TWI820105B - 成形品及成形品之製造方法 - Google Patents
成形品及成形品之製造方法 Download PDFInfo
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- TWI820105B TWI820105B TW108111145A TW108111145A TWI820105B TW I820105 B TWI820105 B TW I820105B TW 108111145 A TW108111145 A TW 108111145A TW 108111145 A TW108111145 A TW 108111145A TW I820105 B TWI820105 B TW I820105B
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- porous body
- resin
- continuous porous
- film layer
- molded article
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Abstract
本發明係提供剛性與輕量性均優異、且具備防液性的成形品,及成形品之製造方法。本發明的成形品,係在厚度方向具有連續空隙的連續多孔質體上,形成含有固態狀添加劑與樹脂之薄膜層的成形品;其中,從上述成形品形成有上述薄膜層之面的水滲透度係10%以下。
Description
本發明係關於防液性優異的成形品及成形品之製造方法。
近年相關汽車、飛機、運動製品等產業用製品,市面上針對輕量性提升的要求正逐年提高。為能因應此種要求,輕量、且力學特性優異的纖維強化複合材料被廣泛利用於各種產業用途。尤其在更進一步輕量化之目的下,提案有由樹脂、強化纖維及空隙構成,且力學特性優異的構造體(例如參照專利文獻1)。
使用纖維強化複合材料的製品,在賦予設計性之目的下,會有需要設置裝飾層的情況(例如參照專利文獻2)。在厚度方向具有連續空隙的纖維強化複合材料,當使用於在室外使用的製品等時,若液體經由空隙滲入內部,便會發生質量增加等問題,因而必需賦予防液性。例如揭示有:在具空隙的連續氣泡性烯烴系樹脂層上,積層非發泡性烯烴系樹脂層並一體化的烯烴系樹脂積層薄片(例如參照專利文獻3)。又,亦提案有:在連續多孔質體的表面上設置表皮材的技術(例如參照專利文獻4)。
專利文獻1:日本專利第6123965號公報
專利文獻2:日本專利特開2016-78451號公報
專利文獻3:日本專利特開平5-124143號公報
專利文獻4:國際公開第2015/029634號
然而,專利文獻3的非發泡性烯烴系樹脂層、及專利文獻4的表皮層,相關防液性並無考慮在內。又,在未發泡狀態物上形成表皮層等製造方法亦有受限定、且繁雜。
本發明係有鑑於上述而完成者,且目的在於提供:剛性與輕量性均優異、具備有防液性的成形品、及成形品之製造方法。
本發明的成形品,係在厚度方向具有連續空隙的連續多孔質體上,形成含有固態狀添加劑與樹脂之薄膜層的成形品;其中,從上述薄膜層所形成面的水滲透度係10%以下。
再者,本發明的成形品,係在厚度方向具有連續空隙的連續多孔質體上,形成含有固態狀添加劑與樹脂之薄膜層的成形品;其中,根據JIS R3257(1999)所測定玻璃基板上的接觸角為60°以下之溶液,從形成有上述薄膜層之面的滲透度係30%以下。
再者,本發明的成形品之製造方法,係上述中任一項所記載成形品的製造方法,將上述固態狀添加劑與上述樹脂的樹脂混合物,塗佈於上述連續多孔質體之後,藉由施行加熱而形成薄膜層。
根據本發明的成形品及成形品之製造方法,可輕易獲得剛性與輕量性均優異,且具備防液性的成形品。
1‧‧‧強化纖維
1a~1f‧‧‧單纖維
2‧‧‧二次元配向角
3‧‧‧沖壓機熱板
4‧‧‧模具
5‧‧‧先質
6‧‧‧間隔物
7‧‧‧成形品
圖1(a)及(b)係本發明強化纖維氈中,強化纖維的分散狀態之一例的示意圖。
圖2係本發明強化纖維氈的製造裝置之一例的示意圖。
圖3(a)及(b)係本發明連續多孔質體之製造的說明圖。
圖4(a)至(c)係本發明具有半球形狀之連續多孔質體的說明圖。
以下,針對本發明的成形品、及成形品之製造方法進行說明。
本發明實施形態1的成形品係由在厚度方向具有連續空隙的連續多孔質體上,形成含有固態狀添加劑與樹脂之薄膜層而成的成形品;其中,從上述成形品形成有上述薄膜層之面的水滲透度係在10%以下。
本發明成形品中,連續多孔質體係含有:強化纖維、基質樹脂、及空隙。
本發明的連續多孔質體中,強化纖維係可例示:鋁、黃銅、不鏽鋼等金屬纖維;PAN系、縲縈系、木質素系、瀝青系碳纖維、石墨纖維、玻璃等絕緣性纖維;聚芳醯胺、PBO(聚苯并唑)、聚苯硫醚、聚酯、丙烯酸、尼龍、聚乙烯等有機纖維;碳化矽、氮 化矽等無機纖維。又,亦可對該等纖維施行表面處理。表面處理係除利用導電體金屬進行的被黏處理之外,尚有利用偶合劑施行的處理、利用上漿劑施行的處理、利用集束劑施行的處理、利用添加劑施行的附著處理等。又,該等纖維係可單獨使用1種、亦可併用2種以上。其中,從輕量化效果的觀點,較佳係使用比強度、比剛性優異的PAN系、瀝青系、縲縈系等碳纖維。又,從提高所獲得連續多孔質體之經濟性的觀點,較佳係使用玻璃纖維,特別係從力學特性與經濟性均衡的觀點,較佳係併用碳纖維與玻璃纖維。又,從提高所獲得連續多孔質體的衝擊吸收性或塑形性的觀點,較佳係使用聚芳醯胺纖維,特別係從力學特性與衝擊吸收性均衡的觀點,較佳係併用碳纖維與聚芳醯胺纖維。又,從提高所獲得連續多孔質體(A)之導電性的觀點,亦可使用由具導電性之金屬所構成的金屬纖維,或經鎳、銅、鐿等金屬被覆的強化纖維。該等之中,更佳係使用從強度與彈性模數等力學特性優異的金屬纖維、瀝青系碳纖維、及PAN系碳纖維所構成群組中選擇的強化纖維。
