TW202212108A - 造形物及其製造方法 - Google Patents
造形物及其製造方法 Download PDFInfo
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- TW202212108A TW202212108A TW110122549A TW110122549A TW202212108A TW 202212108 A TW202212108 A TW 202212108A TW 110122549 A TW110122549 A TW 110122549A TW 110122549 A TW110122549 A TW 110122549A TW 202212108 A TW202212108 A TW 202212108A
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- 239000011701 zinc Substances 0.000 description 1
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Abstract
本發明提供一種製造容易且能夠於使用三維列印之造形中有效地提高機械特性之造形物之製造方法。
該造形物之製造方法包括以下步驟:準備樹脂組合物之步驟,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200;以及使用上述樹脂組合物,利用熱熔積層方式三維列印進行造形,藉此製造造形物之步驟。利用上述熱熔積層方式三維列印進行造形時之積層間距未達0.20 mm,且造形線寬未達0.20 mm。
Description
本發明係關於一種造形物及其製造方法,上述造形物及其製造方法使用了含有無機纖維及熱塑性樹脂之樹脂組合物。
三維列印無需射出成形中所使用之模具就能夠造形出無法藉由射出成形而成形之複雜之立體構造,因此近年來作為多種少量生產技術而備受關注。三維列印係根據由CAD(Computer Aided Design,電腦輔助設計)等輸入之三維資料而計算出較薄之剖面之形狀,基於該計算結果將材料積層為多層而造形立體物之技術,該三維列印亦稱為增材製造技術(Additive Manufacturing Technology)。另一方面,射出成形中,由於樹脂之流動狀態會因其於模具模腔內所處之位置而所有不同,故難以提高纖維配向。纖維配向較低意味著難以獲得纖維狀填料所帶來之補強效果,從而難以提高機械特性。
對於三維列印用材料(亦稱為增材製造材料),已知有各種方式,但從成本方面而言,其中材料擠出方式(亦稱為熱熔積層方式)較為有利,故而逐漸得以廣泛使用;上述材料擠出方式係藉由擠出頭內部之加熱機構使被稱為長絲之具有絲狀等形狀之熱塑性樹脂流動化,而後將其自噴嘴噴出至平台上,根據目標造形物之剖面形狀,一面一點一點地積層,一面進行冷卻固化,藉此進行造形。
熱熔積層方式三維列印中,若使用未調配添加劑之熱塑性樹脂(所謂的純淨樹脂)進行造形,則存在造形物之層間剝離、造形物之翹曲等問題。又,熱熔積層方式三維列印中,若使用調配有玻璃纖維、碳纖維等纖維狀填料之熱塑性樹脂組合物,則存在擠出頭堵塞、擠出頭磨耗等導致造形困難之問題。進而,若調配無機填料,則會阻礙造形物中之層間熔合,使層間之剝離強度下降,使造形物之機械特性下降。
對此,下述專利文獻1中記載有以下內容:藉由使用含有無機纖維及熱塑性樹脂之樹脂組合物,製造容易,且能夠於使用三維列印之造形中改善造形物之層間剝離、造形物之翹曲及收縮,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200。
[先前技術文獻]
[專利文獻]
[專利文獻1]國際公開第2018/043231號
[發明所欲解決之問題]
近年來,關於藉由纖維狀填料得以強化之造形物,業界對其用於汽車構件或電子機器構件等多種多樣之用途進行了研究,其機械特性需要進一步提高。
然而,專利文獻1之造形物中,亦存在難以更加充分地提高機械特性之問題。又,為了提高機械特性,考慮過增加無機纖維之添加量,但發現若高度填充無機纖維,則會使熔融流動性下降。因此,存在下述問題,即,利用高度填充有無機纖維之樹脂組合物之三維列印的造形較為困難。
本發明之目的在於提供一種製造容易且能夠於使用三維列印之造形中有效地提高機械特性之造形物及其製造方法。
[解決問題之技術手段]
本發明提供以下造形物及其製造方法。
第1項:一種造形物之製造方法,其包括:準備樹脂組合物之步驟,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200;及使用上述樹脂組合物,利用熱熔積層方式三維列印進行造形,藉此製造造形物之步驟;且利用上述熱熔積層方式三維列印進行造形時之積層間距未達0.20 mm,且造形線寬未達0.20 mm。
第2項:如第1項所記載之造形物之製造方法,其中於將上述熱塑性樹脂之MFR值設為MFR1,將上述樹脂組合物之MFR值設為MFR2時,由MFR2/MFR1所表示之MFR之比為0.10以上0.90以下。
第3項:如第1項或第2項所記載之造形物之製造方法,其中於上述樹脂組合物之合計量100質量%中,上述無機纖維之含量為1質量%以上45質量%以下。
第4項:如第1項至第3項中任一項所記載之造形物之製造方法,其中造形速度為20 mm/秒以上200 mm/秒以下。
第5項:如第1項至第4項中任一項所記載之造形物之製造方法,其中上述無機纖維之莫氏硬度為5以下。
