TW201708334A - 熱塑性樹脂發泡粒子 - Google Patents
熱塑性樹脂發泡粒子 Download PDFInfo
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- TW201708334A TW201708334A TW105118157A TW105118157A TW201708334A TW 201708334 A TW201708334 A TW 201708334A TW 105118157 A TW105118157 A TW 105118157A TW 105118157 A TW105118157 A TW 105118157A TW 201708334 A TW201708334 A TW 201708334A
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Abstract
本發明之熱塑性樹脂發泡粒子含有包含選自無機粉體及無機纖維之1種以上之機能性添加劑,並且包括由熱塑性樹脂所形成之芯層、與由熱塑性樹脂所形成之發泡狀態之被覆層,其中,被覆層與芯層之質量比為99:1至50:50,芯層中之該機能性添加劑之含量(X)為5至90質量%,被覆層中之該機能性添加劑之含量比芯層中之該機能性添加劑之含量(X)少。藉此提供一種熱塑性樹脂發泡粒子,其係含有機能性添加劑,並可獲得尺寸安定性、熔接性及外觀優異,且均質的發泡粒子成形體。
Description
本發明係關於含有機能性添加劑之熱塑性樹脂發泡粒子。
熱塑性樹脂發泡粒子可配合用途而於模內成形為各種形狀。由該發泡粒子藉由模內成形所得之熱塑性樹脂發泡粒子成形體可用於介電體、電波屏蔽體、隔熱材、電子零件用包裝材料、衝擊吸收材、運送箱等廣範用途。
例如,專利文獻1、2記載含有無機粉體、無機纖維等機能性添加劑之發泡粒子成形體可用於作為介電體、電波吸收體。
[專利文獻1]日本特表2008-512502號公報
[專利文獻2]日本特開平4-56298號公報
然而,如同專利文獻1所記載,熱塑性樹脂發泡粒子大量含有機能性添加劑時,發泡粒子之2次發泡性降低,有發泡粒子成形體之熔接性、外觀降低之虞。因此,在此種狀況,欲獲得良好的成形體,必須提高模內成形時之成形壓力、或預先將發泡粒子加壓等,在生產性方面仍殘留有課題。又,專利文獻2所記載之電波吸收體中,使用附著有介電體之發泡粒子與未附著介電體之發泡粒子形成發泡粒子成形體。然而,該方法由於發泡粒子成形體成形時難以使該等2種發泡粒子完全均勻地混合,故發泡粒子成形體間之特性有產生不均之虞,生產管理困難,在製造上仍殘留有課題。
本發明係有鑑於上述以往之問題點而成者,課題係提供一種熱塑性樹脂發泡粒子,其係含有機能性添加劑,並可獲得尺寸安定性、熔接性及外觀優異,且均質的發泡粒子成形體。
本發明提供以下所記載之熱塑性樹脂發泡粒子。
〈1〉一種熱塑性樹脂發泡粒子,其係含有選自無機粉體及無機纖維之1種以上之機能性添加劑,並且,該熱塑性樹脂發泡粒子包括由熱塑性樹脂所形成之芯層、與由熱塑性樹脂所形成之發泡狀態之被覆層,其中,前述被覆層與前述芯層之質量比為99:1至50:50,前述芯層中之機能性添加劑之含量(X)為5至90質量%,前述被覆層中之機能性
添加劑之含量比前述芯層中之機能性添加劑之含量(X)少。
〈2〉如〈1〉所述之熱塑性樹脂發泡粒子,其中,前述被覆層中之機能性添加劑之含量未達20質量%(包含0)。
〈3〉如〈1〉或〈2〉所述之熱塑性樹脂發泡粒子,其中,前述機能性添加劑為導電性碳。
〈4〉如〈1〉或〈2〉所述之熱塑性樹脂發泡粒子,其中,形成前述芯層之熱塑性樹脂及形成前述被覆層之熱塑性樹脂皆為聚烯烴系樹脂。
若依據本發明之熱塑性樹脂發泡粒子,因機能性添加劑被高度填充於包括芯層與發泡狀態之被覆層之發泡粒子之芯層,故成形體中之機能性添加劑之分布均質化,可獲得有效地發揮機能性添加劑之機能之發泡粒子成形體。再者,相對於芯層之機能性添加劑之含量,被覆層之機能性添加劑之含量較少,故可提供充分地2次發泡、形成發泡粒子成形體之發泡粒子彼此之熔接性提升、外觀優異、且均質的發泡粒子成形體。
1‧‧‧熱塑性樹脂發泡粒子