強化纖維較佳係不連續,且在連續多孔質體中呈無規分散。又,更佳係分散狀態為略單絲狀。藉由將強化纖維設為此種態樣,當對薄片狀連續多孔質體的先質施加外力進行成形時,便可輕易塑造成複雜形狀。又,藉由將強化纖維設為此種態樣,利用強化纖維所形成的空隙便緻密化,連續多孔質體中的強化纖維之纖維束端弱部可極小化,故除優異的補強效率與可靠度之外,亦賦予等向性。又,即便將連續多孔質體的形狀設為平板之外,例如半球狀或凹凸形狀等複雜形狀的情況,仍可輕易成形,並可保持剛性。
此處所謂略單絲狀係指依強化纖維單絲未滿500支 的細纖度股條存在。更佳係單絲狀,即依單絲分散的狀態。
此處,所謂略單絲狀、或分散呈單絲狀係指連續多孔質體中任意選擇的強化纖維中,其二次元配向角為1°以上的單纖維比例(以下亦稱纖維分散率)為80%以上,換言之,係指連續多孔質體中由2支以上單纖維接觸的平行束未滿20%。所以,此處特佳係指至少強化纖維中,長絲數100支以下的纖維束質量分率為100%者。
再者,強化纖維更佳係呈無規分散。此處所謂強化纖維呈無規分散係指連續多孔質體中任意選擇的強化纖維之二次元配向角之算術平均值在30°以上且60°以下的範圍內。該二次元配向角係指由強化纖維的單纖維、與該單纖維所交叉的單纖維形成之角度,且定義為所交叉的單纖維彼此間形成之角度中,在0°以上且90°以下之範圍內的銳角側之角度。
針對該二次元配向角使用圖式進行更詳細說明。圖1(a)、(b)中,若以單纖維1a為基準,則單纖維1a係與其他單纖維1b~1f呈交叉。此處所謂交叉係指所觀察的二次元平面中,觀察到作為基準之單纖維與其他單纖維呈交叉的狀態,而單纖維1a與單纖維1b~1f未必一定要有接觸,當投影觀看時有被觀察到呈交叉的狀態亦非屬例外。即,觀看成為基準之單纖維1a時,單纖維1b~1f全部為二次元配向角的評價對象,圖1(a)中,二次元配向角係所交叉的2支單纖維形成之2個角度中,在0°以上且90°以下之範圍內的銳角側之角度。
測定二次元配向角的方法並無特別的限制,可例示如:從構成要件的表面觀察強化纖維(A1)配向的方法。二次元配向 角的平均值係依照下述順序測定。即,測定隨機選擇單纖維(圖1中的單纖維1a),與所交叉的所有單纖維(圖1中的單纖維1b~1f)之二次元配向角的平均值。例如:當某單纖維所交叉的其他單纖維係多數的情況,所交叉的其他單纖維亦可代用隨機選擇20支測定的算術平均值。此項測定係以其他單纖維為基準重複合計施行5次,再計算出其算術平均值並設為二次元配向角的算術平均值。
藉由強化纖維呈略單絲狀且無規分散,便可將上述利用呈略單絲狀分散的強化纖維所賦予的性能提高至最大極限。又,對連續多孔質體可於力學特性上賦予等向性。從此觀點,強化纖維的纖維分散率較佳係90%以上,越接近100%越好。又,強化纖維的二次元配向角之算術平均值較佳係在40°以上且50°以下的範圍內,越接近理想角度45°越好。二次元配向角的較佳範圍係可將上述上限的任一值設為上限,亦可將上述下限的任一值設為下限。
另一方面,強化纖維非呈不連續狀的形態例,係有:強化纖維朝單一方向排列的薄片基材、織物基材、及無捲曲基材等。因為該等形態的強化纖維呈規則性緻密配置,因而連續多孔質體中的空隙變少,基質樹脂的含浸極為困難,會有形成未含浸部、或含浸手段與樹脂種類之選擇項受大幅限制的情況。另外,從活用強化纖維緻密配置、提升成形品之防液性的觀點,亦可組合使用非採此種不連續狀形態的強化纖維。
強化纖維的形態,係可為與連續多孔質體相同程度長度的連續性強化纖維、或被切斷為既定長度的有限長度不連續性強化纖維中之任一者,從可輕易使基質樹脂含浸、或容易調整其量的觀點,較佳係不連續性強化纖維。
本發明的連續多孔質體中,強化纖維的質量平均纖維長較佳係1mm以上且15mm以下的範圍內。藉此,可提高強化纖維的補強效率,且能對連續多孔質體賦予優異的力學特性。當強化纖維的質量平均纖維長為1mm以上時,因為可效率佳地形成連續多孔質體中的空隙,因而可降低密度,換言之,可獲得具相同厚度且輕量的連續多孔質體,故較佳。另一方面,當強化纖維的質量平均纖維長為15mm以下時,連續多孔質體中的強化纖維不易因自重而彎曲,且不會抑制力學特性的顯現,故較佳。質量平均纖維長係利用燒磬或溶出等方法去除連續多孔質體的基質樹脂成分,再從剩餘的強化纖維中隨機選擇400支,並測定其長度至10μm單位,便可計算出該等的質量平均纖維長。
強化纖維從基質樹脂對強化纖維之含浸容易度的觀點,較佳係設為不織布狀的形態。又,藉由強化纖維具有不織布狀的形態,除不織布自體的操作性容易度之外,當一般呈高黏度的熱可塑性樹脂之情況,仍可輕易含浸,故較佳。此處,所謂不織布狀的形態係指強化纖維的股條及/或單絲不規則性呈面狀分散的形態,可例示:切股氈、連續纖維股氈、抄紙毛毯、梳理墊(carding mat)、氣流成網氈(air laid mat)等形態(以下將該等統稱為強化纖維氈)。
本發明的連續多孔質體中,基質樹脂係可例示熱可塑性樹脂或熱硬化性樹脂。又,本發明亦可摻合熱硬化性樹脂與熱可塑性樹脂。
本發明連續多孔質體之一形態,基質樹脂較佳係含有至少1種以上的熱可塑性樹脂。熱可塑性樹脂係可例示從:「聚對 苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚對苯二甲酸丙二酯(PTT)、聚萘二甲酸乙二酯(PEN)、液晶聚酯等聚酯;聚乙烯(PE)、聚丙烯(PP)、聚丁烯等聚烯烴;聚甲醛(POM)、聚醯胺(PA)、聚苯硫醚(PPS)等聚伸芳硫醚、聚酮(PK)、聚醚酮(PEK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚腈(PEN)、聚四氟乙烯等氟系樹脂、液晶聚合物(LCP)」等結晶性樹脂;「苯乙烯系樹脂、以及聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、聚伸苯醚(PPE)、聚醯亞胺(PI)、聚醯胺醯亞胺(PAI)、聚醚醯亞胺(PEI)、聚碸(PSU)、聚醚碸、聚芳酯(PAR)」等非晶性樹脂;其他尚可例示:酚系樹脂、苯氧樹脂、以及聚苯乙烯系、聚烯烴系、聚胺酯系、聚酯系、聚醯胺系、聚丁二烯系、聚異戊二烯系、氟系樹脂、及丙烯腈系等;熱可塑彈性體等;或該等的共聚合體及改質體等之中選擇的熱可塑性樹脂。其中,從所獲得連續多孔質體的輕量性之觀點,較佳係聚烯烴,從強度的觀點,較佳係聚醯胺,從表面外觀的觀點,較佳係如聚碳酸酯或苯乙烯系樹脂般的非晶性樹脂,從耐熱性的觀點,較佳係聚伸芳硫醚,從連續使用溫度的觀點,較佳係聚醚醚酮,又從耐藥性的觀點,較佳係使用氟系樹脂。
