TW201527371A - 聚烯烴系樹脂發泡粒子 - Google Patents

聚烯烴系樹脂發泡粒子 Download PDF

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TW201527371A
TW201527371A TW103139575A TW103139575A TW201527371A TW 201527371 A TW201527371 A TW 201527371A TW 103139575 A TW103139575 A TW 103139575A TW 103139575 A TW103139575 A TW 103139575A TW 201527371 A TW201527371 A TW 201527371A
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polyolefin
based resin
core layer
inorganic filler
resin
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TWI633138B (zh
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Shota Takagi
Akinobu Hira
Kazutoshi Sasaki
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Jsp Corp
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Abstract

本發明之課題在於提供一種含有無機填充劑之聚烯烴系發泡粒子，其雖含有無機填充劑但成形時不易連續氣泡化，並具有優異之熔接性，且可形成良好之聚烯烴系發泡粒子成形體。作為解決手段之含無機填充劑之聚烯烴系樹脂發泡粒子乃由芯層及被覆層構成，前述芯層形成發泡構造，該發泡構造是使以第1聚烯烴系樹脂為基材樹脂之發泡性樹脂組成物發泡而成，前述被覆層是以樹脂組成物被覆前述芯層而成，且該樹脂組成物以第2聚烯烴系樹脂為基材樹脂。聚烯烴系樹脂發泡粒子中，前述被覆層與前述芯層之重量比為1：99~20：80，前述芯層以相對於構成該芯層之發泡性樹脂組成物的摻合比率計為5重量%以上且90重量%以下之範圍含有無機填充劑，且比例上前述被覆層所含之無機填充劑的摻合量小於芯層所含之摻合量(但，包含0)。

Description

聚烯烴系樹脂發泡粒子 技術領域
本發明係有關於一種包含無機填充劑之聚烯烴系樹脂發泡粒子。
背景技術
以提升機械強度或賦與難燃性等機能特性為目的，正在開發一種於聚烯烴系樹脂發泡粒子中摻合有無機填充劑之技術。含有無機填充劑之聚烯烴系樹脂發泡粒子成形體(亦稱含無機填充劑之成形體)可有效地活用於例如，如專利文獻1記載之作為導電體使用。
先前技術文獻 專利文獻
專利文獻1：日本專利特表2008-512502號公報
發明概要
然而，聚烯烴系樹脂發泡粒子含有大量無機填充劑時，於成形含無機填充劑之發泡粒子時將產生問題。換言之，含有無機填充劑之聚烯烴系樹脂發泡粒子有成形時 容易連續氣泡化、或熔接性容易不充分的問題。聚烯烴系樹脂發泡粒子之熔接性不充分時，含無機填充劑之成形體將變得極為脆弱，尤其在厚的成形體方面，聚烯烴系樹脂發泡粒子之熔接性容易變得不充分。
因此，為實現使聚烯烴系樹脂發泡粒子具充分之熔接性，於進行聚烯烴系樹脂發泡粒子之模內成形時提高了模製壓力。然而，提高模製壓力時，有聚烯烴系樹脂發泡粒子連續氣泡化之虞，或恐因含有無機填充劑之成形體表面附近的發泡粒子本身受到損害，於前述成形體表面附近與內部之間的密度差變大，以致前述成形體表面附近與內部存在於成形體每單位體積中之無機填充劑容易分散不均。無機填充劑分散不均時，亦恐致無機填充劑所賦予之成形體的機能性變得不均、或變得不充分。
本發明之目的在於提供一種含有無機填充劑之聚烯烴系發泡粒子，且其即使含有無機填充劑仍具有優異之熔接性等模內成形性。