2‧‧‧芯層
3‧‧‧被覆層
第1圖係示意性表示本發明之熱塑性樹脂發泡粒子之一實施形態之概略透視圖。
第2圖係第1圖之熱塑性樹脂發泡粒子之A-A剖面之實體之電子顯微鏡照片。
第3圖係第1圖之熱塑性樹脂發泡粒子之B-B剖面之
實體之電子顯微鏡照片。
以下,列舉發明實施形態,更詳細地說明本發明之熱塑性樹脂發泡粒子。第1圖係示意性表示本發明之熱塑性樹脂發泡粒子之一實施形態之概略透視圖,第2圖表示其A-A剖面之實體之電子顯微鏡照片,第3圖表示其B-B剖面之實體之電子顯微鏡照片。
[熱塑性樹脂發泡粒子1]
本實施形態之熱塑性樹脂發泡粒子1係如第1圖所示,具備:由熱塑性樹脂所形成之芯層2、由熱塑性樹脂所形成之發泡狀態之被覆層3。
(芯層2)
芯層2係由熱塑性樹脂而形成,並含有選自無機粉體及無機纖維之1種以上之機能性添加劑作為必須成分。再者,芯層2之構造可為發泡狀態,亦可為非發泡狀態。
(熱塑性樹脂)
就形成芯層2之熱塑性樹脂而言,可列舉例如:聚乙烯系樹脂、聚丙烯系樹脂等聚烯烴系樹脂;或聚苯乙烯系樹脂、聚碳酸酯樹脂、聚氯乙烯樹脂、聚甲基丙烯酸系樹脂、丙烯腈系樹脂、聚酯系樹脂、聚醯胺系樹脂、熱塑性聚胺甲酸酯樹脂及該等之摻合聚合物等。
該等之中,較佳係使用聚烯烴系樹脂。又,使用聚烯烴系樹脂與其他樹脂之混合樹脂時,混合樹脂較佳係含有50%以上之聚烯烴系樹脂,更佳係含有70質量%
以上,再更佳係含有90質量%以上。
就前述聚乙烯系樹脂而言,可列舉例如:低密度聚乙烯、高密度聚乙烯、直鏈狀低密度聚乙烯、超低密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸共聚物及其分子間以金屬離子交聯之離子聚合物系樹脂等。
又,就前述聚丙烯系樹脂而言,可列舉:丙烯均聚物、源自丙烯之結構單元為50質量%以上之丙烯系共聚物。就該共聚物而言,可例示:乙烯-丙烯共聚物、丙烯-丁烯共聚物、丙烯-乙烯-丁烯共聚物等丙烯與乙烯或碳數4以上之α烯烴之共聚物;或丙烯-丙烯酸共聚物、丙烯-馬來酸酐共聚物等。再者,該等共聚物可為嵌段共聚物、隨機共聚物、接枝共聚物之任一者。
就容易形成後述機能性添加劑均勻地混合之狀態之點而言,熱塑性樹脂較佳係使用無交聯之熱塑性樹脂。
(機能性添加劑之種類)
芯層2所含之機能性添加劑係選自無機粉體及無機纖維之1種以上。具體而言,係金屬、礦物、金屬化合物、其他無機物之粉粒體或纖維,可列舉碳黑、石墨、石墨烯、碳奈米管、碳奈米纖維、碳微纖維、碳微線圈、碳奈米線圈等碳類;玻璃纖維、金屬纖維、碳纖維等纖維;碳酸鈣、碳酸鎂、碳酸鋇等金屬碳酸鹽;硫酸鈣、硫酸鎂、硫酸鋁等金屬硫酸鹽;氧化鐵、肥粒鐵氧化鋁、氧化鋅、氧化矽、
氧化鉛、氧化鎂、氧化鈷、氧化鈦、氧化鈣等金屬氧化物;其他白土、高嶺土、沸石等黏土或天然礦物等。該等之中,就機能性添加劑而言,較佳係碳類、金屬氧化物,其中,就樹脂中之均勻分散性等優異之點而言,可適宜使用碳類。再者,就碳類而言,較佳係使用導電性碳,更佳係使用DBP吸收量為150至700cm3/100g之導電性碳。
又,從樹脂中之分散性之觀點而言,上述機能性添加劑之粒徑較佳係細者,較佳係0.001至500μm,更佳係0.01至100μm。
(機能性添加劑之含量)
從賦予發泡粒子更高程度之機能性之觀點而言,芯層2中之機能性添加劑之含量之下限,於構成芯層2之熱塑性樹脂中,係5質量%,較佳係8質量%,更佳係10質量%。另一方面,從生產性之觀點而言,其上限係90質量%,較佳係70質量%,更佳係60質量%,再更佳係30質量%。
再者,芯層2含有2種以上機能性添加劑時,將該等之合計量作為芯層2中之機能性添加劑之含量。
(被覆層3)
被覆層3必須以發泡狀態存在。被覆層3之構造係藉由使熱塑性樹脂發泡而形成。使發泡粒子含有多量機能性添加劑而發揮機能性時,有發泡粒子之2次發泡性降低之虞,或發泡粒子之樹脂本身之熔接性降低之虞。在此情形,使含有多量機能性添加劑之發泡粒子模內成形所得之發泡粒子成形體之熔接率及尺寸安定性、外觀有降低之虞。另
一方面,欲提升發泡粒子之熔接性,在使發泡粒子模內成形時,必須進行提高成形壓力、或預先將發泡粒子加壓等操作。然而,若提高成形壓力,則成形體之收縮率會變大,成形體之尺寸安定性、外觀變得容易低落。又,欲將發泡粒子加壓,需要有加壓步驟,就生產性之觀點而言仍殘留有課題。