本發明連續多孔質體之一形態,基質樹脂較佳係含有至少1種以上的熱硬化性樹脂。熱硬化性樹脂係可例示:不飽和聚酯、乙烯酯、環氧樹脂、酚樹脂、脲樹脂、三聚氰胺樹脂、熱硬化性聚醯亞胺、該等的共聚合體、改質體、及經摻合該等之至少2種的樹脂。
再者,在不致損及本發明目的之範圍內,本發明連續多孔質體係作為基質樹脂的成分之一,亦可含有彈性體或橡膠成分 等耐衝擊性提升劑、其他填充材或添加劑。填充材或添加劑之例係可例示:無機填充材、難燃劑、導電性賦予劑、結晶核劑、紫外線吸收劑、抗氧化劑、減震劑、抗菌劑、防蟲劑、除臭劑、抗著色劑、熱安定劑、脫模劑、抗靜電劑、可塑劑、滑劑、著色劑、顏料、染料、發泡劑、抑泡劑、或偶合劑。
本發明的連續多孔質體係具有空隙。本發明中所謂空隙係指由基質樹脂被覆的強化纖維成為柱狀支撐體,並由其重疊或交叉所形成的空間。例如將使強化纖維預先含浸基質樹脂的連續多孔質體之先質,施行加熱而獲得連續多孔質體時,因加熱導致基質樹脂熔融或軟化,藉由強化纖維起毛而形成空隙。此現象係在多孔質體的先質中,利用加壓呈壓縮狀態的內部之強化纖維,根據源於其彈性模數之起毛力而出現起毛的性質。空隙係至少在厚度方向上連續。此處所謂「厚度方向」係由如圖3所示模具所成形之板狀成形品的平面部(投影面積最大之一面)朝相對向面的方向,空隙在該方向上呈連續。又,當由圖4所示模具成形經賦予半球形狀的成形品時,便為構成成形品的構件厚度方向。此時,藉由空隙在厚度方向上連續,連續多孔質體便具有通氣性。又,配合目的,亦可在厚度方向的垂直方向上連續。
本發明的連續多孔質體較佳係強化纖維的體積含有率(%)為0.5~55體積%、基質樹脂的體積含有率(%)為2.5~85體積%、空隙的體積含有率(%)為10~97體積%。
連續多孔質體中,若強化纖維的體積含有率為0.5體積%以上,可使源於強化纖維的補強效果充足,故較佳。另一方面,若強化纖維的體積含有率為55體積%以下,則基質樹脂相對於強化 纖維的體積含有率相對性增加,連續多孔質體中的強化纖維彼此間會相黏結,可使強化纖維的補強效果充足,所以能滿足連續多孔質體的力學特性、特別係彎曲特性,故較佳。
連續多孔質體中,若基質樹脂的體積含有率為2.5體積%以上,則連續多孔質體中的強化纖維彼此間會黏結,可使強化纖維的補強效果充足,且能滿足連續多孔質體的力學特性、特別係彎曲彈性模數,故較佳。另一方面,若基質樹脂的體積含有率為85體積%以下,則不會阻礙空隙的形成,故較佳。
連續多孔質體中,強化纖維係被基質樹脂所被覆,而所被覆的基質樹脂厚度(被覆厚度)較佳係1μm以上且15μm以下的範圍內。由基質樹脂被覆的強化纖維之被覆狀態,係在至少構成連續多孔質體的強化纖維之單纖維彼此間交叉處有被被覆之前提下,從連續多孔質體的形狀安定性、或厚度控制容易度及自由度的觀點已屬足夠,更佳態樣係基質樹脂依上述厚度被覆著強化纖維周圍的狀態。此狀態係強化纖維的表面因基質樹脂而沒有露出,換言之,強化纖維係利用基質樹脂形成電線狀皮膜。藉此,連續多孔質體更進一步具有形狀安定性,且可充分顯現力學特性。又,由基質樹脂被覆的強化纖維之被覆狀態,並不需要該強化纖維全部均受被覆,只要在不致損及本發明連續多孔質體的形狀安定性、或彎曲彈性模數、彎曲強度的範圍內便可。
連續多孔質體中,空隙的體積含有率較佳係10體積%以上且97體積%以下的範圍內。藉由空隙含有率為10體積%以上,便可降低連續多孔質體的密度,所以能滿足輕量性,故較佳。另一方面,若空隙的含有率為97體積%以下,換言之,在強化纖維 周圍所被覆基質樹脂的厚度充足,因而連續多孔質體中的強化纖維彼此間可充分補強,而提高力學特性,故較佳。空隙之體積含有率的上限值較佳係97體積%。本發明中,體積含有率係將構成連續多孔質體的強化纖維、基質樹脂、及空隙的各體積含有率合計設為100體積%。
連續多孔質體中,空隙係藉由使連續多孔質體之先質的基質樹脂黏度降低,而使強化纖維起毛,再藉由回復原本狀態時的復原力所形成。依此,藉由強化纖維係經由基質樹脂結合,便可顯現更堅固的壓縮特性與連續多孔質體的形狀保持性,故較佳。
連續多孔質體的密度ρ較佳係0.9g/cm3以下。若連續多孔質體的密度ρ為0.9g/cm3以下,便意味著成為連續多孔質體時的質量會減少,結果有助於成為製品時的質量輕量化,故較佳。更佳係0.7g/cm3以下、特佳係0.5g/cm3以下。相關密度的下限並沒有設定限制,但一般具有強化纖維與基質樹脂的連續多孔質體,可將從其構成成分的強化纖維、基質樹脂、及空隙的各自體積比例所計算的值作為下限。本發明的成形品中,連續多孔質體自身的密度係依照所使用的強化纖維、基質樹脂而有所差異,從維持連續多孔質體之力學特性的觀點,較佳係0.03g/cm3以上。
本發明的成形品中,所謂薄膜層係至少具有防液性的層。所謂具有防液性的層係具有能防止液體穿透之機能的層,將薄膜層設為最終製品之成形品的外表面時,可防止液體滲入於連續多孔質體,當設為內表面時,可賦予不會使已滲入連續多孔質體中的液體穿透 而予以儲存的功用。本發明中,從更加提高防液性的觀點,薄膜層較佳係由2層以上構成。又,藉由此種構成,可減少薄膜層形成時所使用的固態狀添加劑及樹脂之使用量,便可獲得輕量性優異的成形品。
