表觀密度爲15〜65 g/L。如此，高發泡時氣泡成長過程中使高分子型抗靜電劑定向，則添加量少亦可大大提升抗靜電性能。亦即，將後敘特定高分子型抗靜電劑添加於特定聚烯烴樹脂，且擠出發泡使發泡物之表觀密度爲〗5〜 65 g/ L，以少量高分子型抗靜電劑添加，所得發泡物之表面電阻率可爲ΙχΙΟ8〜1χ1〇】3(Ω)。且高分子型抗靜電劑之效果獨立於放置時間、溫度條件等，則製造後起發泡物表面電阻率即可係1 X 1 〇 8〜1 X 1 0 1 3 ( Ω )。剛製造後鲁起發泡物表面即充分出現電阻率，以丁院等可燃性物理發泡劑進行擠出發泡之際，可得防止靜電引火意外之優良效果。使發泡物之表觀密度在上述範圍內之方法，主要係以物理發泡劑之添加量作調節。上述物理發泡劑有例如，丙烷、正丁烷、異丁烷、正戊烷、異戊烷、環戊烷、正己烷、異己烷、環己烷等脂肪族烴、氯甲烷、氯乙烷等氯化烴、1，1，1，2 —四氯乙烷鲁、1，1 一二氯乙院等氟化烴等有機物理發泡劑，氧、氮、二氧化碳、空氣等無機物理發泡劑。這些物理發泡劑可以混合2種以上使用。其中聚烯烴樹脂選用聚乙條樹脂時，從與樹脂之相溶性、發泡性之觀點係以有機物理發泡劑爲 . 佳’其中以正丁烷、異丁烷或這些之混合物爲主要成分者較合適。製造發泡物之際有氣泡調整劑之添加。氣泡調整劑有硼酸鋅、硼酸鎂、硼砂等硼酸金屬鹽、氯化鈉、氫氧化鋁 -32- 200530307 (30) 、滑石、沸石、氧化矽、碳酸鈣、重碳酸鈉、碳酸一 2 , 2 —亞甲雙（4，6—三級丁苯基）鈉、苯甲酸鈉、苯甲酸鈣、本甲酸錦、硬脂酸鈉等。檸檬酸及重碳酸鈉、檸檬酸之鹼鹽與重碳酸鈉等之組合物亦可用作氣泡調整劑。這些氣泡調整劑可以混合2種以上使用。上述發泡劑之添加量係隨發泡劑之種類，目標發泡物之表觀密度調整。氣泡調整劑之添加量主要隨目標氣泡徑調節。例如，發泡劑係用異丁烷3 0重量％及正丁烷7 0重量鲁 %之Ί院混合物時’丁院混合物之添加量係聚嫌烴樹脂每 100重量份4〜35重量份，5〜30重量份較佳，6〜25重量份更佳。氣泡調整劑係用例如，對於聚乙烯樹脂1 00重量份 ’以滑石1 1 · 8重量份、檸檬酸鈉5.9重量份之配合量製作之母料時，氣泡調整劑之添加量係聚烯烴樹脂每1 00重量份〇 . 3〜1 〇重量份，〇 . 5〜5重量份較佳。用於本發明方法之高分子型抗靜電劑，結晶溫度在 1 1 0°C以下，且1 90°C之熔融黏度（Mb )爲80〜1 000 Pa · s _ 〇結晶溫度超過1 1 0 °c時，與聚烯烴樹脂之混練性不充分，難得發泡物之抗靜電特性。尤以高分子型抗靜電劑之結晶溫度高於聚烯烴樹脂之結晶溫度時，抗靜電劑之結晶、溫度過高，則於擠出機內部結晶，有阻礙發泡之虞。 _ 唯高分子型抗靜電劑之結晶溫度下限爲6 0 °c左右。結晶溫度過低，樹脂組成物有物性差之虞。本發明方法中，高分子型抗靜電劑以少量含有，而使 -33- 200530307 (31) 發泡物出現優良抗靜電性，須以擠出發泡使抗靜電劑定向，並於擠出發泡步驟中高分子型抗靜電劑均勻分散於發泡性聚烯烴樹脂熔體中，經擠出發泡形成導電網路。因而，上述高分子型抗靜電劑之結晶溫度，及發泡性聚烯烴樹脂熔體之混練中聚烯烴樹脂及高分子型抗靜電劑之黏度均衡很重要。用於本發明方法之高分子型抗靜電劑於1 90 °C之熔融黏度（Mb)係80〜1000 Pa· s。亦即，熔融黏度（Mb) φ 須滿足以下（5 )式。 80Pa· s^Mb^lOOOPa· s (5) 該熔融黏度之高分子型抗靜電劑因可與聚烯烴樹脂充分混練’容易形成較佳導電性網路。從以上觀點以1 5 〇〜 800 Pa· s爲佳。150 〜500 Pa· s更佳。用於本發明之聚烯烴樹脂於19(TC之熔融黏度（Ma) 以250〜6000 Pa· s爲佳，300〜5000 Pa· s更佳。熔融黏度（Ma)超過6 000 Pa · 8則施加於擠出機之負荷過高，擠春出之際不易控制，發泡時樹脂延伸不足，恐不得外觀良好之發泡物。熔融黏度（Ma)未達250 Pa· s則與高分子型抗靜電劑之混練性差，有礙於高分子型抗靜電劑之均勻分散性，有抗靜電效果差之虞。聚烯烴樹脂選用聚乙烯烯樹脂時，以用1 9 〇 °C熔融黏度300〜1600 Pa· s者爲佳，700〜1500 Pa· s更佳。聚乙嫌樹脂製之發泡物者，多用於有緩衝性之要求的用途，氣泡亦微細。而因高分子型抗靜電劑之熔融黏度不適於發泡 -34- 200530307 (32) ’爲其彌補以選用熔融張力高之聚乙烯樹脂爲佳。聚綠烴樹脂選用聚丙烯樹脂時，以使用1 9 0 t之熔融黏度在2000〜6000 Pa· s範圍內者爲佳，3000〜550〇 pa· s更佳，4000〜50〇〇 Pa · s之高黏度者尤佳。該高黏度聚丙烯樹脂有前敘高熔體張力型聚丙烯樹脂。本發明方法中，高分子型抗靜電劑及聚烯烴樹脂於 1 9 0 °C之熔融黏度並須控制爲滿足下述（4 )式。The amount of the hydrophilic polymer (b2) constituting the block polymer (A2) is usually 20 to 80% by weight, and preferably 30 to 70% by weight, based on the weight of (A2). The Mn of (A2) is usually 2000 to 60,000, and preferably 5000 to 400,000. In the structure of the block polymer (a 2), the average repeating number (Nn) of the repeating units (Nn) of the blocks of the polyolefin (a) -28- 200530307 (26) and the block of the hydrophilic polymer (b) is usually It is preferably 0.4 to 2.1, 0.5 to 2.0, more preferably 0.6 to 1.9, and particularly preferably 0.7 to 1.8. [Block polymer (A3)] The block polymer (A3), the hydrophilic polymer (b) has 2 to 80 molecules separated by nonionic molecular chains (cl) in the molecule, preferably 3 to 3 The cationic polymer (b3) block having 60 cationic groups (c2) has a structure in which polyolefin (a) and (b3) are repeatedly and alternately combined. The Mn of (A3) is usually 2,000 to 60,000, preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000. The content of the cationic group (C2) in (A3) is 2 ~ 500 per molecule, preferably 100 ~ 300, and particularly preferably 15 ~ 250. The Mn of each cation group (c2) (A3) is usually 120 to 30,000, preferably 200 to 6000, and particularly preferably 300 to 4000. In the structure of the block polymer (A 3), the average repeating number (Nn) of the repeating unit (Nn) of the block 'of the polyolefin (a) and the block of the hydrophilic polymer (b) is usually 2 to 50, and 2.3 ~ 30 is preferable, 2.7 ~ 20 is more preferable, and 3 ~ 10 is more preferable. [Block Polymer (A4)] The block polymer (A4) is a hydrophilic polymer (b). Dicarboxylic acid (el), diol (b0), or polyether (bl) having a fluorene group are necessary. A constituent unit having 2 to 80, preferably 3 to 60 sulfofluorenyl anionic polymer (b4) blocks in the molecule, having (a) and (b4) repeating parent-29- 200530307 ( 27) The structure of the combination. The Mn of (A4) is usually 2,000 to 60,000, preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000. The content of sulfofluorenyl group in (Α4) is 2 to 500 per 1 (Α4) molecule, preferably 10 to 300, and most preferably 15 to 250. The Mn of each sulfonyl group (A4) is usually 120 to 30,000, preferably 200 to 6000, and particularly preferably 300 to 4000. In the structure of the block polymer (A4), the block of the polyolefin (a), The average repeating number (Nn) of the repeating units of the block of the hydrophilic polymer (b) is usually 2 to 50, more preferably 2.3 to 30, more preferably 2.7 to 20, and most preferably 3 to 10. The above-mentioned polymer antistatic agents can be used individually or in combination. The foam of the present invention exhibits antistatic performance independently of environmental conditions such as humidity. 