針對此情形,本發明中,發泡粒子包括芯層與被覆層,並且將該等設為特定質量比。又,芯層含有機能性添加劑,同時被覆層3之機能性添加劑之含量比芯層的少。再者,被覆層3為發泡狀態。藉此,該發泡粒子在模內成型時被覆層3充分2次發泡並且抑制構成被覆層3之樹脂本身之熔接性之降低,故發泡粒子彼此可充分熔接,可形成良好的發泡粒子成形體。因此,由本發明之發泡粒子所得之發泡粒子成形體即使調配有機能性添加劑,熔接率仍不降低,成為尺寸精度、外觀優異之發泡粒子成形體。
(熱塑性樹脂)
就形成被覆層3之熱塑性樹脂而言,可使用與構成上述芯層2之熱塑性樹脂相同者。
(被覆層3中之機能性添加劑之存在與否)
被覆層3中可含有機能性添加劑,亦可不含機能性添加劑,但被覆層3之機能性添加劑之含量比芯層2之含量少。從提升被覆層3之發泡性之觀點而言,被覆層3中之機能性添加劑之含量,在構成被覆層3之熱塑性樹脂中,
較佳係未達20質量%(包含0),更佳係未達10質量%(包含0),再更佳係未達5質量%(包含0)。再者,機能性添加劑亦可芯層2與被覆層3添加不同機能性添加劑。又,被覆層3含有2種以上機能性添加劑時,將該等之合計量設為被覆層3中之機能性添加劑之含量。
(其他添加劑等)
本發明之熱塑性樹脂發泡粒子1中之芯層2、被覆層3,在不阻礙本發明之效果之範圍,可依需要而調配其他添加劑。就其他添加劑而言,可列舉例如:抗氧化劑、紫外線防止劑、抗靜電劑、金屬減活化劑、阻燃劑、阻燃助劑、染料、顏料、成核劑、潤滑劑、親和劑等。
就前述抗靜電劑而言,可列舉聚醚與聚烯烴之嵌段共聚物等高分子型抗靜電劑。又,就前述阻燃劑而言,可列舉溴化雙酚系化合物等溴化有機化合物、溴化丁二烯系聚合物及溴化聚苯乙烯等溴化聚合物等。
(芯層2與被覆層3之質量比)
本發明之熱塑性樹脂發泡粒子1中,芯層2與被覆層3之質量比係1:99至50:50,較佳係2:98至40:60,更佳係3:97至20:80。藉由設為如此質量比,機能性添加劑含量多之芯層更確實地由被覆層被覆並且被覆層3變得可發泡,且發泡粒子之2次發泡性亦受到保障,故可使機能性添加劑含量多並且獲得模內成形時之熔接性優異之發泡粒子。再者,上述質量比中之質量包含熱塑性樹脂與熱塑性樹脂所含有之機能性添加劑、其他添加劑之質量。
再者,本發明之發泡粒子,除了芯層2與被覆層3之外,還可設為例如於最外層、或芯層與被覆層之間形成其他層之構造。
[熱塑性樹脂發泡粒子1之機能]
本發明之熱塑性樹脂發泡粒子1中,芯層2以特定調配比率含有機能性添加劑作為必須條件。然後,熱塑性樹脂發泡粒子1中,芯層2係分布有更多機能性添加劑之層,被覆層3係機能性添加劑之含量少或機能性添加劑不存在之層。若依據具有此種條件之熱塑性樹脂發泡粒子1,即使發泡粒子整體多量含有機能性添加劑,熱塑性樹脂發泡粒子1之2次發泡性仍不會受到阻礙,可維持發泡粒子成形體之熔接性。因此,在使發泡粒子模內成形時,即使不進行提高成形壓力、或預先將發泡粒子加壓等操作,仍可多量含有機能性添加劑,並且獲得熔接率高、尺寸安定性及外觀優異之發泡粒子成形體。又,針對使用熱塑性樹脂發泡粒子1而形成之熱塑性樹脂發泡粒子成形體,可調整機能性添加劑之種類、添加量,故可獲得賦予有各樣機能性之發泡粒子成形體。
[熱塑性樹脂發泡粒子1之調製方法]
熱塑性樹脂發泡粒子1可藉由例如以下方法而調製。具體而言,準備2台擠壓機,於其中一擠壓機混練用以形成芯層2之熱塑性樹脂組成物,於另一擠壓機混練用以形成被覆層3之熱塑性樹脂組成物。之後,藉由進行從附設於擠壓機之出口側之特定形狀之模具共擠壓,獲得包括芯
層(R)、被覆芯層(R)之被覆層(R)之鞘芯型繩狀複合體。然後,藉由使用具備拉取機之切斷機以特定質量或大小將經共擠壓之繩狀複合體切斷,而可獲得包括非發泡之芯層(R)與被覆層(R)之柱狀複合樹脂粒子。再者,樹脂粒子之重量較佳係0.1至10mg。
就發泡劑而言,可列舉有機系物理發泡劑、無機系物理發泡劑。就有機系物理發泡劑而言,可列舉脂肪族烴,例示如:丙烷、丁烷、戊烷、己烷、庚烷、環丁烷、環戊烷、環己烷等。就無機系物理發泡劑而言,例示如:空氣、氮、二氧化碳、氧、氬、水等。