本發明的成形品中,薄膜層係具有固態狀添加劑與樹脂。固態狀添加劑與樹脂的混合比例,從固態狀添加劑之機能顯現的觀點,較佳係0.1體積%以上且50體積%以下。若固態狀添加劑的體積比例未滿0.1體積%,會有無法充分顯現固態狀添加劑之機能的情況,若超過50體積%,則成形品的重量會增加。又,在形成薄膜層時,樹脂黏度會提高且處置性降低。薄膜層中的固態狀添加劑之混合比例更佳係1體積%以上且40體積%以下。特佳係3體積%以上且30體積%以下。
若亦考慮將本發明成形品作為最終製品處置,則薄膜層較佳係亦具備有設計性的層。從此觀點,固態狀添加劑係在對成形品防止液體滲入於連續多孔質體的空隙,且賦予著色及珠光感或金屬感等設計性之目的下添加。
固態狀添加劑係可舉例如:顏料或玻璃珠等。具體而言係可舉例如:偶氮顏料、酞菁藍等有機顏料;由鋁、黃銅等金屬粉末構成的金屬顏料;氧化鉻、鈷藍等無機顏料。其中,從耐熱性的觀點,較佳係金屬顏料、無機顏料。又,當強化纖維係碳纖維或聚芳醯胺纖維等深色的情況,較佳係使用具有2層以上不同折射率之構造的顏料。例如:經氧化鈦或氧化鐵被覆的天然雲母、人工雲母、氧化鋁碎片、二氧化矽碎片、玻璃碎片。藉由設為該層構造,便可利用可見光區域光的干涉、繞射、散射等光學現象進行發色。 若利用光的干涉、繞射、散射等光學現象,便可利用特定波長光的反射進行發色,所以當使用深色強化纖維時可較佳地使用。從堵塞連續多孔質體之空隙(連續多孔質體表面的孔)的觀點,較佳係在形成薄膜層時不會與樹脂相溶的固體,而在形成薄膜層後的狀態並無限定。
固態狀添加劑的形態並無特別的限定,可為球狀、纖維狀、碎片狀等形態。本發明中,因為堵塞在連續多孔質體厚度方向上連續的空隙係屬於固態狀添加劑的目的之一,因而可配合空隙形狀適當選擇。固態狀添加劑的最大尺寸較佳係200μm以下。此處所謂固態狀添加劑的最大尺寸係指固態狀添加劑的一次粒子最大尺寸,或當固態狀添加劑進行凝集等情況時二次粒子的最大尺寸。藉由固態狀添加劑的最大尺寸為200μm以下,薄膜層表面便呈平滑,而提升設計性。又,固態狀添加劑的最大尺寸較佳係1μm以上。藉由固態狀添加劑的最大尺寸為1μm以上,便可提升薄膜層的防液性。又,固態狀添加劑的最大尺寸與後述連續多孔質體的空隙徑(孔徑)的關係,較佳係成為連續多孔質體的空隙徑(孔徑)≦固態狀添加劑的最大尺寸,更佳係連續多孔質體的空隙徑(孔徑)×1.1<固態狀添加劑的最大尺寸之關係,特佳係連續多孔質體的空隙徑(孔徑)×1.3<固態狀添加劑的最大尺寸之關係。固態狀添加劑的最大尺寸係使用電子顯微鏡觀察固態狀添加劑,從影像經放大至可測定尺寸至少至1μm單位為止的影像中,隨機選擇任意100個固態狀添加劑,將依各個固態狀添加劑之外側輪廓線上的任意2點間距離成為最大的方式選擇時的長度設為最大長度所測得之值的平均值。固態狀添加劑的長寬比並無特別的限定,較佳係50以下、更佳係30以下。從薄膜層形成容易度(樹脂組成物的處置性)的觀點,長寬比較佳係5以下,長寬比越接近1則添加物越能抑制薄膜層的特性變動。另一方面,當連續多孔質體中所形成的孔較大時,從減少薄膜層厚度的觀點,較佳係將長寬比設為10以上。
固態狀添加劑的最大尺寸特佳係150μm以下、特佳係100μm以下。又,固態狀添加劑的最大尺寸更佳係5μm以上、特佳係10μm以上。
從抑制薄膜層及成形品之質量增加的觀點,較佳係使用固態狀添加劑之內部呈空洞的中空構造體。尤其就輕量化的觀點,較佳係中空玻璃珠或多孔的樹脂粒子等。或者,亦可使用甜甜圈狀或三角狀、框架狀的中空構造體。藉由使用此種固態狀添加劑,便可在將負責堵塞住連續多孔質體厚度方向上連續空隙功用的固態狀添加劑,維持最大尺寸的狀態下,抑制重量增加。
本發明的薄膜層中,樹脂係可使用熱硬化性樹脂、或熱可塑性樹脂。
本發明的薄膜層中,熱硬化性樹脂係含有熱硬化性樹脂與硬化劑。熱硬化性樹脂並無特別的限定,可使用環氧樹脂、不飽和聚酯、酚樹脂等任意熱硬化性樹脂。熱硬化性樹脂係可單獨使用、亦可適當調配。當使用賦予設計性的固態狀添加劑時,較佳係使用高透明性的環氧樹脂或不飽和聚酯。
硬化劑係例如:脂肪族聚胺、芳香族聚胺、雙氰胺、聚羧酸、聚羧酸醯肼、酸酐、聚硫醇、聚酚等進行化學計量反應的化合物,以及如咪唑、路易士酸錯合物、鎓鹽般進行觸媒作用的化合物。當使用進行化學計量反應的化合物時,硬化促進劑會有更進
一步調配例如:咪唑、路易士酸錯合物、鎓鹽、尿素衍生物、膦等的情況。硬化劑中,從所獲得纖維強化複合材料的耐熱性或力學特性優異之觀點,較佳係使用分子中含有胺基、醯胺基、咪唑基、尿素基、醯肼基等具氮原子基的有機氮化合物。硬化劑係可僅使用1種、亦可組合使用複數種。
本發明的薄膜層中,23℃下的熱硬化性樹脂黏度較佳係1×101Pa‧s以上且1×104Pa‧s以下。藉由23℃下的樹脂黏度為1×101Pa‧s以上,可抑制樹脂對連續多孔質體的滲透。又,藉由熱硬化性樹脂黏度為1×104Pa‧s以下,便可輕易執行對多孔質的塗佈,可形成均勻厚度的薄膜層。23℃下的熱硬化性樹脂黏度更佳係1×102Pa‧s以上且5×103Pa‧s以下。
本發明的薄膜層中,依50℃加熱30分鐘時的熱硬化性樹脂黏度較佳係1×104Pa‧s以上。熱硬化性樹脂經塗佈於連續多孔質體後,最好馬上硬化,便不會過度滲透於連續多孔質體的空隙中。藉由依50℃加熱30分鐘時的熱硬化性樹脂黏度為1×104Pa‧s以上,便可抑制熱硬化性樹脂對連續多孔質體的滲透。又,更佳係1×105Pa‧s以上。
本發明的薄膜層中,熱可塑性樹脂並無特別的限定,可使用丙烯酸樹脂、胺酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、氯乙烯樹脂等任意熱可塑性樹脂。熱可塑性樹脂係可單獨使用、亦可適當調配。又,亦可與構成連續多孔質體的樹脂同樣選擇。
當薄膜層的固態狀添加劑係使用顏料,且具有熱硬化性樹脂時,顏料與熱硬化性樹脂硬化物的折射率差較佳係0.1以下。折射率差越小,則薄膜層的透明度越獲提升,因而可強烈顯現