'It is not easy to adhere to 麈, so it is suitable for cushioning materials, building insulation materials, food. Containers and the like do not contaminate the surface of the package and are therefore suitable as a buffer material for the package. The foamed product of the present invention is also suitable for reuse because the foamed product is washed without losing its antistatic performance. Hereinafter, the manufacturing method of the polyolefin resin foam of the present invention will be described in detail. The manufacturing method of the present invention includes, for example, an extrusion foaming method in which a τ die and a round die are installed at the tip of an extruder. Among them, it is easy to produce foamed sheet or foamed board with a width of more than 000 mm, and it is used to uniformly extend the use of foamable polyolefin resin solution to extrude the extruder with a round die equipped with antistatic performance. Soak method is better. Specifically, the above-mentioned polyolefin resin, high-molecular-weight electrostatic inhibitor, and bubble regulator are supplied from the raw material supply port of the extruder to the extruder. The foaming agent is kneaded together with the polyolefin resin melt in the extruder to form a foamable polyolefin resin melt. The foamable polyolefin resin melt is adjusted to a foaming temperature, and then extruded and foamed from a round die. A cylindrical foam is formed, and one end thereof is cut to obtain a polyolefin resin foam. The foaming temperature of the above-mentioned foamable polyolefin resin melt in an extruder is to obtain a foam system having a low apparent density. Fully viscoelastic resin temperature. Specifically, the foaming temperature is preferably equal to or higher than [crystallization temperature + 5 t] of polyolefin resin and [crystallization temperature + 30C] or lower. In the method of the present invention, extrusion foaming is performed to obtain a foam having a surface resistivity of 1 X 1 0 8 to 1 X 1 0 13 (Ω). To this end, 2 to 14 parts by weight of a polymer type antistatic agent is added to 100 parts by weight of the polyolefin resin. If the amount of polymer antistatic agent is too much, foaming will be hindered, continuous foaming rate will be low, and foam with low apparent density must not be used. Foams with high continuous cell ratios have poor cushioning properties and have limited applications due to the large cell volume. For this reason, the addition amount of the polymer antistatic agent is preferably 11 parts by weight or less, more preferably 9 parts by weight or less, 8 parts by weight or less is more preferable, 7 parts by weight or less is more preferable, and 6.5 parts by weight or less is particularly preferable. good. If the amount of the polymer-type antistatic agent is too small, the surface resistivity 发泡 of the foamed material will not exceed ΙχΙΟ13 (Ω). Therefore, the addition amount of the polymeric antistatic agent is preferably 3 parts by weight or more, and more preferably 3.8 parts by weight or more. The polymer type antistatic agent is the one described above. The method of the present invention is to form a foam by extrusion foaming, so that the apparent density of the obtained foam -31-200530307 (29) is 15 ~ 65 g / L. In this way, if the polymer antistatic agent is oriented during the bubble growth during high foaming, the addition amount is small and the antistatic performance can be greatly improved. That is, a specific polymer-type antistatic agent described later is added to a specific polyolefin resin, and the apparent density of the foam is 5 to 65 g / L by extrusion foaming, and a small amount of polymer-type antistatic agent is added. , The surface resistivity of the obtained foam can be 1 × 10 8 to 1 × 10] 3 (Ω). And the effect of the polymer type antistatic agent is independent of the storage time, temperature conditions, etc., the surface resistivity of the foamed material after manufacturing can be 1 X 1 0 8 to 1 X 1 0 1 3 (Ω). Immediately after manufacturing, the surface of the foam rises to the point where the electrical resistivity fully appears. When extruded and foamed with a flammable physical foaming agent such as Ding Yuan, the excellent effect of preventing static ignition can be obtained. The method for making the apparent density of the foam within the above range is mainly adjusted by the amount of the physical foaming agent added. Examples of the physical blowing agent include aliphatic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, n-hexane, isohexane, and cyclohexane, methyl chloride, and ethyl chloride. Organic physical blowing agents such as chlorinated hydrocarbons, 1,1,1,2-tetrachloroethane, fluorinated hydrocarbons such as 1,1-dichloroethane, and inorganic physical blowing agents such as oxygen, nitrogen, carbon dioxide, and air. These physical blowing agents can be used in combination of two or more. When the polyolefin resin is a polyethylene resin, the organic physical foaming agent is preferred from the viewpoint of compatibility with the resin and foamability. It is better to use n-butane, isobutane or a mixture of these as the main components. More suitable. The foam regulator is added during the production of foam. Bubble regulators include metal borates such as zinc borate, magnesium borate, borax, sodium chloride, aluminum hydroxide-32-200530307 (30), talc, zeolite, silica, calcium carbonate, sodium bicarbonate, carbonate 2-2 —Methylenebis (4,6-tert-butylphenyl) sodium, sodium benzoate, calcium benzoate, bromate, sodium stearate, etc. Compositions of citric acid and sodium bicarbonate, alkali salts of citric acid, and sodium bicarbonate can also be used as bubble regulators. These bubble regulators can be used in combination of two or more. The amount of the foaming agent added is adjusted according to the type of the foaming agent and the apparent density of the target foam. The added amount of the bubble regulator is mainly adjusted according to the target bubble diameter. For example, when the foaming agent is a 30% by weight isobutane and 70% by weight n-butane mixture, the addition amount of the butane compound is 4 to 35 parts by weight per 100 parts by weight of the polyalkylene resin. 