第6項:如第1項至第5項中任一項所記載之造形物之製造方法,其中上述無機纖維為鈦酸鉀及矽灰石中之至少一者。
第7項:如第1項至第6項中任一項所記載之造形物之製造方法,其中上述熱塑性樹脂為選自由聚烯烴樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚縮醛樹脂、聚碳酸酯樹脂、脂肪族聚醯胺樹脂、半芳香族聚醯胺樹脂、聚苯硫醚樹脂、聚醚醯亞胺樹脂、及聚醚醚酮樹脂所組成之群中之至少一種。
第8項:一種造形物,其藉由如第1項至第7項中任一項所記載之造形物之製造方法而獲得。
第9項:一種造形物,其係包含樹脂組合物之熱熔積層方式三維列印造形物,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200,上述造形物之積層間距未達0.20 mm且造形線寬未達0.20 mm。
第10項:如第9項所記載之造形物,其中於將上述熱塑性樹脂之MFR值設為MFR1,將上述樹脂組合物之MFR值設為MFR2時,由MFR2/MFR1所表示之MFR之比為0.10以上0.90以下。
第11項:如第9項或第10項所記載之造形物,其中於上述樹脂組合物之合計量100質量%中,上述無機纖維之含量為1質量%以上45質量%以下。
[發明之效果]
根據本發明,能夠提供一種製造容易且能夠於使用三維列印之造形中有效地提高機械特性之造形物及其製造方法。
以下,對實施本發明之較佳形態之一例進行說明。但,以下實施方式僅為示例。本發明不受以下實施方式任何限定。
[造形物之製造方法]
本發明之造形物之製造方法包括以下步驟:準備樹脂組合物之步驟,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200(步驟Ⅰ);及使用樹脂組合物,利用熱熔積層方式三維列印進行造形,藉此製造造形物之步驟(步驟II)。本發明中,利用熱熔積層方式三維列印進行造形時之積層間距未達0.20 mm,且造形線寬未達0.20 mm。
本發明之造形物之製造方法中,使用了含有平均纖維長度為1 μm~300 μm且平均長徑比為3~200之無機纖維之樹脂組合物,因此,能夠於使用三維列印之造形中改善造形物之層間剝離、造形物之翹曲等。
又,利用熱熔積層方式三維列印進行造形時之積層間距未達0.20 mm,且造形線寬未達0.20 mm,因此製造容易,且能夠賦予造形物更加優異之機械特性。
再者,於先前藉由使用三維列印之造形所獲得之造形物中,存在難以更加充分地提高機械特性之問題。又,為了提高機械特性,考慮過增加無機纖維之添加量之方法,但若高度填充無機纖維,則熔融流動性呈現下降趨勢。因此,存在下述問題:難以利用高度填充有無機纖維之樹脂組合物之三維列印進行造形。
對此,本發明人等著眼於利用熱熔積層方式三維列印進行造形時之積層間距及造形線寬,發現藉由將上述積層間距及造形線寬設為未達特定值,能夠賦予造形物更加優異之機械特性。
又,本發明人等發現,若將上述積層間距及造形線寬設為未達上述特定值,出乎意料地,即使於使用高度填充有無機纖維之樹脂組合物之情形時,該樹脂組合物亦能於熔融時穩定地流動,從而利用三維列印之造形成為可能。本發明人等認為,由於樹脂被穩定地噴出,故積層之樹脂易於彼此密接,機械強度提高。
因此,根據本發明之造形物之製造方法,製造容易,且能夠於使用三維列印之造形中改善造形物之層間剝離、造形物之翹曲等,還能夠有效地提高機械特性。
再者,本發明中,「造形物」亦包括「造形體」、「成形體」、「成形物」。
以下,對本發明之造形物之製造方法之各步驟進行說明。
<步驟Ⅰ>
步驟Ⅰ中,準備樹脂組合物,上述樹脂組合物含有平均纖維長度為1 μm~300 μm且平均長徑比為3~200之無機纖維(A)、及熱塑性樹脂(B),視需要進而含有其他添加劑(C)。
(無機纖維(A))
本發明中所使用之無機纖維係包含纖維狀粒子之粉末,平均纖維長度為1 μm~300 μm,且平均長徑比為3~200。平均纖維長度較佳為1 μm~200 μm,更佳為3 μm~100 μm,進而較佳為5 μm~50 μm。平均長徑比較佳為3~100,更佳為5~50,進而較佳為8~40。藉由使用具有上述平均纖維長度及平均長徑比之無機纖維,能夠於使用三維列印之造形中進一步改善造形物之層間剝離、造形物之翹曲等。藉由提高造形物之剝離強度,能夠更進一步提高造形物之機械特性。
從擠出頭磨耗之方面而言,本發明中所使用之無機纖維之莫氏硬度較佳為5以下,更佳為1~5,進而較佳為2~5。作為無機纖維,例如可列舉:鈦酸鉀、矽灰石、硼酸鋁、硼酸鎂、硬矽鈣石、氧化鋅、鹼式硫酸鎂等。從機械特性之方面而言,上述各種無機纖維中,較佳為選自鈦酸鉀及矽灰石中之至少一者。所謂莫氏硬度,係表示物質硬度之指標,將礦物彼此摩擦,受損一方為硬度較小之物質。
鈦酸鉀可廣泛使用先前公知者,可列舉四鈦酸鉀、六鈦酸鉀、八鈦酸鉀等。鈦酸鉀之尺寸只要處於上述無機纖維之尺寸之範圍內則並無特別限制,通常情況下,平均纖維直徑為0.01 μm~1 μm,較佳為0.05 μm~0.8 μm,更佳為0.1 μm~0.7 μm,平均纖維長度為1 μm~50 μm,較佳為3 μm~30 μm,更佳為10 μm~20 μm,平均長徑比為10以上,較佳為10~100,更佳為15~35。本發明中亦可使用市售品,例如可使用大塚化學公司製之「TISMO D」(平均纖維長度15 μm,平均纖維直徑0.5 μm)、「TISMO N」(平均纖維長度15 μm,平均纖維直徑0.5 μm)等。