本發明之要旨如下。(1)一種聚烯烴系樹脂發泡粒子，其包含無機填充劑，該聚烯烴系樹脂發泡粒子由第1聚烯烴系樹脂所形成之發泡狀態的芯層、與第2聚烯烴系樹脂所形成之被覆層構成，前述被覆層與前述芯層之重量比為1：99~20：80，前述芯層以5重量%以上且90重量%以下之範圍包含無機填充劑，且比例上前述被覆層所含之無機填充劑的摻合量小於前述芯層所含之無機填充劑的摻合量 (但，包含0)；(2)如前述(1)記載之聚烯烴系樹脂發泡粒子，其中前述芯層以30重量%以上且90重量%以下之範圍包含無機填充劑；(3)如前述(1)或(2)記載之聚烯烴系樹脂發泡粒子，其中形成前述芯層之聚烯烴系樹脂包含羧酸或羧酸酐改質聚烯烴系樹脂，且形成前述芯層之聚烯烴系樹脂中的羧酸或羧酸酐成分之含量為0.15~10重量%。
依據本發明，可提供一種含有無機填充劑之聚烯烴系發泡粒子，且其即使含有無機填充劑仍具有優異之熔接性等模內成形性。
1‧‧‧聚烯烴系樹脂發泡粒子
2‧‧‧芯層
3‧‧‧被覆層
圖1A係示意性顯示本發明之聚烯烴系樹脂發泡粒子之一例的概略側視圖。圖1B係示意性顯示圖1A之A-A線截面之概略狀態的概略截面示意圖。
圖2係顯示相對於無機填充劑添加量之下羧酸成分含量之較佳範圍的圖表。
用以實施發明之形態
[聚烯烴系樹脂發泡粒子1]
本發明之聚烯烴系樹脂發泡粒子1係包含無機填充劑者，如圖1A、圖1B所示，係具有發泡狀態之芯層2與被覆該芯層2之被覆層3的構造。又，圖1A、圖1B之例中， 聚烯烴系樹脂發泡粒子1係形成為圓柱狀，芯層2之兩端露出於外側。
(無機填充劑)
並未特別限定聚烯烴系樹脂發泡粒子1所含之無機填充劑，但粒烴小者因容易均一地分散於聚烯烴系樹脂中故為佳。又，若無機填充劑係可均一地分散於熱可塑性樹脂中之者時，將可調製更均一地分散有無機填充劑的聚烯烴系樹脂發泡粒子1。
本發明所使用之無機填充劑，可舉例如：碳黑、黑鉛等碳類、玻璃纖維、金屬纖維、碳纖維等纖維、氫氧化鋁、氫氧化鈣、氫氧化鎂等無機氫氧化物、碳酸鈣、碳酸鎂、碳酸鋇等無機碳酸鹽、亞硫酸鈣、亞硫酸鎂等無機亞硫酸鹽、硫酸鈣、硫酸鎂、硫酸鋁等無機硫酸鹽、氧化鐵、氧化鋁、氧化鋅、氧化矽、氧化鉛、氧化鎂、氧化鈷、氧化鈦、氧化鈣等無機氧化物、硼酸鋅、硼酸鈣、硼酸鎂、硼酸鋁等硼酸鹽、其他滑石、黏土、高嶺土、沸石等黏土或天然礦物。
無機填充劑以前述無機氧化物為佳，其中由均一分散性、耐摩性、刮痕抗性等優異之點來看，以使用金屬氧化物為佳，金屬氧化物可舉例如：氧化鐵、氧化鋁、氧化鋅、氧化矽、氧化鉛、氧化鎂、氧化鈷、氧化鈦等。
金屬氧化物中特別由耐摩性優異之點來看，可適當地選擇氧化鈦作為無機填充劑。
此處，屬於前述氧化鈦之化合物中，除了僅包 含鈦之金屬種類的化合物以外，亦包含除了鈦以外亦含有鈦之金屬種類的化合物。
另，無機填充劑可使用選自於前述化合物之1種，亦可使用選自於各種化合物之2種以上後併用該等經選擇的化合物。
(芯層2)
芯層2係由發泡狀態所構成。形成芯層2之發泡構造係使聚烯烴系樹脂發泡而成的構造。另，芯層2係藉由於聚烯烴系樹脂添加後述之發泡劑後，使用預定之裝置與預定之條件使發泡性樹脂組成物發泡所形成。
(發泡劑)
另外，發泡劑可舉有機系物理發泡劑、或無機系物理發泡劑為例。有機系物理發泡劑可舉例如：丙烷、丁烷、戊烷、己烷及庚烷等脂肪族烴、環丁烷及環己烷等脂環式烴等。無機系物理發泡劑可舉空氣、氮、二氧化碳、氧、氬、水等為例。
(聚烯烴系樹脂)
本發明之聚烯烴系樹脂係指烯烴之同元聚合物、僅為烯烴或包含烯烴之共聚物、或2個以上該等之混合物。僅為烯烴之共聚物係指2個以上烯烴群的共聚物，包含烯烴之共聚物係指烯烴與其他單體成分的共聚物，且為烯烴成分比率在50重量%以上之共聚物。又，聚烯烴系樹脂除了前述同元聚合物及/或共聚物以外，亦可為包含其他熱可塑 性樹脂及/或彈性體的樹脂組成物。此時，係表示組成物中之烯烴成分比率為50重量%以上的樹脂組成物。
烯烴之同元聚合物可舉聚丙烯、聚乙烯、聚丁烯、聚戊烯為例。僅為烯烴或包含烯烴之共聚物，可舉例如：乙烯-丙烯共聚物、乙烯-丁烯共聚物、乙烯-乙酸乙酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-順丁烯二酸酐共聚物等乙烯成分比率為50重量%以上的乙烯系共聚物、經金屬離子交聯前述乙烯-甲基丙烯酸共聚物分子之間的乙烯系離子聚合物、丙烯-乙烯共聚物、丙烯-丁烯共聚物、丙烯-乙烯-丁烯三元共聚物、丙烯-丙烯酸共聚物、丙烯-順丁烯二酸酐共聚物等丙烯成分比率為50重量%以上的丙烯系共聚物。該等共聚物可為嵌段共聚物、無規共聚物、接枝共聚物之任一者。
