TWI576376B - 樹脂複合體的製造方法 - Google Patents

樹脂複合體的製造方法 Download PDF

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Publication number
TWI576376B
TWI576376B TW104131397A TW104131397A TWI576376B TW I576376 B TWI576376 B TW I576376B TW 104131397 A TW104131397 A TW 104131397A TW 104131397 A TW104131397 A TW 104131397A TW I576376 B TWI576376 B TW I576376B
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TW
Taiwan
Prior art keywords
sheet
resin
fiber
polyester
foamed sheet
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TW104131397A
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English (en)
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TW201627367A (zh
Inventor
桑原佑輔
人見一迅
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積水化成品工業股份有限公司
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Publication of TW201627367A publication Critical patent/TW201627367A/zh
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    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
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Description

樹脂複合體的製造方法 [參照之相關申請案]
本案係主張日本專利申請案第2014-198419號之優先權，並藉由引用而予以納入本案說明書之揭示。
本發明係關於一種樹脂複合體之製造方法及一種聚酯系樹脂發泡體，該樹脂複合體係使芯材與纖維強化樹脂片材之兩個樹脂製構件積層一體化而成者，該聚酯系樹脂發泡體係利用作為前述芯材者。
以往，纖維強化樹脂(FRP)片材係被廣泛地利用作為用以構成船舶、貨車的主體。
該纖維強化樹脂片材，通常係具備包含玻璃纖維等強度優良的纖維之織物或不織布作為基材片材，並使樹脂含浸至該基材片材者。
因此，纖維強化樹脂片材係具有較未以纖維強化的一般樹脂片材優良的強度。
近年來，正檢討使如此之纖維強化樹脂片材與含有樹脂發泡體之芯材積層一體化，藉此製作出兼具優良的強度 與輕量性的樹脂複合體(參照下述專利文獻1)。
此種樹脂複合體，係於表面具備藉由纖維強化樹脂片材形成的高強度之纖維強化樹脂層，並且，於芯材係使用輕量的樹脂發泡體。
因此，使得此種樹脂複合體於例如風力發電用的風車之翼板、電子機器的外殼、汽車零件等追求輕量性與高機械強度的領域中之用途擴大。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開2014-028920號公報