矽灰石為包含偏矽酸鈣之無機纖維。矽灰石之尺寸只要處於上述無機纖維之尺寸之範圍內則並無特別限制,通常情況下,平均纖維直徑為0.1 μm~15 μm,較佳為1 μm~10 μm,更佳為2 μm~7 μm,平均纖維長度為3 μm~180 μm,較佳為10 μm~100 μm,更佳為20 μm~40 μm,平均長徑比為3以上,較佳為3~30,更佳為5~15。本發明中亦可使用市售品,例如可使用大塚化學公司製之「Baystal W」(平均纖維長度25 μm,平均纖維直徑3 μm)等。
上述平均纖維長度及平均纖維直徑可藉由掃描式電子顯微鏡(SEM)之觀察而測定,平均長徑比(平均纖維長度/平均纖維直徑)可由平均纖維長度及平均纖維直徑算出。例如,可藉由掃描式電子顯微鏡(SEM)對複數個無機纖維進行拍攝,從其觀察圖像中任意選擇300個無機纖維,測定該等無機纖維之纖維長度及纖維直徑,將所有纖維直徑之和除以個數所得者作為平均纖維長度,將所有纖維直徑之和除以個數所得者作為平均纖維直徑。
本發明中,所謂纖維狀之粒子,係指於將外接於粒子之長方體中體積最小之長方體(外接長方體)之最長邊定義為長軸L,第二長之邊定義為短軸B,最短邊定義為厚度T(B>T)時,L/B及L/T中之任一者均為3以上之粒子,長軸L相當於纖維長度,短軸B相當於纖維直徑。所謂板狀之粒子,係指L/B小於3且L/T為3以上之粒子。
關於無機纖維,為了提高其與熱塑性樹脂之潤濕性,進一步提高所獲得之樹脂組合物之機械特性等物性,可於本發明所使用之無機纖維之表面形成包含表面處理劑之處理層。作為表面處理劑,可列舉矽烷偶合劑、鈦偶合劑等。該等之中,較佳為矽烷偶合劑,進而較佳為胺基系矽烷偶合劑、環氧系矽烷偶合劑、乙烯基系矽烷偶合劑、烷基系矽烷偶合劑。該等可單獨使用1種,亦可混合使用2種以上。
作為胺基系矽烷偶合劑,例如可列舉:N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷等。
作為環氧系矽烷偶合劑,例如可列舉:3-縮水甘油氧基丙基(二甲氧基)甲基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、二乙氧基(3-縮水甘油氧基丙基)甲基矽烷、三乙氧基(3-縮水甘油氧基丙基)矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等。
作為乙烯基系矽烷偶合劑,例如可列舉:乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等。
作為烷基系矽烷偶合劑,例如可列舉:甲基三甲氧基矽烷、二甲基二甲氧基矽烷、三甲基甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、正丙基三甲氧基矽烷、異丁基三甲氧基矽烷、異丁基三乙氧基矽烷、正己基三甲氧基矽烷、正己基三乙氧基矽烷、環己基甲基二甲氧基矽烷、正辛基三乙氧基矽烷、正癸基三甲氧基矽烷等。
於無機纖維之表面形成包含表面處理劑之處理層之方法可使用公知之表面處理方法,例如可使用:使表面處理劑溶解於促進水解之溶劑(例如:水、醇或該等之混合溶劑)中製成溶液,將該溶液噴霧至無機纖維之濕式法;將無機纖維及表面處理劑調配至樹脂組合物中之整體摻合法等。
於藉由表面處理劑對本發明之無機纖維之表面進行處理時,該表面處理劑之量並無特別限定,於濕式法之情形時,可以下述方式噴霧表面處理劑之溶液:相對於無機纖維100質量份,表面處理劑較佳為0.1質量份~5質量份,更佳為0.3質量份~2質量份。又,於整體摻合法之情形時,可以下述方式將表面處理劑調配至樹脂組合物:相對於無機纖維100質量份,表面處理劑為0.1質量份~20質量份。藉由使表面處理劑之量處於上述範圍內,能夠進一步提高與熱塑性樹脂之密接性,進一步提高無機纖維之分散性。
(熱塑性樹脂(B))
作為用於樹脂組合物之熱塑性樹脂,只要是具有下述熔融時之流動特性之可於熱熔積層方式三維列印中使用者,即,能夠穩定地噴出而不會降低後述頭部進給速度,則可使用結晶性樹脂及非結晶性樹脂中之任一者,從流動性之方面而言,較佳為結晶性樹脂。所謂結晶性樹脂,係指存在分子鏈有規律地排列之結晶、且具有明確之熔點的熱塑性樹脂。再者,熔點可藉由示差掃描熱析法(DSC)而特定出。
更具體而言,作為熱塑性樹脂,例如可例示:聚丙烯(PP)樹脂、聚乙烯(PE)樹脂、環狀聚烯烴(COP)樹脂、環狀烯烴共聚物(COC)樹脂等聚烯烴樹脂;聚苯乙烯(PS)樹脂、對排聚苯乙烯(SPS)樹脂、耐衝擊性聚苯乙烯(HIPS)樹脂、丙烯腈-丁烯-苯乙烯共聚物(ABS)樹脂等聚苯乙烯系樹脂;聚乳酸(PLA)樹脂、聚對苯二甲酸乙二酯(PET)樹脂、聚對苯二甲酸丁二酯(PBT)樹脂等聚酯系樹脂;聚縮醛(POM)樹脂;聚碳酸酯(PC)樹脂;聚醯胺6樹脂、聚醯胺66樹脂、聚醯胺11樹脂、聚醯胺12樹脂、聚醯胺46樹脂、聚醯胺6樹脂與聚醯胺66樹脂之共聚物(聚醯胺6/66樹脂)、聚醯胺6樹脂與聚醯胺12樹脂之共聚物(聚醯胺6/12樹脂)等脂肪族聚醯胺(PA)樹脂;聚醯胺MXD6樹脂、聚醯胺MXD10樹脂、聚醯胺6T樹脂、聚醯胺9T樹脂、聚醯胺10T樹脂等包含具有芳香環之結構單位及不具有芳香環之結構單位之半芳香族聚醯胺(PA)樹脂;聚苯硫醚(PPS)樹脂;聚醚碸(PES)樹脂;液晶聚酯(LCP)樹脂;聚醚酮(PEK)樹脂、聚醚醚酮(PEEK)樹脂、聚醚酮酮(PEKK)樹脂、聚醚醚酮酮(PEEKK)樹脂等聚醚芳香族酮樹脂;聚醚醯亞胺(PEI)樹脂;聚醯胺醯亞胺(PAI)樹脂;熱塑性聚醯亞胺(TPI)樹脂等。
上述熱塑性樹脂之中,較佳為聚烯烴樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚縮醛樹脂、聚碳酸酯樹脂、脂肪族聚醯胺樹脂、半芳香族聚醯胺樹脂、聚苯硫醚樹脂、聚醚醯亞胺樹脂、聚醚醚酮樹脂,更佳為脂肪族聚醯胺樹脂、半芳香族聚醯胺樹脂、聚苯硫醚樹脂、聚醚醚酮樹脂。