本發明之發泡粒子可由下述方法而得。首先,對在可加壓之密閉容器(例如,高壓釜)內之水性媒介(通常水)中與分散劑一起分散之包括前述芯層(R)與前述被覆層(R)之樹脂粒子,在特定加壓、加溫下含浸發泡劑而獲得發泡性樹脂粒子。之後,在適宜發泡之溫度條件下將容器內容物與水性媒介一起由容器內壓力釋放至低壓區域而使發泡性樹脂粒子發泡,藉此可獲得發泡粒子。
又,對所得之發泡粒子進行由空氣等氣體所致之加壓處理,使發泡粒子之氣泡內壓力提高後,將其以蒸汽等加熱而使其發泡(二階段發泡),藉此可獲得發泡倍率更高之發泡粒子。
就前述分散劑而言,可列舉氧化鋁、第三磷酸鈣、焦磷酸鎂、氧化鋅、高嶺土、雲母等難溶於水之無機物質;聚乙烯基吡咯啶酮、聚乙烯醇、甲基纖維素等
水溶性高分子系保護膠體劑。又,亦可使用十二基苯磺酸鈉、烷磺酸鈉等陰離子系界面活性劑等。
(體密度)
從輕量性之觀點而言,前述發泡粒子之體密度較佳係0.3g/cm3以下。前述發泡粒子即使體密度為0.3g/cm3以下,仍可獲得優異的二次發泡性,並且模內成形性亦優異。前述體密度更佳係0.01至0.25g/cm3,再更佳係0.02至0.2g/cm3。
(平均氣泡徑)
本發明之發泡粒子之被覆層3之平均氣泡徑係40至300μm。平均氣泡徑未達40μm時,發泡粒子成形體之壓縮永久應變、反發彈性模數等物性有降低之虞。另一方面,平均氣泡徑超過300μm時,有變得難以獲得良好的發泡粒子成形體之虞。從上述觀點而言,前述平均氣泡徑較佳係40至280μm,更佳係50至250μm。
(獨立氣泡率)
從模內成形性之觀點而言,前述發泡粒子之獨立氣泡率較佳係70%以上,更佳係80%以上,再更佳係90%以上。
再者,平均氣泡徑、體密度、及獨立氣泡率可由後述實施例所記載之方法而求得。
本發明之發泡粒子為聚丙烯系樹脂發泡粒子時,具有二次結晶,該二次結晶之由示差熱分析所得之熔解熱量較佳係1至30J/g。
亦即,將前述聚丙烯系樹脂發泡粒子2至10mg,藉由
熱流示差掃描熱量測定法,以10℃/分鐘之昇溫速度從23℃加熱至220℃時所得之DSC曲線(第1次加熱之DSC曲線)具有聚丙烯系樹脂固有之吸熱峰值A(以下,亦簡稱為「固有峰值」)、與位於該固有峰值之高溫側之源自前述二次結晶之1個以上之吸熱峰值B(以下,亦簡稱為「高溫峰值」),該高溫峰值之熔解熱量(以下,亦簡稱為高溫峰值熱量)較佳係1至30J/g。藉由使該高溫峰值熱量為上述範圍內,可獲得成形熔接性優異之發泡粒子成形體。
再者,就獲得具有前述DSC曲線中之高溫峰值之發泡粒子之方法而言,首先,前述發泡粒子製造步驟中,將密閉容器在比聚烯烴系樹脂之熔點(Tm)低20℃之溫度(Tm-20)℃以上、且未達聚烯烴系樹脂之熔解結束溫度(T)之範圍內之任意溫度(Ta)保持充分時間,較佳係保持10至60分鐘左右(第一階段保持步驟)。然後,將密閉容器調節為比熔點(Tm)低15℃之溫度至熔解結束溫度(T)+10℃之範圍之任意溫度(Tb)。此時,依需要而將密閉容器於該溫度進一步保持充分時間,較佳係保持10至60分鐘左右(第二階段保持步驟)。然後,將發泡性樹脂粒子由密閉容器內釋放至低壓下而發泡。藉由如此方法,可獲得具有高溫峰值之發泡粒子。
(熱塑性樹脂發泡粒子成形體)
本發明之熱塑性樹脂發泡粒子成形體係使用熱塑性樹脂發泡粒子1藉由模內成形而成形。又,熱塑性樹脂發泡粒子成形體係亦可併用本發明之熱塑性樹脂發泡粒子1、
與公知之熱塑性樹脂發泡粒子而成形。熱塑性樹脂發泡粒子成形體之形狀無特別限定,可適宜設定為板狀、柱狀、或各種立體形狀。
[熱塑性樹脂發泡粒子成形體之成形方法]
熱塑性樹脂發泡粒子成形體可使用例如模內成形法而調製。具體而言,首先,準備設計為所期望的形狀之模具。然後,將上述熱塑性樹脂發泡粒子1填充於模具內,將蒸汽供給至模具內而將模具內加熱。此時,相鄰之熱塑性樹脂發泡粒子1之被覆層3互相熔接,進一步熱塑性樹脂發泡粒子1進行二次發泡而填補發泡粒子間之間隙,填充於模具內之多數熱塑性樹脂發泡粒子1一體化。之後,將模具冷卻並從模具內取出內容物,獲得熱塑性樹脂發泡粒子成形體。
(表觀密度)