就構成樹脂複合體之纖維強化樹脂片材的基材片材而言，通常以為不織布之情形容易使樹脂含浸。
另一方面，基材片材為織物者則容易使纖維強化樹脂層成為高強度者。
然而，即使使用基材片材為織物的纖維強化樹脂片材，也會有在與芯材的積層時基材片材的纖維成為紊亂狀態而無法於樹脂複合體發揮充分的強度之情形，因而尋求其對策。
本發明係以滿足此種需求為課題，並以提供強度優良的樹脂複合體為課題。
為了解決上述課題，本發明者經精心研究後發現，由錨定效應(anchor effect)等觀點來看，一般所使用之芯材係以使其表面粗度變粗之方式為條件而進行製作。
而且，本發明者發現，由於芯材的表面粗度粗之故，會有無法於樹脂複合體發揮充分地強度之情形。
因此，本發明者發現當以聚酯系樹脂作為芯材的主原料時，可藉由賦予芯材預定的表面性狀而解決上述之問題，遂完成本發明。
亦即，用以解決上述課題的本發明之聚酯系樹脂發泡體，其係用於包含樹脂發泡體的芯材與纖維強化樹脂片材積層一體化的樹脂複合體之形成，係使用作為前述芯材之聚酯系樹脂發泡體；前述纖維強化樹脂片材係具備包含纖維織物的基材片材、與含浸至該基材片材的樹脂，積層該纖維強化樹脂片材之面的表面粗度為2.5μm以下。
而且，用以解決上述課題的本發明之樹脂複合體的製造方法，其係使用纖維強化樹脂片材與包含樹脂發泡體的芯材，並實施使前述芯材與前述纖維強化樹脂片材進行積層一體化而形成樹脂複合體之積層步驟之樹脂複合體的製造方法；前述纖維強化樹脂片材係具備：包含纖維織物的基材片材、與含浸至該基材片材的樹脂；前述芯材係具有2.5μm以下的表面粗度(Ra)之聚酯系樹脂發泡體；前述積層步驟係於前述聚酯系樹脂發泡體之具有前述表面粗度(Ra)的面積層前述強化樹脂片材。
再者，於本說明書中之「表面粗度(Ra)」之用語，只要沒有特別的說明，即意指於JIS B 0601-2013所規定的算術平均粗度(Ra)。
根據本發明，可提供一種強度優良的樹脂複合體。
以下說明本發明之實施型態。
首先，說明樹脂複合體。
本實施型態的樹脂複合體係纖維強化樹脂片材與包含聚酯系樹脂發泡體的芯材經積層一體化而成者。
纖維強化樹脂片材係具備：包含纖維織物的基材片材、以及含浸至該基材片材的樹脂。
樹脂複合體，係藉由該纖維強化樹脂片材而成為於芯材表面上具備纖維強化樹脂層的構造。
作為此處之前述芯材，可列舉例如：聚酯系樹脂發泡片材(以下，亦略稱為「發泡片材」)或以聚酯系樹脂發泡顆粒於模內成形之顆粒發泡成型體。
以下，主要係以芯材為發泡片材之情形為例，對於本發明的實施型態進行說明。
以下說明用以構成前述芯材的發泡片材
該發泡片材，從其生產效率層面而言，較佳為使以聚 酯系樹脂作為主成分的聚酯系樹脂組成物擠出發泡者。
該發泡片材係至少於單面具有2.5μm以下的表面粗度(Ra)。
發泡片材係為了在具有如此表面粗度的面上積層纖維強化樹脂片材而使用。
再者，一般的擠出發泡法中，係發泡片材難以成為2.5μm以下的表面粗度(Ra)。
因此，發泡片材較佳為一度製作成表面粗度(Ra)超過2.5μm的狀態後，再另外以使表面粗度(Ra)成為2.5μm以下之方式進行處理。
再者，就難以直接得到具有2.5μm以下表面粗度(Ra)的芯材之點而言，對於顆粒發泡成形體來說亦相同。
作為成為前述發泡片材的主原料之聚酯系樹脂，係可採用例如二羧酸與多元醇經縮合反應而得之高分子量的線狀聚酯。
該聚酯樹脂可列舉例如芳香族聚酯樹脂。
該聚酯樹脂亦可為聚乳酸系樹脂等脂肪族聚酯樹脂。
芳香族聚酯樹脂通常含有芳香族二羧酸成分與二元醇成分。
作為該芳香族聚酯樹脂，係可列舉：聚對酞酸乙二酯樹脂、聚對酞酸丙二酯樹脂、聚對酞酸丁二酯樹脂、聚對酞酸環己基二甲酯樹脂、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯等。
前述發泡片材所含有之芳香族聚酯樹脂，較佳係聚對 酞酸乙二酯樹脂。