亦可使用選自上述熱塑性樹脂之具有相容性之2種以上熱塑性樹脂彼此之混合物,即聚合物合金等。
(其他添加劑(C))
本發明中所使用之樹脂組合物可於不損及其較佳物性之範圍內含有其他添加劑。作為其他添加劑,可列舉:耐衝擊改良劑;芳香族聚醯胺纖維、聚伸苯基苯并㗁唑(PBO)纖維、玻璃纖維、碳纖維、氧化鋁纖維、硼纖維、碳化矽纖維、碳酸鈣、硫酸鋇、雲母、雲母(mica)、絹雲母、伊利石、滑石、高嶺石、蒙脫石、軟水鋁石、膨潤石、蛭石、二氧化鈦、二氧化矽、鈦酸鉀、鈦酸鈉、鈦酸鎂鉀、鈦酸鋰鉀、軟水鋁石、玻璃珠、氧化鋁等上述無機纖維(A)以外之無機填充材;聚四氟乙烯(PTFE)、低密度聚乙烯、直鏈狀低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、超高分子量聚乙烯等聚烯烴樹脂、石墨、二硫化鉬、二硫化鎢、氮化硼等固體潤滑劑;銅化合物等熱穩定劑;受阻酚系光穩定劑等光穩定劑;成核劑;陰離子性抗靜電劑、陽離子性抗靜電劑、非離子系抗靜電劑等抗靜電劑;抗老化劑(抗氧化劑);耐候劑;金屬減活劑;二苯甲酮系紫外線吸收劑、苯并三唑系紫外線吸收劑、三𠯤系紫外線吸收劑、水楊酸酯系紫外線吸收劑等紫外線吸收劑;防菌防黴劑;防臭劑;碳系導電劑、金屬系導電劑、金屬氧化物系導電劑、界面活性劑等導電性賦予劑;分散劑;聚酯系塑化劑、甘油系塑化劑、多元羧酸酯系塑化劑、磷酸酯系塑化劑、聚伸烷基二醇系塑化劑、環氧系塑化劑等軟化劑(塑化劑);碳黑、氧化鈦等顏料、染料等著色劑;磷腈系化合物、磷酸酯、縮合磷酸酯、無機磷系阻燃劑、鹵素系阻燃劑、矽酮系阻燃劑、金屬氧化物系阻燃劑、金屬氫氧化物系阻燃劑、有機金屬鹽系阻燃劑、氮系阻燃劑、硼化合物系阻燃劑等阻燃劑;抗滴落劑;制振劑;中和劑;抗黏連劑;流動性改良劑;脂肪酸、脂肪酸金屬鹽等脫模劑;潤滑劑等,可含有該等中之1種或2種以上。
作為耐衝擊改良劑,例如可列舉:(乙烯及/或丙烯)/α-烯烴系共聚物、(乙烯及/或丙烯)/(α,β-不飽和羧酸及/或不飽和羧酸酯)系共聚物、離子聚合物等烯烴系聚合物;苯乙烯系彈性體、胺基甲酸酯系彈性體、氟系彈性體、氯乙烯系彈性體、聚酯系彈性體、聚醯胺系彈性體等彈性體;聚硫(Thiokol)橡膠、多硫(polysulfide)橡膠、丙烯酸系橡膠、矽酮橡膠、聚醚橡膠、表氯醇橡膠等合成橡膠;天然橡膠等,從耐熱性之方面而言,較佳為烯烴系共聚物。可含有該等中之1種或2種以上。
上述(乙烯及/或丙烯)/α-烯烴系共聚物係使乙烯及/或丙烯與碳數為3以上之α-烯烴共聚而成之聚合物,作為碳數為3以上之α-烯烴,可列舉:丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一烯、1-十二烯、1-十三烯、1-十四烯、1-十五烯、1-十六烯、1-十七烯、1-十八烯、1-十九烯、1-二十烯、3-甲基-1-丁烯、4-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、9-甲基-1-癸烯、11-甲基-1-十二烯、12-乙基-1-十四烯、以及該等之組合。又,亦可共聚以下非共軛二烯之多烯:1,4-戊二烯、1,4-己二烯、1,5-己二烯、1,4-辛二烯、1,5-辛二烯、1,6-辛二烯、1,7-辛二烯、2-甲基-1,5-己二烯、6-甲基-1,5-庚二烯、7-甲基-1,6-辛二烯、4-亞乙基-8-甲基-1,7-壬二烯、4,8-二甲基-1,4,8-癸三烯(DMDT)、二環戊二烯、環己二烯、二環辛二烯、亞甲基降莰烯、5-乙烯基降莰烯、5-亞乙基-2-降莰烯、5-亞甲基-2-降莰烯、5-亞異丙基-2-降莰烯、6-氯甲基-5-異丙烯基-2-降莰烯、2,3-二亞異丙基-5-降莰烯、2-亞乙基-3-亞異丙基-5-降莰烯、2-丙烯基-2,2-降莰二烯等。
上述(乙烯及/或丙烯)/(α,β-不飽和羧酸及/或不飽和羧酸酯)系共聚物係使乙烯及/或丙烯與α,β-不飽和羧酸及/或不飽和羧酸酯單體共聚而成之聚合物,作為α,β-不飽和羧酸單體,可列舉丙烯酸、甲基丙烯酸,作為α,β-不飽和羧酸酯單體,可列舉該等不飽和羧酸之甲酯、乙酯、丙酯、丁酯、戊酯、己酯、庚酯、辛酯、壬酯、癸酯等,或該等之混合物。
上述離子聚合物係烯烴與α,β-不飽和羧酸共聚物之羧基之至少一部分藉由金屬離子之中和而離子化者。烯烴較佳為使用乙烯,α,β-不飽和羧酸較佳為使用丙烯酸、甲基丙烯酸,但並不限定於此處所例示者,亦可共聚不飽和羧酸酯單體。又,至於金屬離子,除了Li、Na、K、Mg、Ca、Sr、Ba等鹼金屬、鹼土類金屬以外,可列舉Al、Sn、Sb、Ti、Mn、Fe、Ni、Cu、Zn、Cd等。
上述耐衝擊改良劑亦可使用經羧酸及/或其衍生物改性之聚合物。藉由此種成分進行改性,例如可將對聚醯胺樹脂具有親和性之官能基導入該分子中。作為對聚醯胺樹脂具有親和性之官能基,可列舉羧酸基、羧酸酐基、羧酸酯基、羧酸金屬鹽基、羧酸醯胺基、環氧基等。
(樹脂組合物之製造方法)
樹脂組合物可藉由將無機纖維(A)及熱塑性樹脂(B),視需要進而將其他添加劑(C)之成分混合及加熱(尤其是熔融混練)而製造。
熔融混練中可使用例如二軸擠出機等公知之熔融混練裝置。具體而言,可藉由下述方法進行製造:(1)藉由混合機(滾筒、亨舍爾混合機等)對各成分進行預混合,藉由熔融混練裝置進行熔融混練,藉由顆粒化機構(造粒機等)使其顆粒化之方法;(2)對所需成分之母料進行調整,視需要混合其他成分,藉由熔融混練裝置進行熔融混練並使其顆粒化之方法;(3)將各成分供給至熔融混練裝置並使其顆粒化之方法等。