顏料的著色效果。薄膜層所使用的樹脂較佳係熱硬化性樹脂。
本發明的成形品中,從成形品形成有薄膜層之面的水滲透度係10%以下。藉由水滲透度為10%以下,便可防止水對連續多孔質體的滲透。水滲透度較佳係8%以下、更佳係5%以下。水對成形品的滲透度係例如從成形品中切取100mm×100mm試驗片,測定質量M0,於試驗片之薄膜層側的表面滴下水30g。經5分鐘後,將試驗片翻面,除去試驗片表面上殘留的水之後,測定試驗片質量M1,再從下式便可計算出。
滲透度[%]={(M1-M0)÷30}×100 式(1)
本發明的成形品中,薄膜層的厚度較佳係10μm以上且500μm以下。若厚度小於10μm,則會有防液性降低的可能性。又,若厚度大於500μm,雖可形成平滑的面或設計性優異的面,但會導致成形品的質量增加,較難顯現成形品的輕量性。薄膜層的厚度更佳係400μm以下、特佳係300μm以下。
本發明的成形品中,薄膜層的密度較佳係2.5g/cm3以下。藉由薄膜層的密度為2.5g/cm3以下,便可抑制成形品的質量增加。薄膜層的密度較佳係2.5g/cm3以下、更佳係2.0g/cm3以下、特佳係1.5g/cm3以下。此時,薄膜層密度的下限值,雖從輕量化的觀點並無特別的限定,但從薄膜層形成容易度的觀點,較佳係0.1g/cm3以上、更佳係0.3g/cm3以上、特佳係0.5g/cm3以上。本發明的成形品中,較佳係薄膜層侵入於連續多孔質體的空隙內。藉由薄膜層侵入於空隙內,便可利用錨定進行機械式接合,可在連續多孔質體的表面上堅固地形成薄膜層。又,本發明的成形品中,較佳係固態狀添加劑的至少一部分存在於連續多孔質體的空隙內。藉由設為此種狀態,便可更進一步防止水與水溶液對連續多孔質體的滲入。又,亦可抑制構成薄膜層的樹脂過度滲入。此時,固態狀添加劑存在於連續多孔質體之空隙的狀態並無特別的限定,較佳係滲入連續多孔質體中的固態狀添加劑,存在於多孔質體內之厚度方向為30μm以上深度位置處,該深度更佳係50μm以上、特佳係100μm以上。
再者,本發明實施形態2的成形品,係由在厚度方向具有連續空隙的連續多孔質體上,形成含固態狀添加劑與樹脂之薄膜層而成的成形品;其中,根據JIS R3257(1999)所測定玻璃基板上的接觸角為60°以下的溶液,從成形品形成有薄膜層之面的滲透度係30%以下。藉由根據JIS R3257(1999)所測定玻璃基板上的接觸角為60°以下的溶液,從成形品形成有薄膜層之面的滲透度為30%以下,即便在洗淨等目的下利用含有界面活性劑的液體(所謂清洗劑)施行處理時,仍可防止清洗劑滲透於連續多孔質體中。根據JIS R3257(1999)所測定玻璃基板上的接觸角為60°以下的溶液,從成形品形成有薄膜層之面的滲透度,更佳係20%以下、特佳係10%以下。又,滲透度為30%以下的溶液之接觸角更佳係45°以下、特佳係30°以下。根據JIS R3257(1999)所測定玻璃基板上的接觸角為60°以下的溶液,從成形品形成有薄膜層之面的滲透度,係可與上述水滲透度同樣地進行測定。清洗劑係可舉例如汽車等洗車時所用者、或衣類等洗滌時所使用者、餐具等清洗時所使用者等主成分係含有界面活性劑的溶液。界面活性劑的種類並無特別的限定,親水性部 分係有離子性與非離子性,而離子性之中係有陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑。從油成分等髒污除去(洗淨)的觀點,主流係含有陰離子界面活性劑者,該等界面活性劑係可直接使用、亦可利用水等稀釋後才使用。另外,實施形態2的成形品中,多孔質體、薄膜層、成形品均係同實施形態1。
針對連續多孔質體的先質、及連續多孔質體之製造方法進行說明。
製造先質的方法係可舉例如:對在強化纖維氈上熔融或軟化狀態的基質樹脂施行加壓或減壓之方法。具體而言,從製造容易度的觀點,較佳係可例示對從強化纖維氈的厚度方向二側及/或中心配置基質樹脂的積層物,施行加熱、加壓而使基質樹脂熔融含浸的方法。
構成連續多孔質體的強化纖維氈之製造方法,係例如:預先將強化纖維呈股條及/或略單絲狀分散,而製造強化纖維氈的方法。強化纖維氈的製造方法的公知技術係可舉例如:將強化纖維利用空氣流施行分散薄片化的氣流成網法;將強化纖維一邊施行機械式梳削、一邊整理形狀而施行薄片化的梳棉法等乾式製程;利用將強化纖維在水中攪拌施行抄紙的萊特萊德(Radoraito)法進行之濕式製程。使強化纖維更接近單絲狀的手段,乾式製程係可例示:設置開纖棒的方法或更進一步使開纖棒振動的方法、縮小梳棉網眼的方法、或調整梳棉旋轉速度的方法等。濕式製程係可例示:調整強化纖維攪拌條件的方法、將分散液之強化纖維濃度稀薄化的方 法、調整分散液黏度的方法、在移送分散液時抑制渦流的方法等。特別係強化纖維氈較佳為利用濕式製程進行製造,藉由增加投入纖維的濃度、或調整分散液的流速(流量)與網格式輸送機的速度,便可輕易調整強化纖維氈的強化纖維比例。例如藉由使網格式輸送機的速度相對較慢於分散液的流速,便可使所獲得強化纖維氈中的纖維配向不易朝拉伸方向,便可製造蓬鬆的強化纖維氈。強化纖維氈係可由強化纖維單體構成,亦可由強化纖維與粉末形狀或纖維形狀的基質樹脂成分混合,或者由強化纖維與有機化合物或無機化合物混合,或者在強化纖維彼此間填塞基質樹脂成分。
用於實現上述各方法的設備較佳係使用壓縮成形機或雙帶沖壓機。批次式的情況便採用前者,藉由形成由加熱用與冷卻用的2台以上並排而成的間歇式沖壓系統,便可達生產性提升。連續式的情況便採用後者,因為可輕易施行連續式加工,因而連續生產性優異。
接著,使先質膨脹而成形為連續多孔質體的步驟,並無特別的限定,較佳係藉由使構成連續多孔質體的基質樹脂黏度降低,再成形為連續多孔質體。使基質樹脂黏度降低的方法,較佳係加熱先質。相關加熱方法並無特別的限定,可舉例如:使接觸於經設定在所需溫度的模具或熱板等而施行加熱的方法;或使用加熱器等依非接觸狀態施行加熱的方法。當構成連續多孔質體的基質樹脂係使用熱可塑性樹脂的情況,只要加熱至熔點或軟化點以上便可,若使用熱硬化性樹脂的情況,則依硬化反應開始進行時的溫度更低溫度施行加熱。