再者，芳香族聚酯樹脂係可單獨使用，亦可2種以上併用。
芳香族聚酯樹脂除了芳香族二羧酸成分及二元醇成分以外，亦可含有三元以上的多元羧酸及其酸酐作為構成成分。
具體而言，芳香族聚酯樹脂亦可含有1,2,4-苯三甲酸等三羧酸、1,2,4,5-苯四甲酸等四羧酸來作為構成成分。
芳香族聚酯樹酯除了芳香族二羧酸成分及二元醇成分以外，亦可含有甘油等三元醇、新戊四醇等四元醇之所謂三元以上的多元醇來作為構成成分。
而且，發泡片材中含有之芳香族聚酯樹脂，亦可為由使用後的保特瓶等回收而再生之循環利用材料。
發泡片材中含有之芳香族聚酯樹脂，只要是在能發揮熱可塑性之範圍內，亦可經施行部分交聯。
作為用以交聯芳香族聚酯樹脂的交聯劑，可列舉例如：1,2,4,5-苯四甲酸二酐等酸二酐、多官能環氧化合物、唑啉化合物、化合物等。
再者，交聯劑係可單獨使用，亦可併用2種以上。
當聚對酞酸乙二酯樹脂係藉由交聯劑交聯時，只要將聚對酞酸乙二酯樹脂與交聯劑一同供給至擠出機，藉此於該擠出機內進行動態交聯即可。
當供給至擠出機之交聯劑的量過少時，會有使聚對酞 酸乙二酯樹脂的熔融黏度不足之疑慮。
而且，當聚對酞酸乙二酯樹脂的熔融黏度過低，則會有於將發泡片材進行擠出發泡時容易產生破泡之疑慮。
另一方面，當交聯劑的量過多時，會有聚對酞酸乙二酯樹脂的熔融黏度變得過高之疑慮。
聚對酞酸乙二酯樹脂的熔融黏度若變得過高，則會有於藉由擠出發泡製造發泡片材時等使擠出機的負荷變得過高，而擠出發泡本身變得困難之疑慮。
因而，以用以構成前述芯材的樹脂組成物之基底樹脂作為交聯聚對酞酸乙二酯樹脂時，相對於前述聚對酞酸乙二酯樹脂100質量份，較佳為以交聯劑為0.01質量份以上、5質量份以下之比例使用而進行交聯。
而且，前述比例更佳為0.1質量份以上、1質量份以下。
作為前述聚乳酸系樹脂，係可使用乳酸與酯鍵結而聚合之樹脂。
使發泡片材中含有的熱可塑性樹脂為聚乳酸系樹脂時，由商業上的取得容易性及賦予發泡性的容易性之觀點而言，該乳酸系樹脂係較佳為D-乳酸(D型)及L-乳酸(L型)的共聚物；D-乳酸或L-乳中之任一者的均聚物；由D-交酯、L-交酯及DL-交酯所成群組中選出之1種或2種以上的交酯之開環聚合物。
再者，聚乳酸系樹脂係可單獨使用，亦可併用2種以上。
聚乳酸系樹脂，亦可含有脂肪族多元醇等 作為乳酸以外的單體成分。
該單體成分係可列舉例如：乙醇酸(glycolic acid)、羥基丁酸、羥基戊酸、羥基己酸、羥基庚酸等脂肪族羥基羧酸；琥珀酸、己二酸、辛二酸、癸二酸、十二烷基二羧酸、琥珀酸酐、己二酸酐、1,2,4-苯三甲酸、丙三甲酸，1,2,4,5-苯四甲酸、1,2,4,5-苯四甲酸酐等脂肪族多元羧酸；乙二醇、1,4-丁二醇、1,6-己二醇、1,4-環己烷二甲醇、新戊二醇、癸二醇、甘油、三羥甲基丙烷、新戊四醇等。
聚乳酸系樹脂亦可具備例如烷基、乙烯基、羰基、芳香族基、酯基、醚基、醛基、胺基、腈基、硝基等官能基。
聚乳酸系樹脂係可藉由異氰酸酯系交聯劑等進行交聯，亦可於主鏈、側鏈具備酯鍵以外的鍵結。
再者，發泡片材係可於如此之基底樹脂適宜地調配發泡劑、氣泡核劑，調製適於擠出發泡的聚酯系樹脂組成物，並將該聚酯系樹脂組成物藉由安裝有圓形模具(circular die)或平模(flat die)之擠出機進行擠出發泡而製作。
前述發泡劑係可適宜地採用化學發泡劑、物理發泡劑。
前述化學發泡劑可列舉例如：偶氮二甲醯胺、二亞硝基五亞甲基四胺、伸肼基二甲醯胺、碳酸氫鈉等。
再者，化學發泡劑係可單獨使用，亦可併用2種以上。
前述物理發泡劑可列舉例如：丙烷、正丁 烷、異丁烷、正戊烷、異戊烷、己烷等飽和脂肪族烴；二甲醚等醚類；氯甲烷、1,1,1,2-四氟乙烷、1,1-二氟乙烷、單氯二氟甲烷等氟氯碳化物；二氧化碳、氮等。
此等之中，於前述發泡片材的製作中使用之發泡劑，較佳為二甲醚、丙烷、正丁烷、異丁烷、二氧化碳等。