熔融混練中之加工溫度只要是熱塑性樹脂(B)能夠熔融之溫度則並無特別限定。通常情況下,將熔融混練所使用之熔融混練裝置之料缸溫度調整至該範圍內。
關於樹脂組合物之熔融黏度特性值,於將熱塑性樹脂(B)之MFR值設為MFR1,將樹脂組合物之MFR值設為MFR2時,由MFR2/MFR1所表示之MFR之比較佳為0.10以上,更佳為0.20以上,進而較佳為0.40以上,尤佳為0.60以上。又,MFR值之比較佳為0.90以下,更佳為0.80以下,進而較佳為0.75以下,尤佳為0.70以下。於MFR之比處於上述範圍內之情形時,能夠賦予造形物更加優異之機械特性。
本發明中所定義之MFR(熔體流動速率)值係表示樹脂熔融時之黏度(流動性)之指標,其係藉由MFR測定裝置於負荷5 kg之條件下依據JIS K7210而測定。若MFR值較大,則表示熔融時之黏度較低(易於流動);若MFR值較小,則表示熔融時之黏度較高(難以流動)。MFR測定裝置之設定溫度係根據三維列印之噴嘴溫度而適宜選擇,例如,於熱塑性樹脂(B)為結晶性樹脂之情形時,將溫度設定為比熔點高50℃左右。於熱塑性樹脂(B)為沒有熔點而有玻璃轉移溫度之非結晶性樹脂之情形時,將溫度設定為比玻璃轉移溫度高100℃左右。
於樹脂組合物之合計量100質量%中,樹脂組合物中之無機纖維(A)之含量較佳為1質量%以上,更佳為15質量%以上,進而較佳為超過25質量%,較佳為50質量%以下,更佳為45質量%以下,進而較佳為40質量%以下。於無機纖維(A)之含量為上述下限值以上之情形時,能夠賦予造形物更加優異之機械特性。又,於無機纖維(A)之含量為上述上限值以下之情形時,能夠進一步提高生產性。
於樹脂組合物之合計量100質量%中,樹脂組合物中之熱塑性樹脂(B)之含量較佳為40質量%以上,更佳為45質量%以上,進而較佳為50質量%以上,較佳為99質量%以下,更佳為97質量%以下,進而較佳為93質量%以下。於熱塑性樹脂(B)之含量為上述下限值以上之情形時,能夠進一步提高生產性。又,於熱塑性樹脂(B)之含量為上述上限值以下之情形時,能夠賦予造形物更加優異之機械特性。
其他添加劑(C)之含量只要處於不損及本發明之樹脂組合物之較佳物性之範圍內則並無特別限制,上述其他添加劑(C)係本發明可使用之上述必須成分以外之添加劑。通常情況下,於樹脂組合物之合計量100質量%中,其他添加劑(C)之含量為未達10質量%,較佳為未達5質量%,較佳為0.1質量%以上,更佳為1質量%以上。
藉由將樹脂組合物之各成分調整至上述範圍內,能夠於使用三維列印之造形中改善造形物之層間剝離、造形物之翹曲等。又,能夠提高造形物之機械特性。
如此,製造發揮所需效果之本發明之造形物所包含之樹脂組合物。
<步驟II>
步驟Ⅱ中,使用步驟Ⅰ中所準備之樹脂組合物,利用熱熔積層方式三維列印(亦稱為增材製造裝置)進行造形,藉此製造造形物。
所謂熱熔積層方式,係指藉由擠出頭內部之加熱機構使顆粒狀、被稱為長絲之具有絲狀等形狀之熱塑性樹脂流動化,而後將其自噴嘴噴出至平台上,一面一點一點地積層,一面進行冷卻固化,以此造形出所需之造形物之方法。藉由將上述樹脂組合物作為造形材料,能夠使用熱熔積層方式三維列印進行造形,而不會產生如使用調配有玻璃纖維、碳纖維等纖維狀填料之樹脂組合物時之擠出頭堵塞、擠出頭磨耗,即使是例如頭部直徑為0.5 mm以下之細噴嘴,亦能夠進行造形而不會產生擠出頭堵塞、擠出頭磨耗。進而,雖然理由尚不清楚,但發明人等認為不僅能夠藉由無機纖維(A)而改善造形物之翹曲,而且能夠藉由積層之層間之界面強度提高而抑製造形物之層間剝離。
製造長絲之方法並無特別限定,可列舉具有下述步驟之方法:擠出步驟,即,將利用上述方法所製造之上述樹脂組合物自成形機之模孔以熔融線料之形式擠出,導入至冷卻水槽,獲得線料;對線料進行加熱延伸而獲得長絲之延伸步驟;及捲取延伸而成之長絲之步驟。
上述長絲之形狀並無特別限定。例如,剖面形狀可例示圓形、方形、扁平狀、橢圓狀、繭狀、三葉狀、及與此類似之形狀之非圓形形狀。從操作之方面而言,較佳為圓形。長絲之長度並無限定,可根據工業上之製造條件或在不妨礙於熱熔積層方式三維列印中利用之範圍內設定為任意值。又,長絲之直徑亦並無特別限定,可例示0.5 mm~3 mm,尤其可例示1 mm~2 mm。再者,長絲之直徑係指對與長絲之長度方向垂直之方向之剖面進行測定所獲得的直徑中之最長者。
上述長絲可併用上述樹脂組合物以外之樹脂成分而製成複合長絲。作為複合長絲之剖面構成,可例示放射狀排列型、並列型、海島型、或芯鞘型之構成。
本發明之造形物之製造方法中,例如,可將包含上述樹脂組合物之長絲供給至熱熔積層方式三維列印而造形出造形物。具體而言,將長絲供給至熱熔積層方式三維列印,藉由擠出頭內部之加熱機構使其流動化,而後將其自噴嘴噴出至平台上,根據目標造形物之剖面形狀,一面一點一點地積層,一面進行冷卻固化,以此製造造形物。
本發明之製造方法中,利用熱熔積層方式三維列印進行造形時之積層間距未達0.20 mm,且造形線寬未達0.20 mm。積層間距較佳為0.15 mm以下,更佳為未達0.10 mm,進而較佳為0.08 mm以下。造形線寬較佳為0.18 mm以下,更佳為0.16 mm以下。藉由將積層間距及造形線寬設為未達上述上限值或上述上限值以下,能夠賦予造形物更加優異之機械特性。本說明書中,所謂積層間距,係指利用三維列印之造形中所形成之一層樹脂層之厚度,所謂造形線寬,係指自噴嘴噴出之樹脂組合物之直徑。
再者,利用熱熔積層方式三維列印進行造形時之積層間距之下限值並無特別限定,從製造之方面而言,例如可設為0.04 mm。又,造形線寬之下限值亦並無特別限定,從製造之方面而言,例如可設為0.07 mm。