作為發泡性樹脂組成物所含之基材樹脂的聚烯烴系樹脂，由剛性、耐摩性、加工性優異、成本低廉且廣為使用之點來看，以聚丙烯系樹脂為佳。聚丙烯系樹脂係指聚丙烯、丙烯-乙烯無規共聚物、丙烯-丁烯無規共聚物、丙烯-乙烯-丁烯三元共聚物等丙烯成分比率為50重量%以上之丙烯系共聚物、或2個以上該等之混合物。
聚烯烴系樹脂可使用經過氧化物或放射線交聯者，但由可輕易地形成均一地混合有後述之無機填充劑的狀態之點來看，以使用無交聯者為佳。
形成本發明之發泡粒子之芯層的聚烯烴系樹脂中，宜摻合作為含極性基聚合物之羧酸或羧酸酐改質烯烴 系聚合物而成，且該羧酸或羧酸酐改質烯烴系聚合物係使選自於乙酐、丁二酸酐、順丁烯二酸酐、鄰苯二甲酸酐等酸酐、甲基丙烯酸、順丁烯二酸、丙烯酸等之1種或2種以上共聚合者，其中以摻合順丁烯二酸酐改質聚丙烯而成尤佳。已形成芯層之聚烯烴系樹脂中，宜以按0.15~10重量%之比率含有前述羧酸成分的方式，摻合羧酸或羧酸酐改質聚合物。前述羧酸或羧酸酐成分之含量，較佳者是0.2~8重量%，且0.3~6重量%更佳。聚烯烴系樹脂亦可併用未改質烯烴系聚合物與酸改質烯烴系聚合物。另，酸改質烯烴系聚合物係指羧酸或羧酸酐改質烯烴系聚合物。未改質烯烴系聚合物係指假定為酸改質烯烴系聚合物改質前之聚合物的聚合物。
形成芯層之聚烯烴系樹脂中的羧酸成分係來自羧酸或羧酸酐改質烯烴系聚合物者，形成芯層之聚烯烴系樹脂中羧酸成分的含量，係由聚烯烴系樹脂中所摻合之前述羧酸或羧酸酐改質烯烴系聚合物的摻合量，與該聚合物中之羧酸或其衍生物的改質率(酸改質烯烴系聚合物之改質率)兩者來決定。
該羧酸或羧酸酐改質烯烴系聚合物中，由聚烯烴系樹脂與無機填充劑之親和性之點來看，羧酸或其衍生物之改質率(酸改質烯烴系聚合物之改質率)以0.5~15重量%為佳，更以1~8重量%為佳。
又，無機填充劑之比例亦有關聯，但前述羧酸或羧酸酐改質烯烴系聚合物宜於芯層中與無機填充劑及聚烯 烴系樹脂等以一共3~30重量%之比率摻合，以5~25重量%之比率摻合較佳，以6~20重量%之比率摻合更佳。已形成發泡粒子之芯層的聚烯烴系樹脂中摻合有羧酸或羧酸酐改質烯烴系聚合物時，無機填充劑與聚烯烴系樹脂之親和性優異，發泡粒子的視密度之不均將變得更小。另，芯層中摻合羧酸或羧酸酐改質烯烴系聚合物之方法，可舉例如：於調整用以得到發泡粒子之樹脂粒子時，將羧酸或羧酸酐改質烯烴系聚合物、抑或羧酸或羧酸酐改質烯烴系聚合物母料與聚烯烴系樹脂及無機填充劑一同進行捏合的方法，或者，捏合業經羧酸或羧酸酐改質烯烴系聚合物進行表面處理之無機填充劑與聚烯烴系樹脂的方法等。如前述，使用具有摻合有羧酸或羧酸酐改質烯烴系聚合物之芯層的樹脂粒子並以眾所周知之方法製造發泡粒子，藉此，可得於構成發泡粒子之基材樹脂中摻合羧酸或羧酸酐改質烯烴系聚合物而成者。
於聚烯烴系樹脂粒子中，隨著無機填充劑之摻合量變多，該無機填充劑將成為斷裂點，而有於發泡時、成形時之二次發泡時氣泡容易破裂的疑慮。因此，以隨著無機填充劑摻合量之增加，調整羧酸或羧酸酐改質烯烴系聚合物之摻合量為佳。芯層中之羧酸或羧酸酐成分之含量(y)(重量%)與無機填充劑之摻合量(x)(重量%)以滿足下述式(1)為佳，藉於該範圍內因可降低於發泡時等發泡粒子之氣泡成為連續氣泡之疑慮或氣泡破裂之疑慮而為佳。
[數1] 0.008x+0.300≧y≧0.008x-0.125…(1)
(芯層2之無機填充劑)
聚烯烴系樹脂發泡粒子1中，無機填充劑至少存在有芯層2。
(芯層2之無機填充劑的含量)
芯層2係以相對於該芯層2之摻合比率計為5重量%以上且90重量%以下之範圍包含無機填充劑，但由可更有效得到藉由發泡粒子賦予高度機能性且無機填充劑之均一分散性優異的聚烯烴系樹脂發泡粒子1之觀點來看，宜以30重量%以上且85重量%以下之範圍摻合無機填充劑，以40重量%以上且80重量%以下之範圍摻合較佳，以50重量%以上且80重量%以下之範圍摻合更佳。
(添加劑)
發泡性樹脂組成物中，除了前述基材樹脂以外，亦可於不阻礙本發明效果之程度內適當地添加添加劑。添加劑可舉例如：抗氧化劑、紫外線吸收劑、抗靜電劑、難燃劑、顏料、染料、核劑及氣泡調整劑等。
(被覆層3)
被覆層3係由樹脂組成物所構成之層，如圖1A、圖1B所示，被覆芯層2的周圍。
被覆層3係由聚烯烴系樹脂所形成。作為基材樹脂之聚烯烴系樹脂可舉可選擇作為構成如前述之芯層2的基材樹脂之聚烯烴系樹脂的樹脂為例。