前述發泡劑更佳為丙烷、正丁烷、異丁烷等，特佳為正丁烷、異丁烷。
又，物理發泡劑係可單獨使用，亦可併用2種以上。
而且，亦可併用化學發泡劑與物理發泡劑。
前述氣泡核劑係可列舉例如：滑石、雲母、氧化矽、矽藻土、氧化鋁、氧化鈦、氧化鋅、氧化鎂、氫氧化鎂、氫氧化鋁、氫氧化鈣、碳酸鉀、碳酸鈣、碳酸鎂、硫酸鉀、硫酸鋇、玻璃珠等無機化合物粒子；聚四氟乙烯等有機化合物粒子等。
而且，用以製作發泡片材的聚酯系樹脂組成物中，另可含有抗氧化劑、抗老化劑、耐候劑、抗菌劑、難燃劑、抗靜電劑、防蟻劑、防鼠劑、顏料等各種添加劑。
該發泡片材通常可採用厚度0.5至5mm者，亦可採用表觀密度為0.01至0.7g/cm3者作為前述芯材。
用以於該發泡片材形成纖維強化樹脂層之前述纖維強化樹脂片材，前述基材片材或前述樹脂並無特別限定。
構成纖維強化樹脂片材之基材片材的纖維，係可列舉例如：不鏽鋼纖維或鋼纖維等金屬纖維；玻璃纖維、碳纖 維、硼纖維、碳化矽纖維、氧化鋁纖維、泰倫諾(Tyranno，音譯)纖維、玄武岩纖維或其他陶瓷纖維的所謂無機纖維；芳綸纖維、聚乙烯纖維、聚對伸苯基苯並二唑(PBO，poly(p-phenylenebenzobisoxazole))纖維等有機纖維等。
其中，構成基材片材的纖維，由具有優良的機械強度及耐熱性而言，較佳為碳纖維、玻璃纖維、芳綸纖維等，更佳為碳纖維。
作為前述基材片材，係可採用例如將併線有複數個前述纖維的併線紗或撚紗進行平織、斜紋織或緞紋織的面材。
前述基材片材係可僅以1片面材構成，亦可積層複數面材而構成。
而且，對於前述纖維強化樹脂層而言，亦不需僅以1片纖維強化樹脂片材構成，也可以複數片纖維強化樹脂片形成纖維強化樹脂層。
又且，含浸至前述基材片材中並與前述基材片材一同利用於纖維強化樹脂層的形成之樹脂並無特別地限制，可列舉例如一般的熱可塑性樹脂或熱硬化性樹脂。
作為前述熱可塑性樹脂並無特別地限制，可列舉例如：烯烴系樹脂、聚酯系樹脂、聚醯胺系樹脂、熱可塑性聚胺酯樹脂、硫醚系樹脂、丙烯酸系樹脂等。
又，熱可塑性樹脂係可單獨使用亦可併用2種以上。
構成前述纖維強化樹脂片材的樹脂，考量到與發泡片材的接著性，於熱可塑性樹脂中較佳為聚酯樹脂。
作為構成纖維強化樹脂片材之前述熱硬化性樹脂並無特別地限制，可列舉例如：環氧樹脂、不飽和聚酯樹脂、酚醛樹脂、三聚氰胺樹脂、聚胺酯樹脂、聚矽氧樹脂、馬來醯亞胺樹脂、乙烯基酯樹脂、氰酸酯樹脂等。
前述熱硬化性樹脂亦可為將馬來醯亞胺樹脂與氰酸酯樹脂預聚合之樹脂。
由耐熱性、彈性率及耐藥品性為優良而言，前述熱硬化性樹脂較佳為環氧樹脂、乙烯基酯樹脂。
又，熱硬化性樹脂係可單獨使用，亦可併用2種以上。
纖維強化樹脂片材中樹脂的含量，較佳為20質量%以上、70質量%以下，更佳為30質量%以上、60質量%以下。
而且，纖維強化樹脂片材的厚度，較佳為0.02mm以上、2mm以下，更佳為0.05mm以上、1mm以下。
於使用如此之纖維強化樹脂片材與前述發泡片材而得到樹脂複合體時，只要例如依序實施下述(a)步驟至(e)步驟即可。
(a)片材製作步驟
將含有發泡劑之聚酯系樹脂組成物於安裝有圓形模具之擠出機內進行熔融混練，將熔融混練物自前述圓形模具之圓環狀的吐出口以筒狀擠出，使該熔融混練物發泡而形成圓筒狀的發泡片材，將該圓筒狀之發泡片材以引取機於擠出方向下游側一邊引取一邊於圓周方向的1個位置或複數個位置處連續地切斷，而製作出長條帶狀的發泡片材之 片材製作步驟。
(b)熟成步驟
將以前述片材製作步驟而得之發泡片材以預定之溫度保管預定的期間，使殘存於內部之發泡劑與外部空氣進行置換同時緩和於擠出發泡時產生的歪斜之熟成步驟。
(c)片材平滑化步驟
將前述熟成步驟後的發泡片材藉由熱壓等進行加熱/加壓，使表面較施壓前更為平滑化之片材平滑化步驟。
(d)預成形體製作步驟