從縮短造形物之製造時間之方面、及無機纖維之配向之方面而言,熱熔積層方式三維列印之印刷速度(頭部進給速度)較佳為20 mm/秒以上,更佳為40 mm/秒以上。但,若印刷速度過快,造形性會變差,因此,通常情況下印刷速度之上限值為200 mm/秒以下。
從頭部進給速度之方面而言,擠出頭之直徑較佳為小於0.5 mm,更佳為0.4 mm以下,進而較佳為0.3 mm以下,較佳為0.1 mm以上。又,積層間距較佳為設為擠出頭直徑之20%~50%,造形線寬較佳為設為擠出頭直徑之60%~80%。
自擠出頭噴出之熔融樹脂之溫度(噴出溫度)可根據所使用之熱塑性樹脂適宜選擇,以達到上述頭部進給速度。
認為於熱熔積層方式三維列印中,於將頭部進給速度控制於上述範圍內之情形時,一面將熔融樹脂中之無機纖維配向於噴出方向,一面於一定方向積層線料狀之樹脂,因此,造形物中之無機纖維之配向進一步提高。又,一面於一定方向積層自擠出頭噴出之線料狀之樹脂,一面製造造形物,因此,進一步難以產生因造形物之部位而導致之無機纖維配向之差異。認為藉此能夠賦予造形物更加優異之機械特性。
[造形物]
本發明之造形物係包含樹脂組合物之熱熔積層方式三維列印造形物,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200。本發明之造形物包含含有平均纖維長度為1 μm~300 μm且平均長徑比為3~200之無機纖維之樹脂組合物,因此製造容易,且能夠於使用三維列印之造形中改善造形物之層間剝離、造形物之翹曲等。再者,本發明之造形物例如可藉由上述造形物之製造方法而製造。因此,樹脂組合物可使用上述製造方法一欄中所說明之樹脂組合物。
關於本發明之造形物,其積層間距(每一層之厚度)未達0.20 mm,且造形線寬未達0.20 mm。積層間距較佳為0.15 mm以下,更佳為未達0.10 mm,進而較佳為0.08 mm以下。造形線寬較佳為0.18 mm以下,更佳為0.16 mm以下。藉由將積層間距及造形線寬設為未達上述上限值或上述上限值以下,能夠賦予造形物更加優異之機械特性。
關於本發明之造形物之樹脂組合物之熔融黏度特性值,於將熱塑性樹脂(B)之MFR值設為MFR1,將樹脂組合物之MFR值設為MFR2時,由MFR2/MFR1所表示之MFR之比較佳為0.10以上,更佳為0.20以上,進而較佳為0.40以上,尤佳為0.60以上。又,上述MFR值之比較佳為0.90以下,更佳為0.80以下,進而較佳為0.75以下,尤佳為0.70以下。於MFR之比處於上述範圍內之情形時,能夠賦予造形物更加優異之機械特性。
本發明之造形物的造形積層方向上之最大厚度較佳為1 mm以上,更佳為2 mm以上,進而較佳為4 mm以上,最小厚度較佳為1 mm以上,更佳為2 mm以上,進而較佳為4 mm以上,其能夠獲得於射出成形中無法獲得之優異效果。
本發明之造形物的無機纖維之配向角度較佳為24°以下。於無機纖維之配向角度為上述上限值以下之情形時,能夠將無機纖維所帶來之基質樹脂之補強效果提昇至最大限度,能夠賦予造形物更加優異之機械特性。
再者,所謂無機纖維之配向角度,係表示造形物內無機纖維之配向狀態者,於本發明中係指於將與造形物之造形時之造形行進方向平行之方向設為0°,將與造形行進方向垂直之方向設為90°時,無機纖維之長軸方向相對於造形行進方向所形成之角度。將無機纖維完全配向於造形行進方向之情形設為0°,無配向之情形設為45°,與造形行進方向垂直配向之情形設為90°。再者,於造形物為藉由射出成形而造形之構件之情形時,造形行進方向表示樹脂之流動方向。
本發明之造形物為機械特性優異者。因此,本發明之造形物可適宜用於需要機械特性之構造構件,例如,齒輪構件、軸承護圈、生產夾具。
[實施例]
以下,基於實施例及比較例具體地進行說明,但本發明不受此任何限定。再者,本實施例及比較例中所使用之原材料具體而言如下所示。又,無機纖維之平均纖維長度、平均纖維直徑、及平均長徑比係使用場發射型掃描電子顯微鏡(SEM,日立高新技術公司製,S-4800)而測定。
(無機纖維)
鈦酸鉀(商品名:TISMO D102,大塚化學公司製,平均纖維長度:15 μm,平均纖維直徑:0.5 μm,平均長徑比:30)
(熱塑性樹脂)
聚醯胺MXD10樹脂(商品名:LEXTER8000,三菱瓦斯化學公司製,熔點188℃)
聚苯硫醚(PPS)樹脂(商品名:TORELINA PPS L2120-60,東麗公司製,熔點280℃)
聚醚醚酮(PEEK)樹脂(商品名:PEEK 381G,VICTREX公司製,熔點343℃)
再者,於測定熔點時,使用示差掃描熱量計(DSC),以10℃/min之升溫速度將測定試樣加熱至預想之熔點以上之溫度。繼而,以10℃/min之降溫速度將測定試樣冷卻至0℃,保持原樣放置1分鐘。其後,測定再次以10℃/min之升溫速度進行加熱升溫時之熔解峰,將其作為熔點。
<樹脂組合物及長絲之製造>
以表1所示之調配比率,使用二軸擠出機進行熔融混練,分別製造顆粒。再者,二軸擠出機之料缸溫度於使用聚醯胺MXD10樹脂之情形時設為190℃~220℃,於使用PPS樹脂之情形時設為280℃~300℃,於使用PEEK樹脂之情形時設為330℃~380℃。
將所獲得之顆粒投入至長絲擠出機,獲得長絲直徑為1.75 mm之長絲。
[表1]
長絲No. | 1 | 2 | 3 | 4 | |
組成 | 聚醯胺MXD10樹脂 (質量%) | 70 | 80 | ||
PPS樹脂 (質量%) | 80 | ||||
PEEK樹脂 (質量%) | 80 | ||||