(被覆層3是否存在無機填充劑)
聚烯烴系樹脂發泡粒子1中，無機填充劑亦可存在於被覆層3。因此，被覆層3亦可為未含有無機填充劑之層。
更詳而言之，被覆層3係使於該被覆層3中摻合之無機填充劑的摻合比例較芯層2中摻合之無機填充劑的摻合比例少地，包含無機填充劑之層、或未含無機填充劑之層。
無論被覆層3係未含有無機填充劑之層、或包含無機填充劑之層，接構成為使被覆層中摻合之無機填充劑的摻合比例小於構成前述芯層之發泡性樹脂組成物中摻合之無機填充劑的摻合比例，故聚烯烴系樹脂發泡粒子1之被覆層3的熔接性較芯層2優異。因此，將聚烯烴系樹脂發泡粒子成形體如後述進行模內成形時，可得到相較於僅以對應芯層2之構造所構成的發泡粒子，容易使相鄰之聚烯烴系樹脂發泡粒子1之間更確實地熔接的效果。因此，為提升熔接性而將發泡粒子成形時，不需提高模製壓力或預先加壓發泡粒子等之操作，即可得良好之成形體。又，可縮小所得成形體的表層與內層之密度差。
另外，由模內成形前述聚烯烴系樹脂發泡粒子時發泡粒子群之熔接優異的觀點來看，以被覆層3之發泡倍率低於芯層2為佳，以係非發泡狀態或實質上係非發泡狀態較佳。
(被覆層3與芯層2之重量比)
聚烯烴系樹脂發泡粒子1中，被覆層3與芯層2之重量比係1：99~20：80。藉由如此之重量比，無機填充劑之 量多之芯層將更確實地被被覆層所被覆，故增加無機填充劑量且可得成形時之熔接性亦優異的發泡粒子。由該觀點來看，被覆層3與芯層2之重量比以1：99~15：85較佳，以1：99~10：90更佳。
被覆層3特別以包含熔點低於形成芯層2之聚烯烴系樹脂、或實質上未顯示熔點之聚烯烴系樹脂為佳。於包含低熔點或未顯示熔點之聚烯烴系樹脂時，前述聚烯烴系樹脂發泡粒子即使以較低之加熱水蒸氣壓模內成形，仍可成為所期的模內成形體。
(被覆層3與芯層2之熔點差)
被覆層3與芯層2以形成被覆層3之聚烯烴系樹脂的熔點與形成芯層2之聚烯烴系樹脂的熔點之熔點差於0~50℃之範圍為佳，以大於0、45℃以下較佳，以5℃以上40℃以下更佳。又，形成被覆層之聚烯烴系樹脂係未具有熔點之非晶性聚烯烴系樹脂時，該非晶性聚烯烴系樹脂之菲卡軟化溫度以較形成芯層2之聚烯烴系樹脂的熔點低為佳，以低於5℃以上較佳。前述熔點與軟化點之差的上限大概係100℃左右。
於聚烯烴系樹脂發泡粒子1中，藉由形成被覆層3之聚烯烴系樹脂與形成芯層2之聚烯烴系樹脂滿足前述範圍地構成，於模內成形發泡粒子時，不需提高用以熔接發泡粒子群之加熱水蒸氣壓，即使以較低之溫度仍可熔接發泡粒子群，可得所期的模內成形體。
本發明之發泡粒子中，藉由熱流微差掃描熱量測 定法，以10℃/分之升溫速度將前述發泡粒子2~10mg由23℃加熱至220℃後所得之DSC曲線(第1次加熱之DSC曲線)，以具有聚烯烴系樹脂固有之吸熱峰值A(以下，亦僅稱為「固有峰值」)、該固有峰值之高溫側之1個以上的吸熱峰值B(以下，亦僅稱為「高溫峰值」)為佳。相對於DSC曲線之全熔融熱量(固有峰值之熔融熱量與高溫峰值之熔融熱量的合計)的該高溫峰值之熔融熱量(以下，亦僅稱為高溫峰值熱量。)的比以0.1以上為佳，較佳者是0.15以上，更佳者為0.2以上。該熔融熱量之比的上限係約0.4左右，較佳者是0.3。若於前述範圍內，可控制發泡粒子之二次發泡力，並使發泡粒子群熔接，可得密度均一之發泡粒子成形體而為佳。
前述第1次加熱之DSC曲線與固有峰值熱量、高溫峰值熱量的測定係藉由依據JIS K 7122(1987年)之測定方法進行。另外，發泡粒子之高溫峰值可以眾所周知的方法調節，具體而言，該調節方法可揭示如例如，日本專利特開2001-151928號等。
聚烯烴系樹脂發泡粒子1之平均粒子徑以0.5~10mm為佳，較佳者是0.8~5mm。更佳者為1~3mm。另，平均粒子徑係如以下測定：自以相對溼度50%、23℃、1atm之條件放置2天後的聚烯烴系樹脂發泡粒子中隨意取出200個以上，再以測徑器測定各聚烯烴系樹脂發泡粒子的最大尺寸(mm)，由該最大尺寸之算術平均值求得。
聚烯烴系樹脂發泡粒子1之體密度，以 0.03~1.5g/cm3為佳，較佳者是0.05~1.2g/cm3。更佳者為0.05~0.8g/cm3。
[聚烯烴系樹脂發泡粒子1之機能]