於經外型加工為預定大小的發泡片材之表面暫時接著纖維強化樹脂片材，以製作預成形體之預成形體製作步驟。
(e)積層步驟
於具有對應製品形狀的模槽(cavity)空間之成形模中置入前述預成形體，將該預成形體藉由熱壓或高壓滅菌釜(autoclave)進行加熱/加壓，使含有發泡片材的芯材與纖維強化樹脂片材積層一體化，而製作出於芯材的表面形成有纖維強化樹脂層的樹脂複合體之積層步驟。
又，於製作樹脂複合體時，並無需實施(a)至(e)的全部步驟。
而且，於製作樹脂複合體時，亦可於(a)至(e)的步驟進一步加入其他的步驟。
於前述積層步驟中，為了不使構成纖維強化樹脂片材之基材片材的纖維產生紊亂，構成預成形體之芯材的表面為平滑且與纖維強化樹脂間顯示良好的平滑性係屬重要。
具體而言，在抑制基材片材之纖維的紊亂之前提下，重要的是使構成預成形體的芯材具有2.5μm以下的表面粗度(Ra)。
另一方面，於片材製作步驟中，係難以得到表面平滑性優良的發泡片材。
於片材製作步驟中，若欲得到表面平滑性優良的發泡片材，則在製造條件上會受到各種限制而有使發泡片材的生產效率降低之虞。
因此，於片材製作步驟中，較佳為製作表面粗度(Ra)為超過2.5μm之狀態的發泡片材。
又，芯材為顆粒發泡成形體時亦同理，在得到良好的樹脂複合體之前提下，重要的是於製作表面粗度(Ra)為超過2.5μm狀態的成形體後，實施與前述之片材平滑化步驟相同的平滑化步驟，而使該成形體的表面粗度(Ra)成為2.5μm以下。
亦即，於本實施型態中對發泡片材或顆粒發泡成形體實施的平滑化步驟，係使含有發泡片材或顆粒發泡成形體之芯材的表面粗度(Ra)成為2.5μm以下者。
實施該平滑化步驟之具體方法，可列舉例如：將經鏡面加工之金屬板抵接於發泡片材、顆粒成形體的表面而實施熱壓；或將以熔點比聚酯系樹脂高的樹脂所製成之表面平滑的樹脂膜抵接於發泡片材或顆粒發泡成形體的表面而實施熱壓之方法。
而且，作為平滑化步驟之具體的實施方法，亦可列舉： 使用經鏡面加工的一對金屬輥，並於金屬輥之間設置略小於該發泡片材、顆粒發泡成形體的厚度之間隙，使發泡片材、顆粒發泡成形體通過該金屬輥間而使該發泡片材、顆粒發泡成形體的表面平滑化之方法。
又，由於使表面粗度(Ra)成為極小值係需過度的手段，因此供給至積層步驟的芯材，較佳為表面粗度(Ra)成為0.5μ以上，更佳為成為1.0μm以上。
又且，發泡片材的表面粗度(Ra)係可以下述方式求得。
(表面粗度(Ra)的求法)
表面粗度係根據JIS B0601：2013而進行測定。
具體而言，表面粗度係使用KEYENCE股份有限公司製的「雙掃描高精密度雷射測定器LT-9500、LT-9010M」作為測定裝置，並使用COMS股份有限公司製的「非接觸式輪廓形狀粗度測定系統MAP-2DS」作為數據處理軟體進行測定。
關於測定條件，測定範圍為18000μm、測定間距為5μm、測定速度為1000μm/秒、評估長度為12.5mm、基準長度為2.5mm、光量設定為40、平均濾波器為2、噪波過濾器為1。
試驗片係將發泡片材裁切製作為寬100mm×長100mm×厚度(片材厚度)者。
試驗片之數目為5個，測定於每個試驗片之正反兩面的流動方向及寬度方向的表面粗度。
算術平均粗度(Ra)，係將從平均線至測定曲線的偏差之絕對值加總，並以基準長度進行平均(n=20)。
又，最大高度係由從平均線至最高峰頂的高度與從平均線至最低谷底的深度之和而求得(n=20)。
而且，表面粗度的輪廓曲線之平均長度(Sm)，係平均線與輪廓線之交點間距離的算術平均值。
又且，於前述片材平滑化步驟中，係可於發泡片材的表面進行加熱，藉此提升構成發泡片材表面的聚酯系樹脂之結晶化度。
因為此片材平滑化步驟後的發泡片材不僅表面平滑且結晶化度經提升而表面為硬質，故在前述積層步驟中於纖維強化樹脂片材間係發揮高平滑性。
而且，因為實施片材平滑化步驟而使發泡片材的耐熱性提升，故於纖維強化片材的加熱硬化時，會變得於發泡片材不易產生尺寸變化。