鈦酸鉀 (質量%) | 30 | 20 | 20 | 20 | |
熔融黏度特性值 | MFR2 (g/10分鐘) | 44.01 | 49.46 | 126.85 | 11.22 |
MFR比 | 0.68 | 0.77 | 0.76 | 0.72 |
<造形物之製造>
(實施例1~8、比較例1~4)
於實施例1~8及比較例1~2中,利用熱熔積層方式三維列印,於表2所示之印刷條件下將上述所獲得之長絲製作成具有圖1所示之形狀之彎曲試驗片(依據ISO 178)。再者,於實施例1~6及比較例1~2中,熱熔積層方式三維列印使用Raise公司所製造之商品名為Raise 3D N2者。又,於實施例7~8中,熱熔積層方式三維列印使用S-Lab公司所製造之商品名為MothMath S3DP222者,尤其是進行調整以使噴嘴頭部之上限值之溫度成為450℃而使用。
造形時,沿著圖1中箭頭X所示之方向,從中心向外側呈同心圓狀地進行造形。將積層方向設為彎曲試驗片之厚度方向。再者,將線與線不密接而剝離成千層糕狀者視為無法造形。
又,於比較例3~4中,使用作為表1所示之長絲之原料的顆粒,設置澆口以使樹脂之流動方向與三維列印之造形行進方向相同而進行射出成形,製作具有圖1所示之形狀之彎曲試驗片(依據ISO 178)。
又,於實施例1~7及比較例1~2中,利用熱熔積層方式三維列印,於表3所示之印刷條件下將上述所獲得之長絲製作成具有圖2所示之形狀之拉伸試驗片(ASTM D638 TypeⅠ)。再者,於實施例1~6及比較例1~2中,熱熔積層方式三維列印使用Raise公司所製造之商品名為Raise 3D N2者。又,於實施例7中,熱熔積層方式三維列印使用S-Lab公司所製造之商品名為MothMath S3DP222者,尤其是進行調整以使噴嘴頭部之上限值之溫度成為450℃而使用。
造形時,沿著圖2中箭頭X所示之方向,從中心向外側呈同心圓狀地進行造形。將積層方向設為拉伸試驗片之厚度方向。再者,將線與線不密接而剝離成千層糕狀者視為無法造形。
又,於比較例3~4中,使用作為表3所示之長絲之原料的顆粒,設置澆口以使樹脂之流動方向與三維列印之造形行進方向相同而進行射出成形,製作具有圖2所示之形狀之拉伸試驗片(ASTM D638 TypeⅠ)。
<評價>
(1)彎曲強度及彎曲彈性模數
利用自動立體測圖儀AG-5000(島津製作所公司製),依據ISO 178,藉由3點彎曲試驗對在表2之條件下所製作之彎曲試驗片進行彎曲強度及彎曲彈性模數之測定,將結果示於表2。
(2)拉伸強度及拉伸彈性模數
利用自動立體測圖儀AG-1(島津製作所公司製),依據ISO 0527-1,對在表3之條件下所製作之拉伸試驗片進行拉伸強度及拉伸彈性模數之測定,將結果示於表3。
(3)MFR比
依據JIS K 7210,於測定溫度(聚醯胺MXD10樹脂:240℃,PPS樹脂:330℃,PEEK樹脂:400℃)、測定負荷5 kg之條件下,測定熱塑性樹脂及樹脂組合物之MFR值,將熱塑性樹脂之MFR值設為MFR1,將樹脂組合物之MFR值設為MFR2。根據所獲得之MFR值算出MFR之比(MFR2/MFR1)。將結果示於上述表1。
[表2]
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | 實施例7 | 實施例8 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | ||
長絲No. | 1 | 1 | 2 | 2 | 3 | 3 | 4 | 4 | 1 | 2 | |||
組成 | 聚醯胺MXD10樹脂 (質量%) | 70 | 70 | 80 | 80 | 70 | 80 | 70 | 80 | ||||
PPS樹脂 (質量%) | 80 | 80 | |||||||||||
PEEK樹脂(質量%) | 80 | 80 | |||||||||||
鈦酸鉀 (質量%) | 30 | 30 | 20 | 20 | 20 | 20 | 20 | 20 | 30 | 20 | 30 | 20 | |
造形條件 | 噴嘴溫度(℃) | 250 | 250 | 250 | 250 | 310 | 310 | 450 | 450 | 250 | 250 | 射出成形 | 射出成形 |
熱床溫度(℃) | 85 | 85 | 85 | 85 | 100 | 100 | 120 | 120 | 85 | 85 | |||
頭部進給速度(mm/sec) | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 | 60 | 60 | |||
頭部直徑(mm) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | |||
造形線寬(mm) | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.20 | 0.20 | |||
積層間距(mm) | 0.05 | 0.10 | 0.05 | 0.10 | 0.05 | 0.10 | 0.05 | 0.10 | 0.20 | 0.20 | |||
造形物之物性 | 彎曲強度(MPa) | 212 | 194 | 193 | 174 | 139 | 128 | 210 | 192 | 無法造形 | 157 | 171 | 140 |
彎曲彈性模數(GPa) | 9.3 | 8.4 | 7.2 | 6.5 | 8.0 | 6.6 | 8.1 | 7.5 | 5.7 | 8.1 | 5.7 |
[表3]