施行連續多孔質體之厚度控制的方法,係在可將經加 熱之先質控制於目標厚度的前提下,方法並無限制,從製造簡便度的觀點,較佳方法係可例示:使用金屬板等約束厚度的方法;利用對先質所賦予的壓力進行厚度控制的方法等。用於實現上述方法的設備,較佳係使用壓縮成形機或雙帶沖壓機。批次式的情況便採用前者,藉由形成由加熱用與冷卻用的2台以上並排而成的間歇式沖壓系統,便可達生產性提升。連續式的情況便採用後者,因為可輕易施行連續式加工,因而連續生產性優異。
本發明的成形品較佳係將固態狀添加劑與樹脂的樹脂混合物塗佈於連續多孔質體後,藉由施行加熱而形成薄膜層。雖亦可在未施行加熱的情況下形成薄膜層,但從生產性、與能抑制薄膜層過度滲入於連續多孔質體內部的觀點,較佳係利用施行加熱形成薄膜層。
固態狀添加劑與樹脂的樹脂混合物之製造,係可利用攪拌機或擠出機實施。
樹脂混合物對連續多孔質體的塗佈,係可利用毛刷、輥、刮刀塗佈機、氣刀、模具塗佈機、半月板塗佈、棒塗機等實施。又,亦可利用壓縮空氣等,藉由吹出形成薄膜層的樹脂混合物而實施。此時雖無特別的限定,但從抑制過度滲入連續多孔質體之空隙的觀點,較佳係依較由後述連續多孔質體之空隙徑(孔徑)測定所獲得壓力P更小的壓力施行樹脂混合物的塗佈。
經塗佈樹脂混合物的連續多孔質體再施行加熱。加熱溫度係熱硬化性樹脂的情況只要為硬化溫度以上便可,若熱可塑性樹脂的情況則只要為熔點或軟化點以上便可。
再者,若構成薄膜層的樹脂係使用熱可塑性樹脂時,在射出成型用模具中安裝連續多孔質體後,藉由施行嵌入成形便可施行塗佈。
依上述方式所製造的本發明成形品,係可適用於例如:「個人電腦、顯示器、OA機器、行動電話、行動資訊終端、PDA(電子記事簿等行動資訊終端)、攝影機、光學機器、音響、空調機、照明機器、娛樂用品、玩具用品、其他家電製品等的框體、托架、機殼、內裝構件、振動板、揚聲器錐、或其箱體」等電氣、電子機器零件;「揚聲器錐」等音響構件;「各種構件、各種框架、各種鉸鏈、各種臂、各種車軸、各種車輪用軸承、各種樑」、「罩體、屋頂、門、擋泥板、汽車後行李箱、側板、後圍板、前車殼、底盤、各種柱、各種構件、各種框架、各種樑、各種支架、各種滑軌、各種鉸鏈」等外板或車體零件;「保險桿、保險桿樑、飾條、車底護板、引擎蓋、整流板、擾流板、前罩板通風孔、空力套件」等外裝零件;「儀表板、片框架、門飾板、車柱飾板、把手、各種模組」等內裝零件;或「馬達零件、CNG槽、汽油槽」等汽車、二輪車用構造零件;「電池載盤、頭燈架、踏板外殼、保護器、燈光反射器、燈殼、噪音消除板、備胎蓋」等汽車、二輪車用零件;「隔音牆、防音牆等牆內構件」等建材;「起落架、翼翹、擾流板、翼緣、梯子、電梯、整流片、肋、座椅」等飛機用零件。從力學特性與形狀塑造性的觀點,較佳係使用於汽車內外裝、電氣‧電子機器框體、腳踏車、運動用品用構造材、飛機內裝材、輸送用箱體、建材。又,當將本發明成形品具防水性之面設為內表面時,便可使用於栽種植物等工廠所使用之吸水海綿(插花專用吸水海綿)或保水性鋪設之柏油的表 面及/或內部。
以下,利用實施例針對本發明進行更詳細說明。
從成形品中切取100mm×100mm試驗片,測定質量M0。接著,準備水或溶液30g,滴下於試驗片之薄膜層側表面上。經5分鐘後,將試驗片翻面,除去試驗片表面上殘留的水或溶液。再度測定試驗片的質量M1,並從下式計算出。
滲透度[%]={(M1-M0)÷30}×100 式(1)
參考JIS R3257(1999)基板玻璃表面潤濕性試驗方法的靜態液滴法,測定滲透度所使用溶液的接觸角。從側面拍攝水滴形狀,並測量高度h與半徑r。從所獲得數值與下式計算出接觸角。另外,清洗劑係將經摻入汽車洗車用陰離子界面活性劑的溶液,利用水施行稀釋後才使用。
接觸角θ[°]=2Tan-1(h/r) 式(2)
從成形品切取長10mm、寬10mm的試驗片,包埋於環氧樹脂中,依成形品厚度方向的垂直截面成為觀察面之方式施行研磨而製作試料。針對試料使用雷射顯微鏡(KEYENCE(股)製、VK-9510)測定薄膜層的厚度。從試料片厚度方向的垂直方向端,等間隔取10 個位置,並從薄膜層表面測定靠多孔質體側的位置。薄膜層的厚度分別針對5片試驗片拍攝10個地方,從合計50個地方的薄膜層之厚度利用算術平均而求得。
將薄膜層形成時所使用的固態狀添加劑與樹脂,依既定比例混合的樹脂混合物,依厚度成為1mm之方式塗佈於具脫模性的薄膜上,再使硬化或固化。從所獲得板狀薄膜層切取25mm×25mm試驗片。從質量與體積計算出薄膜層的密度ρs。
使用雷射顯微鏡測定固態狀添加劑的形狀。固態狀添加劑之最大尺寸的測定係當僅可取得固態狀添加劑的情況,便直接測定。混合於樹脂等之中的固態狀添加劑,係在空氣中依500℃加熱30分鐘,將樹脂成分燒光後才測定最大尺寸。
參考JIS K7244(2005)塑膠-動態機械特性試驗方法-第10部:根據平行平板振動流變儀的複剪切黏度,測定23℃下的樹脂黏度。在TA Instruments製的動態黏彈性裝置中,測定夾具係使用直徑40mm平板的平行板,依板間距離成為1mm之方式安裝樹脂,再利用扭轉模式(測定頻率:0.5Hz)施行測定。
將樹脂安裝於(6)所使用的動態黏彈性裝置上,然後升溫至50℃並保持30分鐘。然後,與(6)同樣地施行黏度測定。
從連續多孔質體中切取試驗片,測定質量Ws後,將試驗片在空氣中依500℃加熱30分鐘而燒光樹脂成分,測定剩餘的強化纖維質量Wf,再依下式計算。
Vf(體積%)=(Wf/ρf)/{Wf/ρf+(Ws-Wf)/ρr}×100
ρf:強化纖維的密度(g/cm3)
ρr:基質樹脂的密度(g/cm3)