熱塑性樹脂發泡粒子成形體之表觀密度無特別限定,較佳係0.015至0.45g/cm3,更佳係0.02至0.3g/cm3,再更佳係0.03至0.2g/cm3。發泡粒子成形體之表觀密度可藉由將成形體之質量除以成形體之體積而求得。成形體之體積可從成形體之外形尺寸等而求得。
(熔接率)
從獲得尺寸安定性、外觀優異之熱塑性樹脂發泡粒子成形體之觀點而言,構成熱塑性樹脂發泡粒子成形體之前述熱塑性樹脂發泡粒子1之熔接率宜為60%以上,較佳係70%以上,更佳係80%以上。
(抗彎強度)
前述發泡粒子成形體之抗彎強度係藉由JIS K7221-2(1999年)所記載之方法而測定。具體而言,首先,從發泡粒子成形體切出120×25×20mm之不具有成形表面之試樣片。然後,針對試樣片,使用島津製作所製AUTOGRAPH裝置,以支點間距離100mm、試驗速度10mm/min之條件進行三點彎曲試驗,而測定成形體之抗彎強度。
(成形體收縮率)
由本發明之發泡粒子所得之發泡粒子成形體具有前述特定氣泡構造,故成形體之收縮率小。成形體之收縮率較佳係3%以下。再者,成形體之收縮率係由後述所記載之方法而測定。
(50%壓縮應力)
由本發明之發泡粒子所得之發泡粒子成形體之50%壓縮應力較佳係5MPa以下。再者,成形體之50%壓縮應力係依據JIS K6767(1999年)而測定。
(實施例)
以下,藉由實施例而更詳細地說明本發明。
使用以下原料而調製原料母料(masterbatch;MB),獲得表3、4所示之實施例1至8及比較例1至4之熱塑性樹脂發泡粒子。
(原料)
熱塑性樹脂:表1所示之聚丙烯系樹脂
機能性添加劑:表2所示之機能性添加劑
[原料母料(MB)之調製]
將表1之PP與表2之機能性添加劑以表3、4所示之調配割合供給至內徑20mm之二軸擠壓機,於200至220℃溶融混練而擠壓為股線(strand)狀,將該股線冷卻、切斷而獲得含有機能性添加劑之芯層形成用母料、被覆層形成用母料。
[熱塑性樹脂粒子(樹脂粒子)之製造]
(實施例1)
準備於內徑65mm之樹脂粒子芯層用擠壓機及內徑30mm之樹脂粒子被覆層用擠壓機之出口側附設有多層股線形成用模具之擠壓機。以成為表3所示之調配之方式,將上述芯層形成用母料供給至內徑65mm之樹脂粒子芯層用擠壓機,又同時將上述被覆層形成用母料供給至內徑30mm之樹脂粒子被覆層用擠壓機。分別於溫度200至220℃加熱,溶融、混練後,供給至前述模具,於模具內合流。然後,從裝設於擠壓機前端之模嘴之細孔,以於芯層側面被覆有被覆層之多層股線之形式共擠壓。然後,將該經共擠壓之股線水冷,使用製粒機以成為2mg、L/D=2.4之方式切斷而獲得形成為2層(鞘芯構造)之圓柱狀之表3所記載之樹脂粒子。再者,以使被覆層中之含量成為1000質量ppm之方式將作為氣泡調整劑之硼酸鋅供給至被覆層用擠壓機。又,芯層:被覆層之質量比設為10:90。
[熱塑性樹脂發泡粒子(發泡粒子)之製造]
將上述樹脂粒子1kg與分散媒介之水3L一起放入5L
之高壓釜內,於分散媒介中分別添加作為分散劑之高嶺土3g、作為分散助劑之烷基苯磺酸鈉0.04g、及硫酸鋁0.1g。以成為表3所示之容器內壓力之方式將作為發泡劑之二氧化碳壓入密閉容器內,一邊攪拌分散媒介一邊將密閉容器加熱昇溫至發泡溫度。將密閉容器於發泡溫度保持15分鐘,調整樹脂粒子之高溫峰值熱量之後,將高壓釜內容物在大氣壓下與水一起放出,而獲得表3所記載之熱塑性樹脂發泡粒子。
[熱塑性樹脂發泡粒子成形體(發泡粒子成形體)之製造]
將前述發泡粒子填充於長250mm(長邊)×寬200mm×厚50mm之平板成形模穴(cavity),進行藉由蒸汽加熱之模內成形而獲得板狀發泡成形體。此時,首先在將兩面之成形模之排洩閥開放之狀態將蒸汽5秒供給至成形模而預備加熱(排氣步驟),然後藉由正式加熱壓力以0.04MPa(G)低壓力進行一方向加熱,然後藉由正式加熱壓力以0.02MPa(G)低壓力從相反方向進行一方向加熱,然後以表3所示之成形加熱蒸氣壓力(成形壓力)加熱,將發泡粒子進行模內成形。
再者,成形壓力係可獲得成形體不會大幅收縮且外觀優異之成形體之最低壓力。加熱結束後,將成形模內放壓,進行水冷直到成形體之發泡力所致之成形體之表面壓力成為0.04MPa(G)為止之後,將成形模開放而將成形體從成形模取出。將所得之成形體於80℃之烘箱中熟