5 to 30 parts by weight is preferred, and 6 to 25 parts by weight is more preferred. For example, when using 100 parts by weight of polyethylene resin as a masterbatch made of talc 1 1.8 parts by weight and 5.9 parts by weight of sodium citrate, the addition amount of the bubble regulator is polyolefin resin. Per 100 weight parts 0.3 to 10 weight parts, 0.5 to 5 weight parts is preferred. The polymer-type antistatic agent used in the method of the present invention has a crystallization temperature below 110 ° C and a melt viscosity (Mb) of 190 ° C of 80 ~ 1 000 Pa · s _ 〇The crystallization temperature exceeds 1 1 0 At ° C, the kneadability with polyolefin resin is insufficient, and the antistatic properties of the foam are difficult to obtain. Especially when the crystallization temperature of the polymer antistatic agent is higher than the crystallization temperature of the polyolefin resin, if the crystallization temperature of the antistatic agent is too high, it will crystallize inside the extruder, which may prevent foaming. _ The lower limit of the crystallization temperature of polymer-based antistatic agents is about 60 ° c. If the crystallization temperature is too low, the resin composition may have poor physical properties. In the method of the present invention, the polymer-type antistatic agent is contained in a small amount, so that -33-200530307 (31) foam has excellent antistatic properties. The antistatic agent must be oriented by extrusion foaming, and in the extrusion foaming step The medium polymer antistatic agent is uniformly dispersed in the foamable polyolefin resin melt, and the conductive network is formed by extrusion foaming. Therefore, it is important to balance the crystallization temperature of the above-mentioned polymer antistatic agent and the viscosity of the polyolefin resin and the polymer antistatic agent in the mixing of the foamable polyolefin resin melt. The polymer type antistatic agent used in the method of the present invention has a melt viscosity (Mb) of 80 to 1000 Pa · s at 1 90 ° C. That is, the melt viscosity (Mb) φ must satisfy the following formula (5). 80Pa · s ^ Mb ^ lOOOPa · s (5) The polymer-type antistatic agent with a melt viscosity can be fully kneaded with a polyolefin resin, and it is easy to form a better conductive network. From the above viewpoints, it is preferably from 150 to 800 Pa · s. 150 to 500 Pa · s is more preferable. The polyolefin resin used in the present invention has a melt viscosity (Ma) of 19 (TC), preferably 250 to 6000 Pa · s, and more preferably 300 to 5000 Pa · s. Melt viscosity (Ma) exceeding 6 000 Pa · 8 is applied When the load of the extruder is too high, it is not easy to control when the spring is squeezed out. The resin does not stretch enough during foaming, so it may not be a good-looking foam. The melt viscosity (Ma) is less than 250 Pa The poor kneading property of the electrostatic agent may hinder the uniform dispersibility of the polymer type antistatic agent and may cause a poor antistatic effect. When the polyolefin resin is a polyvinylene resin, the melt viscosity is 190 ° C 300 ~ 1600 Pa · s is preferred, 700 ~ 1500 Pa · s is more preferred. Polyethylene resin foams are mostly used for applications with cushioning requirements, and the bubbles are also fine. Because of the high molecular antistatic agent, Melt viscosity is not suitable for foaming -34- 200530307 (32) 'It is better to use polyethylene resin with high melt tension for its compensation. Polypropylene resin is used for polypropylene resin, with a melt viscosity of 190 t at 2000 It is preferably in the range of ~ 6000 Pa · s, more preferably in the range of 3000 ~ 550〇pa · s, and 4000 ~ 50〇〇 Pa · s is particularly preferred for high viscosity. The high viscosity polypropylene resin includes the aforementioned high melt tension polypropylene resin. In the method of the present invention, the polymer type antistatic agent and the polyolefin resin are at a temperature of 190 ° C. The melt viscosity must be controlled to satisfy the following formula (4).

Ma > Mb ...... ( 4 ) 春而（4 )式中Ma係聚烯烴樹脂於19(TC之熔融黏度（Ma > Mb ...... (4) Spring and (4) in the formula, the melt viscosity of the Ma-based polyolefin resin at 19 (TC

Pa · s，Mb係高分子型抗靜電劑於19〇 °c之熔融黏度（Pa • s ) °The melt viscosity of Pa · s, Mb polymer antistatic agent at 19 ° C (Pa • s) °

如上述（4 )式，使聚烯烴樹脂之熔融黏度（M a )高於高分子型抗靜電劑之熔融黏度（Mb )，即易於發揮特定之抗靜電性能。而聚烯烴樹脂的熔融黏度（M a )與高分子型抗靜電劑之熔融黏度（Mb )相同或較低，則難以形成高分子型抗靜電劑之導電網路構造。 H 上述Ma及Mb之關係以0.90 Ma>Mb爲佳，0.70 Ma>According to the formula (4) above, the melt viscosity (M a) of the polyolefin resin is higher than the melt viscosity (Mb) of the polymer type antistatic agent, that is, it is easy to exert specific antistatic performance. However, the melt viscosity (M a) of the polyolefin resin is the same as or lower than the melt viscosity (Mb) of the high molecular antistatic agent, and it is difficult to form a conductive network structure of the polymer antistatic agent. H The above relationship between Ma and Mb is preferably 0.90 Ma > Mb, 0.70 Ma >

Mb更佳。而 Mb係以 Mb>0.10 Ma爲佳，Mb>0.15 Ma更佳。本說明書中，熔融黏度係如下測定。測定裝置係用例如TYAST公司製RHEOBIS 2100，使用內徑1 mm、長10 mm之孔洞，以測定溫度1901、剪切速度1 00 sec- 1之條件測定。於高分子型抗靜電劑導電網路構造之形成上，聚烯烴 -35- 200530307 (33) 樹脂及高分子型抗靜電劑之結晶化溫度以滿足下述（1 4 ) 式之關係爲佳。Mb is better. The Mb is preferably Mb> 0.10 Ma, and Mb> 0.15 Ma is more preferable. In this specification, the melt viscosity is measured as follows. The measuring device is, for example, RHEOBIS 2100 manufactured by TYAST, and a hole having an inner diameter of 1 mm and a length of 10 mm is used for measurement at a measurement temperature of 1901 and a shear rate of 100 sec-1. In the formation of the conductive network structure of the polymer antistatic agent, it is preferable that the crystallization temperature of the polyolefin-35-200530307 (33) resin and the polymer antistatic agent satisfy the relationship of the following formula (1 4).

