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TWI650245B - 防護結構 - Google Patents

防護結構 Download PDF

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Publication number
TWI650245B
TWI650245B TW106141852A TW106141852A TWI650245B TW I650245 B TWI650245 B TW I650245B TW 106141852 A TW106141852 A TW 106141852A TW 106141852 A TW106141852 A TW 106141852A TW I650245 B TWI650245 B TW I650245B
Authority
TW
Taiwan
Prior art keywords
protective structure
surface layer
copolymer
layer
item
Prior art date
Application number
TW106141852A
Other languages
English (en)
Other versions
TW201924920A (zh
Inventor
劉峻佑
彭兆民
陳世明
賴韋豪
邱佑宗
Original Assignee
財團法人工業技術研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 財團法人工業技術研究院 filed Critical 財團法人工業技術研究院
Priority to TW106141852A priority Critical patent/TWI650245B/zh
Priority to CN201711390126.4A priority patent/CN109851709B/zh
Priority to US15/853,266 priority patent/US20190160772A1/en
Application granted granted Critical
Publication of TWI650245B publication Critical patent/TWI650245B/zh
Publication of TW201924920A publication Critical patent/TW201924920A/zh

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Abstract

本揭露提供之防護結構，包括孔隙層；以及表面層，位於孔隙層上，其中孔隙層包括第一共聚物、多個孔洞、與多個第一氧化矽粒子，第一共聚物係由第一單體組合物聚合而成，且第一單體組合物包括N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮；其中表面層包括第二共聚物、多個纖維、與多個第二氧化矽粒子，第二共聚物係由第二單體組合物聚合而成，且第二單體組合物包括N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮。