化12小時,而獲得發泡粒子成形體。將所得之發泡粒子成形體之物性表示於表3。
(實施例2至8)
除了變更為表3、4所示之條件以外,以與實施例1同樣方式而獲得樹脂粒子、發泡粒子、發泡粒子成形體。
(實施例9)
除了變更為表4所示之條件以外,以與實施例1同樣方式而獲得樹脂粒子、發泡粒子。針對所得之發泡粒子進行藉由空氣之加壓處理,使發泡粒子之氣泡內壓力提高後,使用蒸汽加熱而發泡,藉此獲得二階段發泡粒子。將二階段發泡粒子以與實施例1同樣之條件進行模內成形,獲得發泡粒子成形體。
再者,賦予於發泡粒子之氣泡內壓力係0.12MPa,二階段發泡時之蒸汽壓係0.09MPa,發泡粒子之芯層平均氣泡徑係27μm。又,將二階段發泡後之發泡粒子之體密度表示於表4。
(比較例1)
以使表1之PP1成為85.9質量%、表2之CB1成為14質量%、及硼酸鋅之含量成為1000質量ppm之方式將該等供給至內徑50mm單軸擠壓機,於200至220℃溶融混練並擠壓成股線狀。將該股線冷卻,使用製粒機以成為2mg、L/D=2.4之方式切斷而獲得表3所記載之單層之樹脂粒子。除此以外,以與實施例1同樣方式而獲得樹脂粒子、發泡粒子、發泡粒子成形體。
(比較例2)
除了變更為表3所示之條件以外,以與實施例1同樣方式而獲得樹脂粒子、發泡粒子、發泡粒子成形體。
(比較例3)
以使表1之PP1成為85.9質量%、表2之CB1成為14質量%、及硼酸鋅之含量成為1000質量ppm之方式將該等供給至內徑50mm單軸擠壓機,於200至220℃溶融混練並擠壓成股線狀。將該股線冷卻,使用製粒機以成為2mg、L/D=2.4之方式切斷而獲得樹脂粒子1。以使表1之PP2成為99.4質量%、表2之CB2成為0.5質量%、及硼酸鋅之含量成為1000質量ppm之方式將該等供給至內徑50mm之單軸擠壓機,於200至220℃溶融混練並擠壓成股線狀。將該股線冷卻,使用製粒機以成為2mg、L/D=2.4之方式切斷而獲得樹脂粒子2。使上述樹脂粒子1以與比較例1同樣條件進行發泡,而獲得體密度0.078g/cm3之發泡粒子1。又,使樹脂粒子2以與實施例1同樣條件進行發泡,而獲得體密度0.065g/cm3之發泡粒子2。將發泡粒子1與2以重量比率成為15:85之方式使用滾筒(tumbler)混合,將其以與實施例1同樣條件進行模內成形,而獲得發泡粒子成形體。
所得之發泡粒子成形體之熔接率係95%,抗彎強度係498kPa,密度係0.054g/cm3,收縮率係2.2%,二次發泡性係△,表面平滑性係△,成形體不均係×,50%壓縮應力係468kPa。
(比較例4)
除了變更為表4所示之條件以外,以與實施例1同樣方式而嘗試製作樹脂粒子。然而,芯層之機能性添加劑之含量過多,故擠壓壓力變得過高,而無法獲得樹脂粒子。因此,放棄發泡粒子成形體之製作。
再者,表3、4中,被覆層/芯層質量比係表示於樹脂粒子總質量中所佔之被覆層、芯層各自之質量比率(%)。
發泡粒子及發泡粒子成形體之物性評估係以下述方法而進行。
[發泡粒子之體密度]
發泡粒子之體密度係以如下述方式而求得。首先,準備1L之量筒,將發泡粒子群填充直到量筒內之1L標記線為止。測定已填充之每1L之發泡粒子群之質量(g/L),進行單位換算而求得發泡粒子之體密度(g/cm3)。
[發泡粒子之獨立氣泡率]
發泡粒子之獨立氣泡率係以如下述方式而測定。將於恆溫室內放置10天之容積體積約20cm3之發泡粒子當作測定用試樣,如下述藉由沉水法而正確地測定表觀體積Va。使已測定表觀體積Va之測定用試樣充分乾燥後,依據ASTM-D2856-70所記載之步驟C,測定藉由東芝‧Beckman股份有限公司製「空氣比較式比重計930」而測定之測定用試樣之真正的體積之值Vx。然後,以該等之體積值Va及Vx為基礎,由下述式計算獨立氣泡率,將5個(N=5)試樣之平均值當作發泡粒子之獨立氣泡率。
(數7)
獨立氣泡率(%)=(Vx-W/ρ)×100/(Va-W/ρ)…(6)其中,
Vx:由上述方法所測定之發泡粒子之真正的體積,亦即構
成發泡粒子之樹脂之容積、與發泡粒子內之獨立氣泡部分之氣泡總容積之和(cm3)
Va:從將發泡粒子沉入有水之量筒時之水位上昇份所測定之發泡粒子之表觀體積(cm3)