聚烯烴系樹脂發泡粒子1中，於芯層2以相對於該芯層2之摻合比率計為5重量%以上且90重量%以下之範圍含有無機填充劑。並且，聚烯烴系樹脂發泡粒子1因將芯層2作成分布有較多無機填充劑之層，且將被覆層3作成分布少或未存在無機填充劑之層，故即使於聚烯烴系樹脂發泡粒子1全體含有大量無機填充劑，仍可維持聚烯烴系樹脂發泡粒子1表面的熔接性。因此，即使是將含有大量無機填充劑者成形作成使用有聚烯烴系樹脂發泡粒子1之聚烯烴系樹脂發泡粒子成形體的情況下，亦可減少於調製聚烯烴系樹脂發泡粒子成形體時提高模製壓力的需求。此外在聚烯烴系樹脂發泡粒子成形體方面，可形成無機填充劑之均一分散性優異者。又，使用聚烯烴系樹脂發泡粒子1所形成之聚烯烴系樹脂發泡粒子成形體，可調製含有各種量之無機填充劑者。
[聚烯烴系樹脂發泡粒子1之調製方法]
聚烯烴系樹脂發泡粒子1可如以下地調製。
準備2台擠壓機，以其中之一的擠壓機捏合用以形成芯層2之樹脂組成物，以另一台擠壓機捏合構成被覆層3之樹脂組成物後，利用自預定形狀之模進行共擠壓，得到由芯層與被覆芯層之被覆層所構成的鞘芯型之條狀複合物。接著，以具有捲取機之裁切機裁切成預定重量或大小 的條狀複合物，得到由非發泡之芯層與被覆層所覆蓋的柱狀顆粒狀之樹脂粒子。
此外，將樹脂粒子與發泡劑收納在密封可開放之壓力容器內後密封閉，使樹脂粒子浸漬並吸收發泡劑。之後，將壓力容器內加熱至構成芯層之基材樹脂的軟化溫度以上，調製發泡性樹脂粒子。並且，藉由開放經密閉之壓力容器，將壓力容器內之發泡性樹脂粒子自密閉容器放出至低壓環境氣體下。此時，芯層將呈發泡狀態形成芯層2。又，隨著芯層2之形成，被覆層將成為被覆芯層2的被覆層3。如此，形成聚烯烴系樹脂發泡粒子1。
[聚烯烴系樹脂發泡粒子成形體]
本發明之聚烯烴系樹脂發泡粒子成形體係將包含如前述具芯層2與被覆層3之聚烯烴系樹脂發泡粒子1的發泡粒子進行模內成形而成者。另，聚烯烴系樹脂發泡粒子成形體可包含僅使用如前述具芯層2與被覆層3的聚烯烴系樹脂發泡粒子1作為發泡粒子進行模內成形而成者。雖以聚烯烴系樹脂發泡粒子成形體為板狀之情形為例，但聚烯烴系樹脂發泡粒子成形體之形狀並未受此所限，可適當地設定。
(視密度)
不需特別限定聚烯烴系樹脂發泡粒子成形體之視密度，但視密度以0.05~0.8g/cm3為佳。發泡粒子成形體之視密度可藉由以成形體之體積除成形體之重量來求得。成形體肢體積可由成形體之外部尺寸等求得。
(熔接率)
聚烯烴系樹脂發泡粒子成形體只要可保持一體性的話，並未特別限定聚烯烴系樹脂發泡粒子1之熔接率，考量到得到機械強度優異之成形體之點，構成聚烯烴系樹脂發泡粒子成形體之前述聚烯烴系樹脂發泡粒子1的熔接率，以60%以上為佳，70%以上更佳，80%以上尤佳。
(熔接率之測定)
聚烯烴系樹脂發泡粒子成形體中，聚烯烴系樹脂發泡粒子4之熔接率可以彎曲試驗之破裂面的材料破壞率進行評價。換言之，觀察發泡粒子成形體之彎曲破裂面(存在發泡粒子100個以上之破裂面)，再藉由目視分別計算經破壞之發泡粒子與界面經剝離的發泡粒子數量。並且，將相對於經破壞之發泡粒子數與界面經剝離之發泡粒子數的合計，經破壞之發泡粒子數的百分率作為熔接率。
[聚烯烴系樹脂發泡粒子成形體之形成方法]
聚烯烴系樹脂發泡粒子成形體可使用例如，模內成形法調製。換言之，首先準備設計成對應欲得之聚烯烴系樹脂發泡粒子成形體的所期之形狀的模具。接著，於模具內填充前述聚烯烴系樹脂發泡粒子1。於模具內供應蒸氣加熱模具內。此時，相鄰之聚烯烴系樹脂發泡粒子1之被覆層3將互相熔接，並且聚烯烴系樹脂發泡粒子1二次發泡後填入發泡粒子間之間隙，填充於模具內之多數聚烯烴系樹脂發泡粒子1將一體化。之後，冷卻模具，自模具內取出內容物，得到聚烯烴系樹脂發泡粒子成形體。
本發明中，利用適當地變更無機填充劑之種類、摻合量，可得到具有各種機能的聚烯烴系樹脂發泡粒子成形體。所得之聚烯烴系樹脂發泡粒子成形體可使用於各種用途。
本發明中，藉由適當地變更無機填充劑之種類、摻合量，可調製作為聚烯烴系樹脂發泡粒子成形體之具有各種機能者。又，於利用模內成形法等調製聚烯烴系樹脂發泡粒子成形體時，由使聚烯烴系樹脂發泡粒子1之被覆層3軟化，並有效率且順利地進行聚烯烴系樹脂發泡粒子1間的熔接來看，可較以往降低實施模內成形法時之模製壓力。
實施例
實施例1~5
[含有無機物之母料的調整]