Tb < 〔 Ta+ 30〇C〕 ...... ( 14 ) 唯（1 4 )式中Tb係高分子型抗靜電劑之結晶溫度（°C )，Ta係聚烯烴樹脂之結晶溫度（°C )。高分子型抗靜電劑及聚烯烴樹脂的結晶溫度之關係滿足上述式，發泡性聚烯烴樹脂熔體的聚烯烴樹脂中高分子型抗靜電劑進一步均勻分散，形成良好導電網路構造。 φ 本說明書中，聚烯烴樹脂及高分子型抗靜電劑之結晶溫度，係採用依以下方法測定之値。本說明書中，高分子型抗靜電劑之結晶溫度係採用依 J I S 7 1 2 2 ( 1 9 8 7 )之方法測定的値。詳細如下。採取2〜4 mg之試樣’用差示掃描熱量計，以加熱速度l〇°C /分鐘從室溫（約23°C )升溫至23 0 °C，然後以10 °C /分鐘之冷卻速度降溫至4 0 °C作測定。此時冷卻得之曲線中’以峰頂溫度爲結晶溫度，發熱尖峰有2以上時，以 · 最大面積之發熱尖峰的頂點溫度爲結晶溫度。唯大發熱尖峰面積有多數存在時，以其中最高溫側之發熱尖峰的頂點爲結晶溫度。用於本發明方法之聚烯烴樹脂內，聚乙烯樹脂係以 1 9 0 °C之熔融張力在3 0〜4 0 0 mN者爲佳。1 9 0 °C之熔融張力未達3 0 mN時，因發泡性低有倍率低、連續氣泡化之虞 ^ 1 9 0 C之熔融張力超過4 0 0 m N時，樹脂黏度上升，濟出之際模內壓力上升而發熱，所得發泡體有連續氣泡率升高 -36 - 200530307 (34) 之虞。聚乙烯樹脂於1 9 0 °C之熔融張力因易得低密度發泡物，以35 mN以上爲佳，40 mN以上更佳。因易得連續氣泡率低的發泡物，聚乙烯樹脂於190 °C之熔融張力以300 mN以下爲佳，250 mN以下更佳，於19(TC測定之理由係，該溫度之熔融物性與發泡時之狀態相關。用於本發明方法之聚烯烴樹脂內，聚丙烯樹脂係以 230 °C之熔融張力30〜400 mN者爲佳。230 °C之熔融張力未達3 0 m N時，因發泡性低有倍率低、連續氣泡化之虞。隹而23 0 °C之熔融張力超過400 mN則樹脂黏度上升，擠出之際模內壓力上升而發熱，所得發泡體有連續氣泡率高之虞。聚丙烯樹脂於2 3 0 °C之熔融張力，爲易得低密度發泡物，以3 5 mN以上，更以40 mN以上，尤以50 mN以上爲佳。爲易得連續氣泡率低之發泡物，聚丙烯樹脂於23 0 °C之熔融張力以在3 00 mN以下爲佳，2 5 0 mN以下更佳。於23 0 °C 測定之理由係，該溫度下熔融物性與發泡之際的狀態相關本說明書中，聚烯烴樹脂的熔融張力：MT可例如以東洋精機製作所（股）製之MELT TENSION TESTER II型等測定。具體而言，測定之聚烯烴樹脂係聚乙烯樹脂時乃如下測定。 _ 使用安裝內徑2 · 〇 9 5 mm，長度8 mm之孔洞的熔體張力測試儀，自上述孔洞以樹脂溫度1 90 °C、擠出主軸速度 1 0 m m /分鐘之條件將樹脂作紐狀濟出，該紐狀物掛於直徑4 5 m m之張力檢測用滑輪後以5 r p m /秒（紐狀物之捲繞 -37- 200530307 (35) 加速度：1.3 χ 1 (Τ 2 m/秒2 )左右之比率緩緩增加捲繞速度以直徑50 mm之捲繞輥捲繞。聚烯烴樹脂之熔融張力的具體求出方法係於捲繞速度 5 00 ( rpm )進行捲繞以連結於張力檢測用滑輪之檢測機檢測之紐狀物的熔融張力歷時測定，縱軸爲Μ T ( mN )，橫軸爲時間（秒）作圖，得振幅圖。其次，取振幅安定部分的振幅中央値（X )。本發明係以該値（X )爲熔融張力。測定之際，罕見之特異振幅予以忽略。 · 掛於張力檢測用滑輪之紐狀物不到捲繞速度5 00 ( rpm )已切斷時，求出紐狀物切斷時之捲取速度R ( rpm )。其次於Rx〇.7 (rpm)之一定捲繞速度，由同上得之圖，以振幅中央値（X )爲熔融張力。聚烯烴樹脂係聚丙烯樹脂時，使樹脂溫度爲23 (TC以外如同聚乙烯樹脂測定。亦可於上述聚烯烴樹脂添加各種添加劑。各種添加劑有例如著色劑、造核劑、抗氧化劑、熱安定劑、耐候劑、 ® 紫外線吸收劑、阻燃劑、無機塡料、抗菌劑、抗收縮劑等。此時之添加量以0 · 0 1〜1 0重量％爲佳，5重量％以下更佳，3重量％以下尤佳。製造本發明之發泡物時，調整平均氣泡徑之方法取決 . 於所用之聚烯烴樹脂，係例如提高模壓縮小平均氣泡徑之方法，可以調整上述氣泡調整劑之量。調整Ζ / X、Ζ / Υ之氣泡形狀之方法亦取決於所用聚烯烴樹脂’例如使氣泡於擠出方向扁平時，具體而言爲使 -38- 200530307 (36) Z/ X値在0.3 5 $ Z / X< 1.0時減少吐出量，可經提高拉取速度等方法調節。使擠出方向氣泡大致爲球狀時，具體而言Z / X値近於1 . 〇時或1 · 〇以上1 · 2以下時，可以增加吐出量，降低拉取速度等方法調節。使寬度方向氣泡扁平時，具體而言Ζ/Υ値0.35SZ/ Υ < 1 · 0時，可調整擠出方法使發泡物於寬度方向加大，使用環模時，可以加大吹塑比（筒狀冷卻裝置心軸之直徑/ 環模吐出口徑）之方法作調整。使寬度方向氣泡爲球狀時，具體而言Ζ / Υ値近於1 · 〇或在1 · 0以上1 · 2以下時，可使發泡物不於寬度方向膨大，以擠出方向調整，使用環模時，可經縮小吹塑比至近於1之方法調整。依本發明方法，使用有特定結晶溫度及特定熔融黏度，且於熔融黏度滿足與聚烯烴樹脂之特定關係的高分子型抗靜電劑，即可以少量高分子型抗靜電劑添加筒便製造本發明之發泡物。亦即，依本發明方法，上述高分子型抗靜電劑因可均勻分散於發泡物中，所得發泡物具優良抗靜電特性，獨立於製造後之放置時間、溫度條件等，製造後隨即出現優良抗靜電性。實施例以下舉實施例更詳細說明本發明。聚烯烴樹脂係用以下。 PE 1 :住友化學工業（股）製低密度聚乙烯「ρ i 〇2」 (結晶溫度 9 7 . 8 °C 密度：9 2 2 g / L，M F R : 0.3 g / 1 〇分鐘 200530307 (37) (1 9 0 °C，荷重 2 1 . 1 7 N )) PE2 ：日本UNICAR (股）製低密度聚乙烯「NUC 8 00 8」（結晶溫度 93.5°C，密度·· 91 7 g / L，MFR : 4.5 g /10分鐘（190 °C，荷重 21.17 N) PP1 : SUNAROMA (股）製丙烯一乙烯共聚物「SD 63 2」（結晶溫度 128°C，密度：900 g / L，MFR : 3·2 g/ 10 分鐘（230°C，荷重 21.17N)) 高分子型抗靜電劑係用以下。 φ 高分子抗靜電劑P 1 ··三洋化成工業（股）製聚醚聚丙烯嵌段共聚物「PELESTAT 3 00」（熔點136t：，數平均分子量 1 4000，密度 990 g/L) 高分子抗靜電劑P.2 :汽巴特化（股）製（聚醚酯醯胺及聚醯胺之混合物）「IRGASTAT P 1 8」（熔點1 80°C，數平均分子量19000，密度1043 g/L) 實施例1 對於聚烯烴樹脂P E 1 (低密度聚乙烯）1 ο 〇重量份，配合氣泡調整劑母料2重量份，將高分子抗靜電劑p 1「 PELESTAT 3 00」相對於低密度聚乙烯1〇〇重量份添加6.4 重量份，供給於內徑90 mm之擠出機原料投入口，加熱混練，調整於約200 °C成樹脂熔體。於上述樹脂熔體將物理發泡劑正丁烷70重量％及異丁烷30重量％之混合丁烷，以 Η於低密度聚乙嫌100重量份可爲25重量份壓入，其次，供給樹脂熔體於上述直徑9 0 m m之擠出機下游側連結之直 -40 - 200530307 (38) 徑120 mm的擠出機，冷卻使樹脂熔體之發泡溫度爲1 l〇t ，調節模壓爲7〜1 0 MPa ( G )成發泡性聚烯烴樹脂熔體，將該發泡性聚烯烴樹脂熔體自直徑9 5 mm之環模擠出形成筒狀發泡物。冷卻擠出之筒狀發泡物沿筒狀拉取切開，得發泡薄片。氣泡調整劑母料係對於低密度聚乙烯1 00重量份，配合滑石（松村產業（股）製商品名「HYFILLER #12」）11. 8重量份，檸檬酸鈉5.9重量份者。實施例2 聚烯烴樹脂以PE2 (低密度聚乙烯）爲主要原料，混合丁烷之配合量爲2 7重量份，發泡溫度調節爲i 〇 8它以外〆如同實施例1得發泡薄片。實施例3 物理發泡劑之配合重爲2 3重夏份’局分子抗靜電劑以 Pi「PELESTAT 3 0 0」4.7重量份添加，調節發泡溫度爲 1 1 1 °C以外，如同實施例1得發泡薄片。實施例4 聚烯烴樹脂用PP 1，物理發泡劑之配合量爲8重量份，發泡溫度調整爲1 5 2 °C，吹塑比及拉取速度調節爲表7之値以外，如同實施例1得發泡薄片。比較例1 -41 - 200530307 (39) 將三洋化成（股）製高分子抗靜電劑PI「PELES TAT 3 0 0」對於低密度聚乙烯1 〇〇重量份以1 7 · 6重量份添加’對於低密度聚乙烯1 0 〇重量份混合丁烷之配合量爲2 5重量份，調整發泡溫度爲1 〇 8 °C以外，如同實施例1得發泡薄片。比較例2 物理發泡劑之配合量爲8重量份，發泡溫度爲11 3 °C，吹塑比、拉取速度調節爲表7之値以外，如同實施例1得發泡薄片。比較例3 高分子抗靜電劑PI「PELESTAT 3 0 0」以1.5重量份添加，調節發泡溫度爲11 1 °C以外，如同實施例1得發泡薄片比較例4 使用高分子型抗靜電劑P2「IRGASTAT P18」以外，如同實施例1進行擠出發泡。但於發泡物產生結晶物，僅得表面凹凸之發泡物，無法測定表面電阻率。發泡物之結晶物應係來自高分子型抗靜電劑P2「IRGASTAT P 1 8」。實施例1〜4，比較例1〜4中聚烯烴樹脂（主要原料）之種類、諸物性如表6。製造條件如表7。實施例1〜4、比較例1〜4得之發泡薄片諸物性如表8 -42- 200530307 (40)Tb < [Ta + 30〇C] ...... (14) Only the crystallization temperature (° C) of the Tb polymer antistatic agent in formula (14), and the crystallization temperature of Ta-based polyolefin resin ( ° C). The relationship between the polymer-type antistatic agent and the crystallization temperature of the polyolefin resin satisfies the above formula. The polymer-type antistatic agent in the polyolefin resin of the foamable polyolefin resin melt is further uniformly dispersed to form a good conductive network structure. φ In this specification, the crystallization temperature of polyolefin resin and polymer antistatic agent is measured by the following method. In this specification, the crystallization temperature of the polymer-type antistatic agent is measured by the method of J I S 7 1 2 2 (19 8 7). The details are as follows. Take a sample of 2 to 4 mg 'with a differential scanning calorimeter, increase the temperature from room temperature (about 23 ° C) to 23 0 ° C at a heating rate of 10 ° C / minute, and then cool at 10 ° C / minute The speed was reduced to 40 ° C for measurement. In the cooled curve at this time, the peak temperature is used as the crystallization temperature, and when the heat generation peak is 2 or more, the apex temperature of the heat generation peak with the largest area is used as the crystallization temperature. When there is a large area of the large heating peak, the apex of the heating peak at the highest temperature side is taken as the crystallization temperature. Among