W:發泡粒子測定用試樣之重量(g)
ρ:構成發泡粒子之樹脂之密度(g/cm3)
[發泡粒子之平均氣泡徑]
發泡粒子之平均氣泡徑係以如下述方式而測定。依據將發泡粒子如第3圖般地將以第1圖之B-B剖面而大略分成二等分之剖面使用顯微鏡所攝影之放大照片,如下述方式而求得。首先,於發泡粒子之剖面放大照片中,以通過發泡粒子之剖面中心之方式取從發泡粒子之上端表面至下端表面之最小距離之線段,畫出相對於該線段之垂直二等分線1。然後,測定從發泡粒子之左端表面至右端表面之線段1之長度。然後,將該長度設為Lc(μm),求取與直線1相交之氣泡之數Nc(個),將Lc除以Nc所得之值(Lc/Nc)當作1個發泡粒子之芯層2之平均氣泡徑。
又,發泡粒子之剖面放大照片中,從右端表面至左端表面畫出通過從發泡粒子之上端表面起100μm內側之曲線。然後,求取其長度Ls(μm)以及與曲線相交之氣泡之數Ns(個),將Ls除以Ns所得之值(Ls/Ns)當作1個發泡粒子之被覆層3之平均氣泡徑。針對10個發泡粒子進行該作業,將各發泡粒子之芯層2、被覆層3之平均氣泡徑進行相加平均所得之值當作發泡粒子之芯層2、被覆層3之平
均氣泡徑。
[發泡粒子之高溫峰值熱量]
將發泡粒子1至3mg藉由熱流示差掃描熱量計從25℃至200℃以10℃/分鐘之昇溫速度加熱時所得之DSC曲線(第1次加熱之DSC曲線)中,顯現熱塑性樹脂固有之具有頂點溫度PTmc之固有峰值Pc。又,該固有峰值之高溫側之溫度區域中顯現具有頂點溫度PTmd之1個以上之吸熱峰值Pd。該吸熱峰值Pd為本發明中之高溫峰值,且相當於發泡粒子之高溫峰值之熔解熱量(D)者為該吸熱峰值Pd之面積。再者,由前述發泡粒子製造時之保持操作所得之高溫峰值Pd,雖在如前述方式而測定之發泡粒子之第1次加熱之DSC曲線中顯現,但在得到第1次加熱之DSC曲線之後,從200℃以10℃/分鐘之冷卻速度冷卻至25℃並再度以10℃/分鐘之昇溫速度加熱至200℃時所得之第2次加熱之DSC曲線中卻不顯現。因此,第2次加熱之DSC曲線中僅顯現與固有峰值Pc同樣之吸熱峰值,故可容易地辨別固有峰值Pc與高溫峰值Pd。再者,將5個(N=5)發泡粒子之高溫峰值熱量之平均值當作發泡粒子之高溫峰值熱量。
[發泡粒子成形體之表觀密度]
發泡粒子成形體之表觀密度係藉由將成形體之質量(g)除以由成形體之外形尺寸所得之體積(cm3)而求得。
[成形體之熔接率]
成形體之熔接率係依據於使發泡粒子成形體破裂時之破裂面露出之發泡粒子中,經材料破壞之發泡粒子之數之
比率而求得。具體而言,首先,從發泡粒子成形體切出試驗片,使用美工刀於各試驗片形成約5mm之切痕後,從切痕部使試驗片破裂。然後,測定發泡粒子成形體之存在於破裂面之發泡粒子之個數(n)、與經材料破壞之發泡粒子之個數(b),將(b)與(n)之比(b/n)以百分率表示並當作熔接率(%)。
[收縮率]
發泡粒子成形體之收縮率[%]係由(250[mm]-成形體之長邊長度[mm])/250[mm]×100而求得。再者,「250[mm]」係指成形用模具之長邊尺寸。又,「成形體之長邊長度[mm]」係指計測將實施例及比較例所得之發泡粒子成形體在80℃環境下熟化12小時後,徐冷,進一步在23℃環境下熟化6小時後之發泡粒子成形體之長邊之長度所得之值。
[表面平滑性]
發泡粒子成形體之表面平滑性係以肉眼觀察成形體表面並依以下基準而評估。
◎:發泡粒子成形體之表面沒有皺褶或收縮、塌陷所致之凹凸而顯示良好的表面狀態。
○:於發泡粒子成形體之表面略微確認到有皺褶或收縮、塌陷所致之凹凸。
△:於發泡粒子成形體之表面明顯確認到有皺褶或收縮、塌陷所致之凹凸。
×:發泡粒子成形體之表面之皺褶或收縮、塌陷所致之凹凸顯著。
[二次發泡性]
發泡粒子成形體之二次發泡性係如下述方式評估。
○:成形體表面之發泡粒子間隙完全被填補。
△:略微確認到成形體表面之發泡粒子間隙。
×:成形體表面之發泡粒子間隙明顯未被填補。
[50%壓縮應力]
藉由測定發泡粒子成形體之50%壓縮應力,評估成形體之機械強度。首先,從成形體之中央部,除了成形時之表層以成為直方體狀之方式切出長50mm×寬50mm×厚25mm之試驗片。然後,針對該試驗片使用AUTOGRAPH AGS-X(島津製作所股份有限公司製),以壓縮速度10mm/分鐘,依據JIS K 6767(1999年),求取50%應變時之荷重。藉由將該荷重除以試驗片之受壓面積而求得50%壓縮應力[kPa]。