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | 實施例7 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | ||
長絲No. | 1 | 1 | 2 | 2 | 3 | 3 | 4 | 1 | 2 | |||
組成 | 聚醯胺MXD10樹脂 (質量%) | 70 | 70 | 80 | 80 | 70 | 80 | 70 | 80 | |||
PPS樹脂 (質量%) | 80 | 80 | ||||||||||
PEEK樹脂(質量%) | 80 | |||||||||||
鈦酸鉀 (質量%) | 30 | 30 | 20 | 20 | 20 | 20 | 20 | 30 | 20 | 30 | 20 | |
造形條件 | 噴嘴溫度(℃) | 250 | 250 | 250 | 250 | 310 | 310 | 450 | 250 | 250 | 射出成形 | 射出成形 |
熱床溫度(℃) | 85 | 85 | 85 | 85 | 100 | 100 | 120 | 85 | 85 | |||
頭部進給速度(mm/sec) | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 60 | 60 | |||
頭部直徑(mm) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | |||
造形線寬(mm) | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.20 | 0.20 | |||
積層間距(mm) | 0.05 | 0.10 | 0.05 | 0.10 | 0.05 | 0.10 | 0.05 | 0.20 | 0.20 | |||
造形物之物性 | 拉伸強度(MPa) | 137 | 110 | 116 | 90 | 79 | 70 | 120 | 無法造形 | 89 | 110 | 90 |
拉伸彈性模數(GPa) | 8.1 | 7.5 | 6.3 | 5.4 | 6.8 | 5.7 | 6.4 | 5.3 | 7.5 | 5.1 |
根據表2及表3可知:於實施例1~4中,將利用熱熔積層方式三維列印進行造形時之積層間距設為未達0.20 mm,且將造形線寬設為未達0.20 mm,藉此機械特性提高。又,確認:如實施例5~8,即使於使用PPS樹脂或PEEK樹脂作為熱塑性樹脂之情形時,藉由將利用熱熔積層方式三維列印進行造形時之積層間距設為未達0.20 mm,且將造形線寬設為未達0.20 mm,與積層間距及造形線寬中之至少一者為0.20 mm以上之情形相比,機械特性提高。
再者,根據比較例1與比較例2之對比可知,通常情況下,若高度填充無機纖維,則難以利用樹脂組合物之三維列印進行造形。相對於此,如實施例1~8,若將積層間距設為未達0.20 mm,且將造形線寬設為未達0.20 mm,則會有如下出乎意料之效果:能夠利用三維列印進行造形,能夠賦予優異之機械特性。
圖1係表示彎曲試驗片之形狀之示意俯視圖。
圖2係表示拉伸試驗片之形狀之示意俯視圖。
Claims (11)
- 一種造形物之製造方法,其包括: 準備樹脂組合物之步驟,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200;及 使用上述樹脂組合物,利用熱熔積層方式三維列印進行造形,藉此製造造形物之步驟; 且利用上述熱熔積層方式三維列印進行造形時之積層間距未達0.20 mm,且造形線寬未達0.20 mm。
- 如請求項1之造形物之製造方法,其中於將上述熱塑性樹脂之MFR值設為MFR1,將上述樹脂組合物之MFR值設為MFR2時,由MFR2/MFR1所表示之MFR之比為0.10以上0.90以下。
- 如請求項1或2之造形物之製造方法,其中於上述樹脂組合物之合計量100質量%中,上述無機纖維之含量為1質量%以上45質量%以下。
- 如請求項1至3中任一項之造形物之製造方法,其中造形速度為20 mm/秒以上200 mm/秒以下。
- 如請求項1至4中任一項之造形物之製造方法,其中上述無機纖維之莫氏硬度為5以下。
- 如請求項1至5中任一項之造形物之製造方法,其中上述無機纖維為鈦酸鉀及矽灰石中之至少一者。
- 如請求項1至6中任一項之造形物之製造方法,其中上述熱塑性樹脂為選自由聚烯烴樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚縮醛樹脂、聚碳酸酯樹脂、脂肪族聚醯胺樹脂、半芳香族聚醯胺樹脂、聚苯硫醚樹脂、聚醚醯亞胺樹脂、及聚醚醚酮樹脂所組成之群中之至少一種。
- 一種造形物,其藉由如請求項1至7中任一項之造形物之製造方法而獲得。
- 一種造形物,其係包含樹脂組合物之熱熔積層方式三維列印造形物,上述樹脂組合物含有無機纖維及熱塑性樹脂,上述無機纖維之平均纖維長度為1 μm~300 μm且平均長徑比為3~200, 上述造形物之積層間距未達0.20 mm,且造形線寬未達0.20 mm。
- 如請求項9之造形物,其中於將上述熱塑性樹脂之MFR值設為MFR1,將上述樹脂組合物之MFR值設為MFR2時,由MFR2/MFR1所表示之MFR之比為0.10以上0.90以下。
- 如請求項9或10之造形物,其中於上述樹脂組合物之合計量100質量%中,上述無機纖維之含量為1質量%以上45質量%以下。
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