從連續多孔質體中切取試驗片,參考JIS K7222(2005)測定連續多孔質體的表觀密度。試驗片的尺寸係設為長100mm、寬100mm。利用測微器測定試驗片的長、寬、厚,再從所獲得數值計算出試驗片的體積V。又,利用電子天秤測定所切取試驗片的質量M。藉由將所獲得質量M與體積V代入下式,計算出連續多孔質體(A)的密度ρp。
ρp[g/cm3]=M[g]/V[cm3]
從成形品中切取含有連續多孔質體與薄膜層的部分作為試驗片,與(9)連續多孔質體的密度ρp同樣地測定成形品的表觀密度,計算出密度ρm。
從連續多孔質體中切取長10mm、寬10mm的試驗片,利用掃描式電子顯微鏡(SEM)(日立先端科技(股)製S-4800型)觀察截面,從連續多孔質體的表面,依1000倍的倍率等間隔拍攝10個地方。針對各個影像,求取影像內的空隙面積Aa。又,藉由將空隙面積Aa除以影像全體面積而計算出空隙率。連續多孔質體之空隙的體積含有率係針對5片試驗片分別各拍攝10個地方,再從合計50個地方的空隙率,利用算術平均求取。
依照下述(a)~(d)測定連續多孔質體的通氣性。將直到JIS規格的試驗條件上限500Pa均可確認到通氣性者評為「具通氣性」。除此以外均評為「無通氣性」。
(a)從連續多孔質體切取100mm×100mm、厚度5mm的試驗片(若在5mm以下便直接使用。若厚於5mm的情況,便利用切削加工等進行厚度調整。)。
(b)將試驗片的端部(裁切面)4面利用膠帶包覆(為防止朝面內方向通氣)。
(c)在JIS L1096(2010)A法(弗雷澤法(Frazier method))可測定的試驗機圓筒一端安裝試驗片。
(d)依傾斜形氣壓計成為500Pa以下壓力的方式,調整抽風機及空氣孔。
從連續多孔質體切取長10mm、寬10mm試驗片,使用JIS R1655(2003)的壓汞法,測定連續多孔質體的空隙徑(孔徑)。連續多孔質體的空隙徑(孔徑)係由下式計算出:d=-4σ(cos θ)/P
d[m]:連續多孔質體的空隙徑(孔徑)
σ[N/m]:水銀的表面張力
θ[°]:水銀與試驗片的接觸角
P[Pa]:賦予水銀的壓力
從成形品切取試驗片,利用雷射顯微鏡觀察試驗片截面。此時,觀察構成薄膜層的固態狀添加劑是否有存在於連續多孔質體的空隙內。
下述實施例與比較例係使用以下材料。
將東麗(股)製「Torayca」T700S-12K利用美工刀裁切成5mm,獲得切股碳纖維。製作由水與界面活性劑(NACALAI TESQUE(股)製、聚氧乙烯月桂醚(商品名))構成的濃度0.1質量%之分散液,使用該分散液與切股碳纖維,並使用圖2所示強化纖維氈的製造裝置,製造強化纖維氈。圖2所示製造裝置係具備有:分散槽,其係在容器下部設有開口旋塞的直徑1000mm的圓筒形狀容器;以及將分散槽與抄紙槽予以連接的直線狀輸送部(傾斜角30°)。在分散槽上面的開口部附設攪拌機,可從開口部丟入切股碳纖維與分散液 (分散介質)。抄紙槽係具備有底部寬500mm抄紙面的網格式輸送機,且將可搬送碳纖維基材(抄紙基材)的輸送機,連接於網格式輸送機。抄紙係將分散液中的碳纖維濃度設為0.05質量%而實施。經抄紙的碳纖維基材在200℃乾燥爐中乾燥30分鐘,獲得表觀密度100g/m2的強化纖維氈。
製作由未改質聚丙烯樹脂(Prime Polymer(股)製「Prime Polypro」(註冊商標)J105G)80質量%、與酸改質聚丙烯樹脂(三井化學(股)製「ADMER」QB510)20質量%構成,且表觀密度100g/m2的樹脂薄片。
依主劑之三菱化學(股)製jER828:100質量份、硬化劑之東京化成工業(股)製三伸乙四胺11質量份的比例進行混合,而準備樹脂1。
將主劑之三菱化學(股)製jER828:85質量份、jER1001:15質量份,一邊加熱至120℃一邊進行混合。接著,依硬化劑之東京化成工業(股)製三伸乙四胺:9.7質量份的比例進行混合,而準備樹脂2。
將未改質聚丙烯樹脂(Prime Polymer(股)製「Prime Polypro」(註冊商標)J709QG)80質量%、酸改質聚丙烯樹脂(三井化學(股)製「ADMER」QB510)20質量%、以及後述固態狀添加劑2:5質量%施行熔融混練後之顆粒,準備作為樹脂3。
固態狀添加劑1係準備3M公司製玻璃微球K20。
固態狀添加劑2係準備Central Glass Fiber(股)製磨碎纖維EFH50-31。
固態狀添加劑3係準備日本板硝子(股)製玻璃碎片「METASHINE」1080。
強化纖維氈係使用強化纖維氈1,樹脂薄片係使用PP樹脂,製作依[樹脂薄片/強化纖維氈/樹脂薄片/強化纖維氈/強化纖維氈/樹脂薄片/強化纖維氈/樹脂薄片]的順序配置之積層物。接著,經由以下步驟(I)~(IV)獲得連續多孔質體的先質。。
步驟(I):將積層物配置於預熱至200℃的沖壓成形用模穴內,再關閉模具。
步驟(II):接著,賦予3MPa的壓力,並保持180秒鐘。
步驟(III):步驟(II)後,在保持壓力的狀態下,將模穴溫度冷卻至50℃。
步驟(IV):打開模具,取出連續多孔質體的先質。
使用連續多孔質體的先質,以及圖3所示具有沖壓機熱板3、模具4,且可製作平板的沖壓成形用模具,經由以下步驟(I)~(V)獲得連續多孔質體。
步驟(I):將連續多孔質體的先質,利用設定為260℃的IR加熱器施行60秒鐘預熱。
步驟(II):預熱後,將先質5配置於設定為120℃的沖壓成形用模穴內。此時,插入用於調整連續多孔質體之厚度的金屬間隔物6。
步驟(III):接著,利用沖壓機熱板3賦予3MPa的壓力,並保持60秒鐘。
步驟(IV):然後,在保持壓力的狀態下,將模穴溫度冷卻至50℃。
步驟(V):打開模具4,取出連續多孔質體。
薄膜層形成用材料係分取樹脂1:100質量份、固態狀添加劑1:15質量份,並製作樹脂混合物A。所獲得樹脂混合物A在連續多孔質體表面上,依表觀密度成為50g/m2的方式施行塗佈,利用爐內溫度設定為50℃的乾燥機施行1小時乾燥而獲得成形品。針對所獲得成形品,使用表1所記載的水與溶液,測定滲透度。結果示於表1。