the polyolefin resins used in the method of the present invention, polyethylene resins are preferably those having a melt tension of 190 ° C between 30 and 400 mN. When the melt tension at 19 ° C is less than 30 mN, there is a risk of low magnification and continuous foaming due to low foamability. ^ When the melt tension of 19 0 C exceeds 400 m N, the viscosity of the resin will increase, which will reduce the viscosity. At the time of exit, the pressure in the mold rises and heat is generated, and the obtained foam may increase the continuous cell ratio by -36-200530307 (34). Polyethylene resins have a melt tension at 190 ° C because low-density foams are easy to obtain, preferably 35 mN or more, and more preferably 40 mN or more. Due to the availability of foams with a low continuous cell ratio, the melt tension of polyethylene resin at 190 ° C is preferably 300 mN or less, and more preferably 250 mN or less. The reason for measuring the temperature at 19 ° C is that The state at the time of foaming is related. In the polyolefin resin used in the method of the present invention, the polypropylene resin preferably has a melt tension of 230 ° C of 30 to 400 mN. When the melt tension of 230 ° C does not reach 30 m N Due to the low foamability, there is a risk of low magnification and continuous foaming. 隹 If the melt tension at 23 ° C exceeds 400 mN, the viscosity of the resin will increase, and the pressure in the mold will increase during extrusion to generate heat. The resulting foam will have continuous Possibility of high cell ratio. The melt tension of polypropylene resin at 230 ° C is easy to obtain low-density foams, more than 35 mN, more than 40 mN, especially more than 50 mN. To obtain a foam with a low continuous cell ratio, the melting tension of the polypropylene resin at 23 0 ° C is preferably below 300 mN, more preferably below 250 mN. The reason for measuring at 23 0 ° C is the temperature. The lower melt properties are related to the state at the time of foaming. In this specification, the melt tension of polyolefin resin: MT can be exemplified. For example, the measurement is made with the MELT TENSION TESTER II type manufactured by Toyo Seiki Seisakusho Co., Ltd. Specifically, the polyolefin resin based polyethylene resin is measured as follows. _ Use the installation inner diameter 2 · 095 5 mm, length 8 Melt tension tester for holes with a diameter of mm. The resin is released from the above holes at a temperature of 1 90 ° C and an extrusion spindle speed of 10 mm / min. The button is hung at a diameter of 4 5 mm. After the pulley for tension detection is used, the winding speed is gradually increased at a ratio of about 5 rpm / second (winding of a button-37- 200530307 (35) acceleration: 1.3 x 1 (Τ 2 m / second 2) to a diameter of 50 Winding roll of mm. The specific method for determining the melt tension of polyolefin resin is to roll the coil at a winding speed of 5 00 (rpm) and connect it to the melt tension of the knuckle detected by the testing machine of the tension detecting pulley. During the measurement, the vertical axis is M T (mN), and the horizontal axis is time (second). The amplitude chart is obtained. Second, the amplitude center 値 (X) of the amplitude stabilization part is taken. The present invention uses this 値 (X) as Melt tension. Rare specific amplitudes are ignored during measurement. · When the button hanging on the pulley for tension detection is below the winding speed of 5 00 (rpm), the winding speed R (rpm) when the button is cut is obtained. Next is Rx0.7 ( The constant winding speed of rpm) is from the graph obtained above, and the center of amplitude (X) is the melt tension. For polyolefin resin polypropylene resin, the resin temperature is 23 (other than TC, it is measured as polyethylene resin). Various additives may be added to the polyolefin resin. Various additives include, for example, colorants, nucleating agents, antioxidants, heat stabilizers, weathering agents, ® UV absorbers, flame retardants, inorganic additives, antibacterial agents, and anti-shrinking agents. The added amount at this time is preferably from 0. 0 1 to 10% by weight, more preferably 5% by weight or less, and even more preferably 3% by weight or less. The method of adjusting the average cell diameter when manufacturing the foam of the present invention depends on the polyolefin resin used, for example, a method of increasing the small average cell diameter of the mold compression, and the amount of the above-mentioned cell regulator can be adjusted. The method of adjusting the shape of the bubbles of Z / X, Z / Υ also depends on the polyolefin resin used. For example, when the bubbles are flattened in the extrusion direction, specifically -38- 200530307 (36) Z / X 値 is 0.3 5 $ Z / X < 1.0 reduces the amount of vomiting, which can be adjusted by increasing the pulling speed and other methods. When the bubbles in the extrusion direction are made approximately spherical, specifically, when Z / X 値 is close to 1.0 or more than 1 · 〇 and 1 · 2 or less, adjustment can be made by increasing the discharge amount and lowering the pulling speed. When flattening the bubbles in the width direction, specifically, Z / Υ 値 0.35SZ / Υ < 1 · 0, the extrusion method can be adjusted to increase the width of the foam. When using a ring die, blow molding can be increased. The ratio (diameter of the cylindrical cooling device mandrel / ring die outlet diameter) is adjusted. When the bubbles in the width direction are made spherical, specifically when Z / Υ 値 is close to 1 · 〇 or 1 · 0 or more