將作為構成芯層之樹脂組成物的表1所示之聚烯烴系樹脂、無機填充劑、羧酸改質聚烯烴系聚合物(羧酸之改質率5%)以表2所示之比例供應至內徑30mm的二軸擠壓機，以200~220℃熔融捏合擠壓成股狀後得到擠壓物，冷卻該股狀之擠壓物、裁切，於芯層得到含有無機物的母料。表2中，樹脂種類之MPP係表示羧酸改質聚烯烴，使用順丁烯二酸酐改質聚丙烯(東洋紡股份公司製，H3000P(羧酸改質率5wt%))。
另外，表2中，羧酸成分之含量係表示芯層組成之聚烯烴系樹脂中所含之羧酸成分的含量。芯層-被覆層之樹脂熔點差係表示構成芯層之聚烯烴系樹脂的熔點與構成被覆層之聚烯烴系樹脂的熔點之差。芯層/被覆層重量比係表示粒子全重量中芯層、被覆層分別所佔的重量比率(%)。
[樹脂粒子之製造]
使用於內徑65mm之芯層形成用擠壓機及內徑30mm之外層形成用擠壓機的出口側設置有多層股形成用模之擠壓機，將如前述所調製之芯層形成用之含有無機物的母料與被覆層形成用之聚烯烴系樹脂，分別以表2所示之比例各自供應至芯層用擠壓機及被覆層用擠壓機加以熔融捏合作成熔融捏揉物後，導入前述多層股形成用模於模內合流後，自裝設於模前端之模口的小孔將被覆有被覆層之芯層擠壓成股，再將經擠壓之股水冷卻，以製粒機裁切後乾燥，得到圓柱狀之樹脂粒子。於實施例1至5中得到多層之樹脂粒子。
[發泡粒子之製造]
將前述所得之樹脂粒子800g與分散介質之水3L加入5L之密閉容器內，分散介質中相對於前述樹脂粒子100重量份，分別添加作為分散劑之高嶺土0.3重量份、界面活性劑(商品名：NEOGEN，第一工業製藥股份公司製，烷基苯磺酸鈉)0.4重量份(作為有效成分)、及硫酸鋁0.01重量份，並於密閉容器內壓入如表3所示之量之作為發泡劑的二氧化碳，攪拌下加熱升溫至較如表3所示之發泡溫度低5 ℃之溫度後保持15分鐘，調整高溫峰值熱量，再加熱升溫至如表3所示之發泡溫度並保持15分鐘後，於大氣壓力下將容器內容物與水一同放出，得到表3所示之視密度(體密度)的發泡粒子。此時，於實施例1至5中得到多層之發泡粒子。又，所得之多層之發泡粒子的物理特性等係如表3所示。此外，此時所得之發泡粒子係本發明之聚烯烴系樹脂發泡粒子。
[發泡粒子成形體]
視需要，將前述所得之聚烯烴系樹脂發泡粒子一面以表4所示之條件進行利用加壓氣體(空氣)提高發泡粒子內之內壓的加壓處理，一面裂解填充至長度300mm×寬度200mm×厚度60mm之平板成形模具，以蒸氣加熱進行模內成形，得到板狀發泡粒子成形體。另，加熱方法係於開放兩面型之排洩閥的狀態下供應蒸氣5秒鐘進行預熱(排氣步驟)後，以較表4所示之成形蒸氣壓低0.08MPa(G)之壓力進行一邊加熱，並且以較表4所示之成形蒸氣壓低0.04MPa(G)之壓力自相反方向進行一邊加熱後，以表4所示之成形蒸 氣壓進行自兩面的正式加熱。結束加熱後，放壓，空氣冷卻30秒鐘後打開模具，將模內成形體自模具中取出。將所得之發泡粒子成形體於80℃之烘箱內養護12小時，得到聚烯烴系樹脂發泡粒子成形體。於表4顯示所得之成形體的物理特性。
比較例1
比較例1中，於芯層使用聚烯烴系樹脂40重量%、作為無機填充劑之氧化鈦60重量%，除了未設置被覆層以外與實施例1同樣地製造發泡粒子。使用發泡粒子與實施例1同樣地實施調製發泡粒子成形體。以與實施例1相同之條件下發泡粒子未熔接，未能得到發泡粒子成形體。為使發泡粒子熔接而提高成形蒸氣壓時，發泡粒子將連續氣泡化，未能得到發泡粒子成形體。
比較例1嘗試了藉賦與發泡粒子內壓後進行模內成形，調製發泡粒子成形體。此時，雖可得發泡粒子成形體，但係熔接性差者。比較例1之發泡粒子雖欲成形為如本 例之厚度厚的發泡粒子成形體，但未能得到良好之發泡粒子成形體。
發泡粒子及發泡粒子成形體之物理特性評價方法係如下述地進行。
[發泡粒子之體密度]
發泡粒子之體密度係如以下地求得。首先，準備1L之量筒，填充發泡粒子群至量筒內之1L標線。測定填充有1L時之發泡粒子群的重量(g/L)，藉由單位換算求出發泡粒子之體密度(g/cm3)。
[發泡粒子成形體之視密度]
發泡粒子成形體之視密度係以由成形體之外部尺寸求出的體積(cm3)除成形體之重量(g)而求出。
[熔接性]
發泡成形體之熔接性係藉由下述方法測定並評價。折彎發泡成形體並使其斷裂，求得存在於破裂面之發泡樹脂粒子的數量(C1)與破壞之發泡樹脂粒子的數量(C2)，算出相對於前述發泡樹脂粒子之破壞的發泡樹脂粒子之比率(C2/C1×100)作為材料破壞率。使用相異之試驗片進行5次前述測定，求出各別之材料破壞率，並將該等之算術平均值作為熔接率(%)。依據藉由前述測定方法求出之熔接率，以如下述之基準區分評價出◎、○、×。另，◎、○顯示熔接性優異，×顯示熔接性差。