除使用固態狀添加劑2之外,其餘均與實施例1同樣地獲得成形品。實施例2所獲得成形品的特性係示於表1。
除使用固態狀添加劑3之外,其餘均與實施例1同樣地獲得成形品。實施例3所獲得成形品的特性係示於表1。
除使用樹脂2,且將乾燥時間設為30分鐘之外,其餘均與實施例1同樣地獲得成形品。實施例4所獲得成形品的特性係示於表1。
除實施例1的樹脂混合物A係每次25g/m2分開2次塗佈之外,其餘均與實施例1同樣地(塗佈25g/m2,乾燥後再塗佈25g/m2並乾燥),獲得成形品。實施例5所獲得成形品的特性係示於表1。
(實施例6)
從連續多孔質體中切取130mm×130mm試驗片。又,薄膜層形成用的材料係使用樹脂3:100質量份、固態狀添加劑2:15質量份,將該等施行乾式摻合後,利用擠筒溫度設定為200℃的雙螺桿擠出機施行混練,製作顆粒狀的樹脂混合物B。接著,在射出成形機(日本製鋼所(股)製J150EII-P)中所安裝的射出成形用模具(模穴厚度:3.5mm)內,嵌入試驗片,依料管溫度220℃、模具溫度50 ℃,於試驗片單面上將樹脂混合物B施行嵌入成形,獲得成形品。實施例6所獲得成形品的特性係示於表1。
除未使用固態狀添加劑之外,其餘均與實施例1同樣地獲得成形品。比較例1所獲得成形品的特性係示於表1。
如表1所示,可確認到本實施例的成形品,能抑制連續多孔質體表面的水、或含界面活性劑之溶液的滲透。實施例1~3的成形品,藉由使用各種固態狀添加劑形成薄膜層,便可對連續多孔質體賦予防水性。特別係實施例1,因為使用中空玻璃珠,因而可從輕量性優異的連續多孔質體,獲得經抑制質量增加的成形品。又,實施例3,因為使用玻璃碎片,因而獲得亦對薄膜層賦予設計性的成形品。相關實施例4,藉由使用硬化速度較快的樹脂,便可抑制樹脂混合物過度滲入連續多孔質體內部,成為防水性高的成形品。相關實施例5,藉由將薄膜層的形成分開為複數次形成,便可提高防水性。另一方面,比較例1,因為僅利用樹脂形成薄膜層,因而在連續多孔質體表面上殘留較多的孔,難以顯現出防水性。
根據本發明可獲得剛性與輕量性均優異、且防液性優異的成形品。
Claims (11)
- 一種成形品,係在厚度方向具有連續空隙的連續多孔質體上,形成含有固態狀添加劑與樹脂之薄膜層的成形品;其中,上述連續多孔質體係含有強化纖維、基質樹脂、及空隙;上述薄膜層的密度係2.5g/cm3以下;從形成有上述薄膜層之面的水滲透度係10%以下,或者,根據JIS R3257(1999)所測定玻璃基板上的接觸角為60°以下之溶液,從形成有上述薄膜層之面的滲透度係30%以下。
- 如請求項1之成形品,其中,上述薄膜層係侵入於上述連續多孔質體的空隙內。
- 如請求項1或2之成形品,其中,上述固態狀添加劑的至少一部分係存在於上述連續多孔質體的空隙內。
- 如請求項1或2之成形品,其中,上述薄膜層的厚度係500μm以下。
- 如請求項1或2之成形品,其中,上述固態狀添加劑的最大尺寸係200μm以下。
- 如請求項1或2之成形品,其中,上述固態狀添加劑係中空構造體。
- 如請求項1或2之成形品,其中,構成上述薄膜層的上述樹脂係熱硬化性樹脂。
- 如請求項7之成形品,其中,23℃下的上述熱硬化性樹脂之黏度係1×101~1×104Pa‧s。
- 如請求項7之成形品,其中,依50℃加熱30分鐘時,上述熱硬化性樹脂的黏度係1×104Pa‧s以上。
- 一種成形品之製造方法,係請求項1至9中任一項之成形品的製造方法,其中,將上述固態狀添加劑與上述樹脂的樹脂混合物塗佈於上述連續多孔質體之後,藉由施行加熱而形成薄膜層。
- 如請求項10之成形品之製造方法,其中,上述薄膜層係由2層以上的層構成。
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2019
- 2019-03-28 US US17/042,305 patent/US20210016549A1/en not_active Abandoned
- 2019-03-28 JP JP2019518002A patent/JP7283382B2/ja active Active
- 2019-03-28 CN CN201980020535.6A patent/CN111886129A/zh active Pending
- 2019-03-28 EP EP19776767.6A patent/EP3778211A4/en active Pending
- 2019-03-28 KR KR1020207027120A patent/KR20200138219A/ko unknown
- 2019-03-28 WO PCT/JP2019/013620 patent/WO2019189583A1/ja active Application Filing
- 2019-03-29 TW TW108111145A patent/TWI820105B/zh active
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JP7283382B2 (ja) | 2023-05-30 |
CN111886129A (zh) | 2020-11-03 |
US20210016549A1 (en) | 2021-01-21 |
WO2019189583A1 (ja) | 2019-10-03 |
KR20200138219A (ko) | 2020-12-09 |
EP3778211A4 (en) | 2021-12-15 |
EP3778211A1 (en) | 2021-02-17 |
TW201945172A (zh) | 2019-12-01 |
JPWO2019189583A1 (ja) | 2021-02-12 |
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