and 1 · 2 or less, the foam can be prevented from expanding in the width direction and adjusted in the extrusion direction. When using a ring mold, it can be adjusted by reducing the blow molding ratio to nearly 1. According to the method of the present invention, a polymer-type antistatic agent having a specific crystallization temperature and a specific melt viscosity, and satisfying a specific relationship with a polyolefin resin at the melt viscosity, that is, a small amount of polymer-type antistatic agent can be added to the cylinder to manufacture the present invention. Of foam. That is, according to the method of the present invention, because the above-mentioned polymer antistatic agent can be uniformly dispersed in the foamed material, the obtained foamed material has excellent antistatic properties, which is independent of the storage time and temperature conditions after manufacturing, etc., immediately after manufacturing. Excellent antistatic properties appear. Examples The present invention will be described in more detail with reference to the following examples. The following polyolefin resins are used. PE 1: Low-density polyethylene "ρ i 〇2" made by Sumitomo Chemical Industry Co., Ltd. (crystallization temperature 97.8 ° C density: 9 2 2 g / L, MFR: 0.3 g / 10 minutes 200530307 (37) (1 9 0 ° C, load 2 1. 1 7 N)) PE2: Japan's UNICAR (stock) low-density polyethylene "NUC 8 00 8" (crystallization temperature 93.5 ° C, density · 91 7 g / L, MFR: 4.5 g / 10 minutes (190 ° C, load 21.17 N) PP1: propylene-ethylene copolymer "SD 63 2" made by SUNAROMA (strand) (crystallization temperature 128 ° C, density: 900 g / L, MFR: 3 · 2 g / 10 minutes (230 ° C, load 21.17N)) Polymer antistatic agent is used below. Φ Polymer antistatic agent P 1 ·· Polyether polypropylene block copolymer made by Sanyo Chemical Industry Co., Ltd. "PELESTAT 3 00" (melting point 136t :, number average molecular weight 1 4000, density 990 g / L) Polymeric antistatic agent P.2: made by Ciba Tetra (Stock) (polyetheresteramide and polyamine Mixture) "IRGASTAT P 1 8" (melting point 1 80 ° C, number average molecular weight 19000, density 1043 g / L) Example 1 For polyolefin resin PE 1 (low density polyethylene) 1 ο 〇 parts by weight, formulated Add 2 parts by weight of air bubble modifier master batch, add polymer antistatic agent p 1 "PELESTAT 3 00" to 100 parts by weight of low-density polyethylene, and add 6.4 parts by weight to feed the extruder with an inner diameter of 90 mm. The mixture is heated and kneaded, and adjusted to a resin melt at about 200 ° C. In the above resin melt, a physical foaming agent of 70% by weight of n-butane and 30% by weight of isobutane is mixed to form a low-density polymer. 100 parts by weight can be pressed in 25 parts by weight. Secondly, the resin melt is supplied to the -40-200530307 (38) extruder with a diameter of 120 mm, which is connected to the downstream side of the extruder with a diameter of 90 mm, and cooled. The foaming temperature of the resin melt is 1 l0t, and the molding pressure is adjusted to 7 to 10 MPa (G) to form a foamable polyolefin resin melt. The foamable polyolefin resin melt has a diameter of 9 5 mm. The ring die is extruded to form a cylindrical foam. The cooled extruded cylindrical foam is pulled and cut along the cylindrical shape to obtain a foamed sheet. The bubble modifier master batch is based on 100 parts by weight of low density polyethylene. Talc (trade name "HYFILLER # 12" made by Matsumura Industry Co., Ltd.) 11. 8 parts by weight, 5.9 sodium citrate Example 2 The polyolefin resin uses PE2 (low-density polyethylene) as the main raw material, the blending amount of mixed butane is 27 parts by weight, and the foaming temperature is adjusted to i 〇 8 except for the same as in Example 1. Bubble flakes. Example 3 The combined weight of the physical foaming agent is 2 3 weights. The summer molecular weight antistatic agent is added with 4.7 parts by weight of Pi "PELESTAT 3 0 0", and the foaming temperature is adjusted to other than 1 1 1 ° C, as in the example. 1 Get a foamed sheet. Example 4 PP 1 for polyolefin resin, the blending amount of the physical foaming agent is 8 parts by weight, the foaming temperature is adjusted to 15 2 ° C, the blowing ratio and the pulling speed are adjusted to be other than those in Table 7 as in the implementation Example 1 gives a foamed sheet. Comparative Example 1 -41-200530307 (39) A polymer antistatic agent PI "PELES TAT 3 0 0" made by Sanyo Kasei Co., Ltd. was added to 1,000 parts by weight of low density polyethylene at 17.6 parts by weight. The blending amount of 100 parts by weight of low-density polyethylene with mixed butane was 25 parts by weight, and the foaming temperature was adjusted to be other than 108 ° C. As in Example 1, a foamed sheet was obtained. Comparative Example 2 The blending amount of the physical foaming agent was 8 parts by weight, the foaming temperature was 11 3 ° C, and the blow ratio and the pulling speed were adjusted to be different from those in Table 7 except that the foamed sheet was obtained as in Example 1. Comparative Example 3 The polymer antistatic agent PI "PELESTAT 3 0 0" was added at 1.5 parts by weight, and the foaming temperature was adjusted to 11 1 ° C. The foamed sheet was obtained as in Example 1. Comparative Example 4 A polymer type antistatic agent was used. Except for P2 "IRGASTAT P18", extrusion foaming was performed in the same manner as in Example 1. However, crystals are formed in the foam, and only the foam having a concave-convex surface is obtained, and the surface resistivity cannot be measured. The crystals of the foam should be derived from the polymer antistatic agent P2 "IRGASTAT P 1 8". The types and physical properties of polyolefin resins (main raw materials) in Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 6. Manufacturing conditions are shown in Table 7. The physical properties of the foamed sheets obtained in Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 8 -42- 200530307 (40)