◎‧‧‧熔接率係80%以上。
○‧‧‧熔接率係60%以上、小於80%。
×‧‧‧熔接率係小於60%。
[高溫峰值熱量]
高溫峰值熱量(J/g)係隨意從所得之發泡粒子群取樣10個發泡粒子，藉由已述之方法測定各發泡粒子的固有峰值熱量與高溫峰值熱量，求得相對於全熔融熱量之高溫峰值熱量的比，將該等測定值進行算術平均後之值，作為相對於發泡粒子之全熔融熱量之高溫峰值熱量的比。
1‧‧‧聚烯烴系樹脂發泡粒子
2‧‧‧芯層
3‧‧‧被覆層

Claims (3)

  1. 一種聚烯烴系樹脂發泡粒子，其包含無機填充劑；前述聚烯烴系樹脂發泡粒子由第1聚烯烴系樹脂所形成之發泡狀態的芯層、與第2聚烯烴系樹脂所形成之被覆層構成；前述被覆層與前述芯層之重量比為1：99~20：80；前述芯層以5重量%以上且90重量%以下之範圍包含無機填充劑；且比例上前述被覆層所含之無機填充劑的摻合量小於芯層所含之無機填充劑的摻合量(但，包含0)。
  2. 如請求項1之聚烯烴系樹脂發泡粒子，其中前述芯層以30重量%以上且90重量%以下之範圍包含無機填充劑。
  3. 如請求項1或2之聚烯烴系樹脂發泡粒子，其中形成前述芯層之聚烯烴系樹脂包含羧酸或羧酸酐改質聚烯烴系樹脂，且形成前述芯層之聚烯烴系樹脂中的羧酸或羧酸酐成分之含量為0.15~10重量%。
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10385178B2 (en) 2014-01-17 2019-08-20 Jsp Corporation Propylene-based resin foam particle and foam particle molded body
EP3309196B1 (en) * 2015-06-10 2021-12-08 JSP Corporation Thermoplastic resin expanded particles
JP6060220B1 (ja) 2015-07-15 2017-01-11 株式会社ジェイエスピー プロピレン系樹脂発泡粒子及び発泡粒子成形体
KR20220027846A (ko) * 2019-06-28 2022-03-08 니폰 제온 가부시키가이샤 전기 화학 소자용 복합 입자 및 그 제조 방법, 전기 화학 소자 기능층용 바인더 조성물 및 그 제조 방법, 전극 합재층용 도전재 페이스트 및 그 제조 방법, 전극 합재층용 슬러리, 전기 화학 소자용 전극, 그리고 전기 화학 소자
CN112759843A (zh) * 2019-10-21 2021-05-07 中国石油化工股份有限公司 聚烯烃复合发泡珠粒及其制备方法
JP7137099B1 (ja) * 2021-06-09 2022-09-14 株式会社ジェイエスピー ポリプロピレン系樹脂発泡粒子、その製造方法及びポリプロピレン系樹脂発泡粒子成形体
CN113583437A (zh) * 2021-08-31 2021-11-02 浙江理工大学绍兴柯桥研究院有限公司 一种高分子复合材料及其制备方法
WO2023054223A1 (ja) * 2021-09-29 2023-04-06 株式会社カネカ ポリプロピレン系樹脂押出発泡粒子、ポリプロピレン系樹脂発泡成形体および積層発泡体

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207378A (en) * 1973-03-16 1980-06-10 Max Klein Expanded styrene-polymers and polyolefin micro-bits and their preparation
JPS57164432A (en) * 1981-04-02 1982-10-09 Fuji Photo Film Co Ltd Magnetic recording medium
JPH09202837A (ja) * 1996-01-25 1997-08-05 Jsp Corp 導電性ポリプロピレン系樹脂発泡粒子及びその製造方法