[電容量]
發泡粒子之電容量係使用山本電機Instrument股份有限公司製之電容量測定器CM113N而測定。探測器(probe)(A1407-8065)係使用檢測電極直徑98mm、保護電極外徑150mm、內徑100mm、電極寬50mm、電極間之絕緣距離2mm者。具體而言,首先,於水平面上設置成為相對電極之金屬板,於其上以圓部分成為底面之方式乘載內徑100mm×外徑150mm×高度100mm之絕緣體製圓筒。然後,於圓筒上以使保護電極與圓筒之間不產生間隙之方式設置測定探測器,測定電容量而進行測定器之原點調整。然後,
將在23℃、50%RH之條件下熟化1天後之發泡粒子以使隙間最少之方式裝填於相對電極上之圓筒內並使其剛剛好裝滿之後,於裝填有發泡粒子之圓筒上乘載測定探測器,測定發泡粒子之電容量。所測定之電容量,實施例1為0.326pF、實施例2為0.369pF。
[發泡粒子成形體之不均]
○:由於以單一發泡粒子構成,故發泡粒子成形體係均質地構成。
×:由於以2種發泡粒子構成,故發泡粒子成形體係不均質地構成。
[評估結果]
實施例1至9之發泡體係於發泡粒子之芯層高度填充機能性添加劑。又,發泡粒子之被覆層已發泡,並且相對於芯層,被覆層係多量含有機能性添加劑,故發泡粒子之模內成形時之2次發泡性優異。因此,即使多量含有機能性添加劑,仍確認可獲得熔接性、尺寸安定性優異,並且發泡粒子之間隙經填補,表面無皺褶或收縮、塌陷,外觀優異之成形體。據此,藉由使用調配有各種機能性添加劑之本發明之發泡粒子,可獲得發揮機能性添加劑之特性,並且收縮率小而尺寸安定性優異之發泡粒子成形體。
另一方面,比較例1係單層發泡粒子成形體之例,且於發泡粒子之芯層高度填充有機能性添加劑。因此,發泡粒子之2次發泡性及成形體之外觀仍殘留有課題,成形體之收縮率大,成形體之尺寸安定性差。
比較例2係因發泡粒子中之高度填充有機能性添加劑之芯層之質量比率高,故發泡粒子之二次發泡性差,成形體之收縮率大,成形體之尺寸安定性及外觀差。
比較例3係由混合有機能性添加劑含量不同之發泡粒子1及2之發泡粒子形成發泡粒子成形體。機能性添加劑含量多且顏色濃之發泡粒子1與顏色淡之發泡粒子2在外觀上有差異,可辨別兩者。比較例3中,可由目視確認成形體中分散存在有發泡粒子1,成形體不均質地構成。又,比較例3之製造方法所製作之複數個發泡粒子成形體之間,也可確認到成形體中之發泡粒子1之分散度程度有差異。再者,成形體中之由碳黑含量多之發泡粒子所成之部分與由碳黑含量少之發泡粒子所成之部分之成形收縮率之差異、二次發泡性之差異大,故所得之成形體之二次發泡性、表面平滑性差。
又,比較例4之芯層中所添加之填充材料濃度非常高,故無法製作樹脂粒子,無法獲得發泡體。
1‧‧‧熱塑性樹脂發泡粒子
2‧‧‧芯層
3‧‧‧被覆層
Claims (4)
- 一種熱塑性樹脂發泡粒子,其係含有選自無機粉體及無機纖維之1種以上之機能性添加劑,並且,該熱塑性樹脂發泡粒子包括由熱塑性樹脂所形成之芯層、與由熱塑性樹脂所形成之發泡狀態之被覆層,其中,前述被覆層與前述芯層之質量比係99:1至50:50,前述芯層中之機能性添加劑之含量(X)係5至90質量%,前述被覆層中之機能性添加劑之含量比前述芯層中之機能性添加劑之含量(X)少。
- 如申請專利範圍第1項所述之熱塑性樹脂發泡粒子,其中,前述被覆層中之機能性添加劑之含量未達20質量%(包含0)。
- 如申請專利範圍第1項或第2項所述之熱塑性樹脂發泡粒子,其中,前述機能性添加劑係導電性碳。
- 如申請專利範圍第1項或第2項所述之熱塑性樹脂發泡粒子,其中,形成前述芯層之熱塑性樹脂及形成前述被覆層之熱塑性樹脂皆為聚烯烴系樹脂。
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USRE48098E1 (en) | 2020-07-14 |
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