因此，藉由實施片材平滑化步驟，會變得容易形成纖維紊亂少的樹脂複合體。
亦即，於片材平滑化步驟後的發泡片材的表層部中，較佳為使聚酯系樹脂具有預定以上的結晶化度，具體而言，較佳為具有15%以上的結晶化度。
關於片材平滑化步驟後的發泡片材之表層部的結晶化度，例如可藉由對從發泡片材的表面至深約0.2mm間採取之試料進行示差掃描熱量分析(DSC)而求得。
前述結晶化度，具體而言，可以下述方式求得。
(結晶化度的求法)
使用示差掃描熱量計裝置(SII nanotechnology公司製的商品名「DSC6220型」)，將前述試料以無間隙的方式填充於鋁製的測定容器的底部，並將試料在氮氣流量為20mL/分鐘的條件下以30℃持續保持2分鐘。
然後，求得將試料以10℃/分鐘之速度從30℃升溫至290℃時的DSC曲線。
此時的基準物質係使用氧化鋁。
結晶化度，係將熔解峰的面積求得之熔解熱量(mJ/mg)與從結晶化峰的面積求得之結晶化熱量(mJ/mg)之差，除以結晶性熱可塑性樹脂的完全結晶之理論熔解熱量△H0而求得。
例如，聚對酞酸乙二酯的△H0為140.1mJ/mg。
試料的結晶化度係依下述式算出。
結晶化度(%)=(｜熔解熱量(mJ/mg)｜-｜結晶化熱量(mJ/mg)｜)/△H0(mJ/mg)×100
以n之數目為5個左右算出上述的相加平均值作為發泡片材之表層部的結晶化度。
以如上述製造方法而製作之樹脂複合體，其芯材的全部表面無需經纖維強化樹脂片材覆蓋。
樹脂複合體，例如於芯材為發泡片材時，可為於該發泡片材的兩面積層有前述纖維強化樹脂片材者，亦可為僅於前述發泡片材的單面積層有前述纖維強化樹脂片材者。
若依據上述之製造方法，可更確實地得到基材片材的纖維紊亂少、且於表面全部區域具有經均質化之強度的樹脂複合體。
又，於上述雖然係以使用發泡片材作為樹脂複合體的芯材之情形為例示，惟本發明之樹脂複合體的芯材亦可為顆粒發泡成形體等。
而且，於本實施型態中，雖然例示如上述之樹脂複合體及其製造方式，惟本發明之樹脂複合體及其製造方法並不限定為上述例示者，亦可為在上述例示加入各種變更者。
[實施例]
接著列舉實施例以進一步詳細地說明本發明，惟本發明並不限定為該等實施例。
(實施例1至2)
將含有聚對酞酸乙二酯樹脂(PET，三井化學公司製的商品名「SA135」，玻璃轉移溫度Tg：79℃、熔點：247.1℃、IV值：0.86)100質量份、滑石0.72質量份及1,2,4,5-苯四甲酸酐0.2質量份的熱可塑性聚酯系樹脂組成物供給至口徑為65mm且L/D比為35的單軸擠出機，並於290℃進行熔融混練。
接著，於至前述單軸擠出機的途中，將含有異丁烷35質量%及正丁烷65質量%的丁烷以相對於聚對酞酸乙二酯100質量份成為1.0質量份之方式擠入。
而後，於前述單軸擠出機中，使丁烷均勻分散於熱可 塑性聚酯系樹脂組成物中。
之後，於單軸擠出機的前端部，將熔融狀態的聚酯系樹脂組成物冷卻至220℃後，自安裝於單軸擠出機前端的圓型模具使擠出發泡為圓筒狀而製造筒狀體。
將此筒狀體緩慢地擴徑後，將之供給至冷卻心軸，進行冷卻以使筒狀體之表面溫度成為25℃。
將冷卻後的筒狀體橫跨內外圓周面(於厚度方向)進行切斷。
切斷係於擠出方向連續地實施，並展開切斷後的筒狀體，藉此得到帶狀的聚對酞酸乙二酯發泡片材。
此時所得之聚對酞酸乙二酯發泡片材為厚度3.2mm、單位面積質量為900g/m2。
又，以下稱冷卻心軸接觸面為發泡片材的表面，相反側之面為背面。
前述發泡片材，係在製造後立即置於25℃的環境下，並於同環境下熟成達48小時。
對於熟成後的發泡片材實施如下的片材平滑化步驟。
從發泡片材裁切出一邊為640mm的平面正方形之片材片。
將裁切之片材片鋪設於設有3.0mm間隔器的加壓機，以140℃的溫度及0.5MPa的壓力進行加壓3分鐘。