US6027806A (en) * 1997-01-16 2000-02-22 Mitsubishi Chemical Basf Company Limited Expanded resin beads
JP3418081B2 (ja) 1996-07-10 2003-06-16 三菱化学フォームプラスティック株式会社 発泡樹脂粒子
US6956067B2 (en) * 2000-09-20 2005-10-18 Jsp Corporation Expanded polypropylene resin bead and process of producing same
MXPA04004175A (es) 2001-11-01 2004-09-06 Jsp Corp Procedimiento para producir molduras espumadas a partir de perlas expandidas de resina de polipropileno y procediento para producir perlas expandidas de resina de polipropileno.
JP4001269B2 (ja) 2002-02-04 2007-10-31 株式会社ジェイエスピー ポリオレフィン系樹脂発泡粒子およびその発泡成形体
JP2004176047A (ja) * 2002-11-13 2004-06-24 Jsp Corp ポリプロピレン系樹脂発泡粒子及びこれを用いた型内成形体
JP4334924B2 (ja) * 2003-06-25 2009-09-30 株式会社ジェイエスピー 型内発泡成形体の製造方法
TW200602402A (en) * 2004-03-23 2006-01-16 Jsp Corp Continuous production of foam molding from expanded polyolefine resin beads
WO2006028300A1 (en) * 2004-09-10 2006-03-16 Jsp Corporation Expanded polypropylene bead for forming a dielectric material and dielectric lens member formed by the expanded polypropylene beads
CN101057370B (zh) 2004-09-10 2011-03-09 住友电气工业株式会社 Luneberg介电透镜及其制造方法
JP4669301B2 (ja) * 2005-02-23 2011-04-13 株式会社ジェイエスピー 導電性を有する熱可塑性樹脂発泡粒子及びその発泡成形体
WO2007023090A1 (de) * 2005-08-23 2007-03-01 Basf Se Verfahren zur herstellung von schaumstoffplatten
TWI361201B (en) * 2006-10-26 2012-04-01 Sekisui Plastics Formable polystyrene resin particles and production process thereof, pre-foamed particles and foam molded product
JP5281317B2 (ja) * 2008-05-22 2013-09-04 株式会社カネカ ポリプロピレン系樹脂予備発泡粒子
KR101523418B1 (ko) * 2009-06-26 2015-05-27 가부시키가이샤 제이에스피 폴리프로필렌계 수지 발포 입자 및 발포 입자 성형체
US20120270052A1 (en) * 2009-11-27 2012-10-25 Basf Se Coating composition for foam particles
JP5727210B2 (ja) * 2010-12-15 2015-06-03 株式会社ジェイエスピー ポリオレフィン系樹脂発泡粒子成形体の製造方法、及びポリオレフィン系樹脂発泡粒子成形体

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