表6 聚烯烴樹脂（主要原料）高分子型抗靜電劑種類熔融黏度熔融張力種類熔融黏度結晶溫度 (Pa-s) (mN) (Pa · s) rc ) 實施例1 PE1 1440 220 P1 270 90 實施例2 PE2 850 50 P1 270 90 實施例3 PE1 1440 220 P1 270 90 實施例4 PP1 4670 220 P1 270 90 比較例1 PE1 1440 220 P1 270 90 比較例2 PE1 1440 220 P1 270 90 比較例3 PE1 1440 220 P1 270 90 比較例4 PE1 1440 220 P2 1110 148Table 6 Polyolefin resin (main raw materials) Type of polymer antistatic agent Melt viscosity Melt tension type Melt viscosity Crystallization temperature (Pa-s) (mN) (Pa · s) rc) Example 1 PE1 1440 220 P1 270 90 Implementation Example 2 PE2 850 50 P1 270 90 Example 3 PE1 1440 220 P1 270 90 Example 4 PP1 4670 220 P1 270 90 Comparative Example 1 PE1 1440 220 P1 270 90 Comparative Example 2 PE1 1440 220 P1 270 90 Comparative Example 3 PE1 1440 220 P1 270 90 Comparative Example 4 PE1 1440 220 P2 1110 148

-43 - 200530307 (41) 表7-43-200530307 (41) Table 7

(製造條件）局分子型抗靜電劑之添加量* (重量份）. 物理發泡劑之注入量* (重量份）發泡溫度 CC) 吹塑比拉取速度 (m/min) 吐出量 (kg/hr) 實施例1 6.4 25 110 3.8 60 90 實施例2 6.4 27 108 3.8 60 90 實施例3 4.7 23 111 3.8 60 90 實施例4 6.4 8 152 3.2 13 90 比較例1 17.6 25 108 3.8 60 90 比較例2 6.4 8 113 2.5 18 90 比較例3 1.5 25 111 3.8 60 90 比較例4 6.4 25 110 3.8 60 90 *相對於聚烯烴樹脂1〇〇重量份之値(Manufacturing conditions) Addition amount of local molecular antistatic agent * (parts by weight). Injection amount of physical foaming agent * (parts by weight) Foaming temperature CC) Blowing ratio pulling speed (m / min) Discharge amount ( kg / hr) Example 1 6.4 25 110 3.8 60 90 Example 2 6.4 27 108 3.8 60 90 Example 3 4.7 23 111 3.8 60 90 Example 4 6.4 8 152 3.2 13 90 Comparative Example 1 17.6 25 108 3.8 60 90 Comparison Example 2 6.4 8 113 2.5 18 90 Comparative Example 3 1.5 25 111 3.8 60 90 Comparative Example 4 6.4 25 110 3.8 60 90 * 100 parts by weight of polyolefin resin

-44- 200530307 (42) -sli- s 外觀之評估〇〇〇〇 X 〇〇 X 氣泡形狀 Ζ (mm) 0.38 0.47 0.35 0.85 0.61 0.33 0.39 1 Z/Y 0.81 0.85 0.83 0.92 1 0.63 j 0.83 0.82 1 Z/X 0.66 0.70 0.72 0.88 1 0.45 0.70 0.67 1 S S 衡 S P i is w Η術 2xl010 5χ10π 5xl012 3χ10π 5x109 3χ1014 5χ1014 1 連續氣泡率 (%) s ο ο m g 厚度 (mm) ρ ο ο ο rn ο ο 〇| 卜 ο 表觀密度 (g/L) m CN m CN m (Ν m m (Ν 發泡物之熔融張力 (mN) 210 215 S οο ，Η 210 215 215 贷 _ _ 纪N _ φ 1 « to νο 實施例1 實施例2 實施例3 實施例4 比較例1 \ 比較例2 比較例3 比較例4 -45- (43) (43)200530307 實施例及比較例中發泡物於擠出方向之平均氣泡徑： X ( m m )、寬度方向之平均氣泡徑：Y ( mm )及厚度方向之平均氣泡徑：Z ( mm )之調整係以，氣泡調整劑添加量，表7之發泡溫度、吐出量、吹塑比及拉取速度爲之。表7 中發泡溫度係環模經由溫調節之模溫。發泡物中高分子抗靜電劑含量，發泡物之熔融張力，乙醇洗淨後之表面電阻率及外觀評估係如下進行。 <高分子抗靜電劑含量> 基於實施例及比較例中擠出發泡之熱經歷，確認高分子型抗靜電劑不熱分解而減少，從發泡物的製造之際高分子型抗靜電劑之添加量求出。 <發泡物之熔融張力> 切細之發泡物試樣，以如同上述原料樹脂的熔融張力測定方法測定。 <乙醇洗淨後表面電阻率之測定> 從發泡物切出縱1 〇〇 mmx橫1 00 mm X厚度：試片厚度之試片，作如下之狀態調整，狀態調整後之試片，立刻於 2 3 °C、50% RH環境下測定表面電阻率。此際，係依 JIS K 6911 ( 1979)之方法施加500 V之施加電壓求出1分鐘後之表面電阻率。測定裝置係用TAKEDA理硏工業（股 )製「TR 8 60 1」。 200530307 (44) 〔試片之狀態調整〕超音波洗淨裝置係用BRANSON公司製「BRANSONIC 22〇」。首先於5〇〇 ml用燒杯中稱取5 00 ml之乙醇，保持乙醇溫度於2 3 °C。其次，用金屬網使試片沈入燒杯中浸泡於純度99.5 Vol%以上之乙醇中。然後，沈有試片之上述燒杯以箔蓋上，於注入23 °C之水1.7公升的上述超音波洗淨裝置之凹狀收容部放入上述燒杯靜置後導入超音波洗淨裝置之電源開始洗淨。從洗淨開始經過8小時後，以及洗淨開始經過1 6小時後，追加2 3 °C之乙醇使燒杯中乙醇爲 5 0 0 m 1。該乙醇之追加係因超音波洗淨而乙j|揮發，比當初燒杯中之存在量減少，爲其補充而作。洗淨開始起經24 小時後，停止超音波洗淨裝置，自燒杯中取出試片，隨即放置該試片於相對濕度3 0 %、溫度3 0 °C之環境下乾燥6小時，完成試片之狀態調整。 <外觀評估> 所得發泡物以目視評估外觀，基準如下。〇：發泡形狀全體均勻，氣泡徑微細，表面平滑性優良。 △:發泡形狀全體均勻，氣泡徑微細，處處僅見巨大氣泡，有部分凹凸可見。 X :見巨大氣泡，部分表面呈疤痕狀態，全體可見凹凸。 -47--44- 200530307 (42) -sli- s Evaluation of appearance 〇〇〇〇 × 〇〇X Bubble shape Z (mm) 0.38 0.47 0.35 0.85 0.61 0.33 0.39 1 Z / Y 0.81 0.85 0.83 0.92 1 0.63 j 0.83 0.82 1 Z / X 0.66 0.70 0.72 0.88 1 0.45 0.70 0.67 1 SS scale SP i is w Ο Apparent density (g / L) m CN m CN m (N mm (N melt tension of the foam (mN) 210 215 S οο, Η 210 215 215 credit _ _ age N _ φ 1 «to νο implementation Example 1 Example 2 Example 3 Example 4 Comparative Example 1 \ Comparative Example 2 Comparative Example 3 Comparative Example 4 -45- (43) (43) 200530307 The average bubbles of the foam in the extrusion direction in the examples and comparative examples Diameter: X (mm), average bubble diameter in the width direction: Y (mm) and average bubble diameter in the thickness direction: Z (mm) The adjustments are based on the amount of bubble regulator added, the foaming temperature and discharge amount in Table 7. , Blowing ratio and pull speed are as follows. The foaming temperature in Table 7 is the mold temperature of the ring mold through temperature adjustment. The content of the polymer antistatic agent, the melt tension of the foam, and the surface resistivity and appearance evaluation after washing with ethanol were performed as follows. &Lt; Polymer antistatic agent content > The thermal history confirms that the polymer antistatic agent decreases without thermal decomposition, and is calculated from the amount of the polymer antistatic agent added when the foam is produced. &Lt; Melting tension of the foam > The foam sample was measured by the same method as the above-mentioned raw material resin. &Lt; Measurement of surface resistivity after washing with ethanol > Cut out from the foam 100 mm x 100 mm X thickness: test piece The thickness of the test piece is adjusted as follows. After the test piece is adjusted, the surface resistivity is immediately measured at 2 3 ° C and 50% RH. At this time, 500 is applied according to JIS K 6911 (1979). The surface