之後，保持壓力並冷卻至30℃，得到具有如表1所記載的厚度、單位面積質量的表面經平滑化之發泡片材(片材片)。
(實施例3至4)
除了係於至單軸擠出機的途中將含有異丁烷35質量%及正丁烷65質量%的丁烷以相對於聚對酞酸乙二酯100質量份成為0.5質量份之方式擠入至熔融狀態的聚酯系樹脂組成物中，製造厚度2.0mm、單位面積質量600g/m2的聚對酞酸乙二酯發泡片材，以及將裁切之片材片鋪設於設有1.5mm間隔器之加壓機而進行加壓之外，與實施例1至2進行相同操作而得到表面平滑化之發泡片材。
(實施例5至6)
除了係於至單軸擠出機的途中將含有異丁烷35質量%及正丁烷65質量%的丁烷以相對於聚對酞酸乙二酯100質量份成為0.3質量份之方式擠入至熔融狀態的聚酯系樹脂組成物中，製造厚度1.7mm、單位面積質量500g/m2的聚對酞酸乙二酯發泡片材，以及將裁切之片材片鋪設於設有1.5mm間隔器之加壓機而進行加壓之外，係與實施例1至2進行相同操作而得到表面平滑化之發泡片材。
(比較例1至2)
以與實施例1至2同樣的方法製作發泡片材，但未施以片材平滑化步驟。
(比較例3至4)
以與實施例5至6同樣的方法製作發泡片材，但未施以片材平滑化步驟。
又，以實施例1至6的發泡片材作為芯材，並於該芯材積層纖維強化樹脂片材後，於基材片材的纖維並未產生顯而易見的紊亂。另一方面，以比較例1至4的發泡片材作為芯材，並於該芯材積層纖維強化樹脂片材後，與芯材的界面部分之基材片材的纖維係產生波狀的紊亂。
由此亦可知，依據本發明，可提供強度優良的樹脂複合體。

Claims (2)

  1. 一種樹脂複合體的製造方法，其係使用纖維強化樹脂片材與包含樹脂發泡體的芯材，並實施使前述芯材與前述纖維強化樹脂片材積層一體化而形成樹脂複合體之積層步驟者；前述纖維強化樹脂片材係具備包含纖維織物的基材片材與含浸至該基材片材的樹脂；前述芯材係具有2.5μm以下的表面粗度(Ra)之聚酯系樹脂發泡體；前述積層步驟係於前述聚酯系樹脂發泡體之具有前述表面粗度(Ra)的面積層前述纖維強化樹脂片材。
  2. 如申請專利範圍第1項所述之樹脂複合體的製造方法，其中，實施下述步驟：片材製作步驟，其係將聚酯系樹脂組成物進行擠出發泡而製作作為前述芯材使用之聚酯系樹脂發泡片材，與片材平滑化步驟，其係使該片材製作步驟所得之聚酯系樹脂發泡片材的表面平滑化；前述片材製作步驟係製作表面粗度(Ra)超過2.5μm的聚酯系樹脂發泡片材；前述片材平滑化步驟係將前述聚酯系樹脂發泡片材的表面以前述表面粗度(Ra)成為2.5μm以下之方式進行平滑化；前述積層步驟係於經前述片材平滑化步驟而表面 已平滑化之聚酯系樹脂發泡片材的前述表面積層前述纖維強化樹脂片材。
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KR101954607B1 (ko) 2019-03-06
JP2016069460A (ja) 2016-05-09
EP3202828A4 (en) 2018-04-25
EP3202828A1 (en) 2017-08-09
KR20170038008A (ko) 2017-04-05
WO2016052207A1 (ja) 2016-04-07
US10723055B2 (en) 2020-07-28
CN106795312A (zh) 2017-05-31
TWI615426B (zh) 2018-02-21
CN106795312B (zh) 2019-12-13
TW201706346A (zh) 2017-02-16
EP3202828B1 (en) 2019-01-30
EP3392015A1 (en) 2018-10-24

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