resistivity after 1 minute was obtained by applying a voltage of V. The measurement device was "TR 8 60 1" manufactured by TAKEDA Ryo Kogyo Co., Ltd. 200530307 (44) [Adjustment of test piece status] Ultrasonic cleaning device system "BRANSONIC 22〇" manufactured by BRANSON Corporation was used. First weigh 500 ml of ethanol in a 500 ml beaker and keep the ethanol temperature at 23 ° C. Next, the test piece was immersed in a beaker with a metal mesh and immersed in ethanol with a purity of 99.5 Vol% or more. Then, cover the beaker with the test piece with a foil cover, and inject the 1.7 liters of water at 23 ° C into the concave receiving part of the ultrasonic cleaning device, place the beaker in a stationary state, and then introduce the power into the ultrasonic cleaning device. Start washing. After 8 hours from the start of washing and 16 hours from the start of washing, ethanol at 2 3 ° C was added to make the ethanol in the beaker 500 m 1. The addition of ethanol is due to the ultrasonic cleaning and the volatilization of Bj | is reduced, which is less than the original amount in the original beaker. After 24 hours from the start of washing, stop the ultrasonic cleaning device, remove the test piece from the beaker, and then place the test piece in an environment of 30% relative humidity and 30 ° C for 6 hours to complete the test piece. State adjustment. < Appearance evaluation > The appearance of the obtained foam was evaluated visually based on the following criteria. ○: The entire foam shape is uniform, the bubble diameter is fine, and the surface smoothness is excellent. △: The foaming shape is uniform throughout, the bubble diameter is fine, and only giant bubbles are seen everywhere, and some unevenness is visible. X: Large bubbles are seen, and part of the surface is scarred. -47-

Claims

200530307 (1) 十、申請專利範圍 1. 一種聚烯烴樹脂發泡物，其特徵爲含有2〜12重量 %之高分子型抗靜電劑，表觀密度15〜65 g/L，使用乙醇以超音波洗淨後表面電阻率1 X 1 0 8〜1 X 1 〇13 ( Ω )，平均氣泡徑滿足下述（1 ) 、（ 2 )及（3 )式，〇·35$ Z/X$ 1.2 ......( 1 ) 0.35 S Z/ YS 1 .2 ......( 2 ) 0.2^ Z ^ 1.4 ......( 3 ) (乂、¥及2係，擠出方向之平均氣泡徑：乂（111111)，寬度方向之平均氣泡徑：Y( mm)及厚度方向之平均氣泡徑： Z ( mm) ) 〇 2 ·如申請專利範圍第1項之聚烯烴樹脂發「泡物，其中聚烯烴樹脂發泡物中高分子型抗靜電劑之含量爲2〜1 0重量％。 3 ·如申請專利範圍第1項之聚烯烴樹脂發泡物，其中聚嫌烴樹脂發泡物中高分子型抗靜電劑之含量爲2〜8重量 %。 4 · 一種聚烯烴樹脂發泡物之製造方法，係以擠出機混練聚烯烴樹脂、高分子型抗靜電劑、氣泡調整劑及物理發泡劑’形成發泡性聚烯烴樹脂溶體，將該發泡性聚烯烴樹脂溶體擠出發泡的如申請專利範圍第1項之聚烯烴發泡物之製造方法，其特徵爲上述高分子型抗靜電劑之添加量係對於聚烯烴樹脂 100重量份爲2〜14重量份， -48- 200530307 (2) 上述高分子型抗靜電劑之結晶溫度在11 o°c以下，上述聚條烴樹脂於測定溫度1 9 0 °c、剪切速度1 0 0 - sec— I之熔融黏度：Ma(Pa.s)，及上述高分子型抗靜電劑於測定溫度190 °c、剪切速度1〇〇 sec_ 1之熔融黏度：Mb (Pa· s)之關係滿足下述（4)及（5)式， Ma > Mb ( 4 ) 80Pa · s ^ Mb ^ 1 OOOPa · s ( 5) 5 .如申請專利範圍第4項之聚烯烴樹脂發泡物之製造 Φ 方法，其中聚烯烴樹脂係，190 °C之熔融張力爲3〇〜4〇〇之聚乙烯樹脂。 6.如申請專利範圍第4項之聚烯烴樹脂發泡物之製造方法，其中聚烯烴樹脂係，2 3 0 °C之熔融張力爲30〜4〇〇 mN之聚丙烯樹脂。200530307 (1) X. Application for patent scope 1. A polyolefin resin foam, which is characterized by containing 2 to 12% by weight of a polymer antistatic agent, and an apparent density of 15 to 65 g / L. After sonic cleaning, the surface resistivity is 1 X 1 0 8 to 1 X 1 〇13 (Ω), and the average bubble diameter satisfies the following formulas (1), (2), and (3). 〇35 $ Z / X $ 1.2 ...... (1) 0.35 SZ / YS 1.2 ....... (2) 0.2 ^ Z ^ 1.4 ...... (3) (乂, ¥ and 2 series, extrusion direction Average bubble diameter: 乂 (111111), average bubble diameter in the width direction: Y (mm) and average bubble diameter in the thickness direction: Z (mm)) 〇 2 Foam, in which the content of the polymer-type antistatic agent in the polyolefin resin foam is 2 to 10% by weight. 3 · The polyolefin resin foam according to item 1 of the patent application scope, wherein the polyalkylene resin foams The content of the polymer-type antistatic agent in the content is 2 to 8% by weight. 4 · A method for manufacturing a polyolefin resin foamed material, which uses an extruder to mix the polyolefin resin, the polymer-type antistatic agent, and bubble adjustment And a physical foaming agent 'to form a foamable polyolefin resin solution, and to extrude and expand the foamable polyolefin resin solution into a polyolefin foamed product such as the item 1 of the scope of patent application, which is characterized by: The amount of the above-mentioned polymer antistatic agent is 2 to 14 parts by weight based on 100 parts by weight of the polyolefin resin. -48- 200530307 (2) The crystallization temperature of the above-mentioned polymer antistatic agent is below 11 ° C. Melt viscosity of the polyparaffinic hydrocarbon resin at a measurement temperature of 190 ° C and a shear rate of 100-sec-I: Ma (Pa.s), and the above-mentioned polymer antistatic agent at a measurement temperature of 190 ° C, shear Melt viscosity at a cutting speed of 100 sec_ 1: The relationship between Mb (Pa · s) satisfies the following formulae (4) and (5), Ma > Mb (4) 80Pa · s ^ Mb ^ 1 OOOPa · s (5 ) 5. The method of manufacturing Φ of polyolefin resin foam according to item 4 of the patent application, wherein the polyolefin resin is a polyethylene resin with a melt tension of 190 ° C of 30 to 400. 6. Method for manufacturing polyolefin resin foamed product according to item 4 of the patent, wherein the polyolefin resin is a melt tension of 230 ° C 30~4〇〇 mN of a polypropylene resin.

-49- 200530307 七、指定代表圖： (一）、本案指定代表圖爲··無 (二）、本代表圖之元件代表符號簡單說明：無八、本案若有化學式時，請揭示最能顯示發明特徵之化學式：無-49- 200530307 VII. Designated representative map: (1). The designated representative map in this case is ... No (II). The component representative symbols of this representative map are simply explained: No. 8. If there is a chemical formula in this case, please reveal the best display. Inventive chemical formula: None