Description

防護結構
本揭露關於防護結構，更特別關於其多層結構中的組成。
鋰電池具有高額定電壓、高儲存能量密度、放電平穩、與品質穩定等優點，其需求量日漸增加。在鋰電池應用普及之下，伴隨著電動載具在使用高容量電池所衍生的意外燃燒風險，逐步成為一重要的課題，目前市售的軟包型式的鋰電池均已導入高安全性的材料，可有效防止內部電流短路所引起的熱爆走反應。然而對於圓筒型與方型的鋰電池而言，一旦受到外力衝擊、穿刺、與輾壓時，將促使電池內部短路而產生劇熱，進而壓力遽增誘使開閥洩漏出可燃性的電解液，伴隨著電流短路產生的局部火花，逐步燃燒與加熱鄰近的電池組，開始一連串的延燒現象。
目前市面上的鋰電池保護盒的材質多為PP/PC、PC/ABS與沖壓鋼板，其具有多種缺點如缺乏有效的重量承載力(或加重電池模組重量)、無法抵禦外來衝擊力、電解液滲漏、與耐腐蝕性不佳，造成電池盒可容納的電池組數量受限，影響鋰電池模組的總容量，僅能提供短程行駛的續航力，而阻礙電動載具的普及應用。市售的電池模組設計上缺乏完善的保護措 施，一旦受到外力衝擊，便曝露在電池燃燒與爆炸的風險之中。一般鋰電池保護盒著重在密封性能與承載能力，但衍生出剛性強度不夠、抗震性差等問題。
現有技術僅片面地改善鋰電池保護盒的缺點，無法全面性兼顧電動載具需要的安全性、承載力、續航力、與耐腐蝕等訴求。綜上所述，目前需要輕量、電絕緣、耐衝擊、防穿刺、與耐酸鹼腐蝕等特性的保護盒材料，以提高鋰電池模組的容納數量、輕量化電池模組重量、並屏蔽外來衝擊，可降低電池失效的風險性。
本揭露一實施例提供之防護結構，包括孔隙層；以及表面層，位於孔隙層上，其中孔隙層包括第一共聚物、多個孔洞、與多個第一氧化矽粒子，第一共聚物係由第一單體組合物聚合而成，且第一單體組合物包括N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮；其中表面層包括第二共聚物、多個纖維、與多個第二氧化矽粒子，第二共聚物係由第二單體組合物聚合而成，且第二單體組合物包括N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮。
本揭露一實施例提供之防護結構，包括孔隙層；以及表面層，位於該孔隙層上。在一實施例中，防護結構為雙 層結構，即孔隙層加表面層。為達防護功效，孔隙層需靠近保護的物件。若孔隙層置於外側，則易因受到外力撞擊而造成表面破損，且降低防護結構的耐撞擊效果。在另一實施例中，防護結構為三層結構，即孔隙層夾設於兩個表面層之間。
上述孔隙層包括第一共聚物、多個孔洞、與多個第一氧化矽粒子。在一實施例中，第一共聚物係由第一單體組合物聚合而成，且第一單體組合物包括N,N-二甲基丙烯醯胺(N,N-dimethylacrylamide，DMAA)與N-乙烯基吡咯烷酮(N-vinylpyrrolidone，NVP)。舉例來說，第一單體組合物中的DMAA與NVP之重量比可介於3：1至7：1之間。若DMAA之比例過高，則造成材料的撕裂強度差。若DMAA之比例過低，則降低防撞吸能效果。在一實施例中，第一共聚物之重均分子量介於1000至50000之間。若第一共聚物之重均分子量過高，則影響剪切增稠膠體的響應特性，造成吸能效果下降。若第一共聚物之重均分子量過低，則會有未反應之單體洩漏問題。在一實施例中，第一單體組合物可包含其他單體如丙烯酸、N-丙烯醯嗎啉、N,N-二乙基丙烯醯胺、或上述之組合，且DMAA與其他單體之重量比例可介於3：1至7：1之間。若其他單體之比例過高，則會產生部份單體析出，造成相異單體間不互溶的情況。在孔隙層中，第一氧化矽粒子與第一共聚物之重量比介於1.5：1至4：1之間，若第一氧化矽粒子之比例過高，則增加混煉加工的難度，並且固化成型後的成品易產生破碎的情況。若第一氧化矽粒子之比例過低，則失去剪切增稠膠體的響應特性。此外，孔隙層可包含35體積%至80體積%的該些孔洞。若孔洞在孔隙 層中的比例過高，則缺乏結構支撐能力，因而容易受到衝擊力貫穿產生材料破壞。若孔洞在孔隙層中的比例過低，則失去壓縮吸能能力並且增加材料重量。在一實施例中，孔洞之粒徑介於50奈米至500微米之間。若孔洞粒徑過大，則會造成連續性多通孔結構，不利於孔隙層的承載能力。若孔洞粒徑過小，則材料顯得厚重。在一實施例中，孔隙層的第一氧化矽粒子粒徑介於50奈米至1毫米之間。若第一氧化矽粒子的粒徑過大，則混煉過程易造成沉降。若第一氧化矽粒子的粒徑過小，則大幅提高混煉加工難度，而不利於灌注成型。
上述表面層包括第二共聚物、多個纖維、與多個第二氧化矽粒子。在一實施例中，第二共聚物係由第二單體組合物聚合而成，且第二單體組合物包括DMAA與NVP。舉例來說，第二單體組合物中的DMAA與NVP之重量比可介於3：1至7：1之間。若DMAA之比例過高，則纖維界面間的接著強度不佳。若DMAA之比例過低，則降低防撞吸能效果。在一實施例中，第二共聚物之重均分子量介於1000至50000之間。若第二共聚物之重均分子量過高，則影響剪切增稠膠體的響應特性。若第二共聚物之重均分子量過低，則有第二共聚物滲出的可能性。在一實施例中，第二單體組合物可包含其他單體如丙烯酸、N-丙烯醯嗎啉、N,N-二乙基丙烯醯胺、或上述之組合，且DMAA與其他單體之重量比例可介於3：1至7：1之間。若其他單體之比例過高，則降低防撞吸能效果。在表面層中，第二氧化矽粒子與第二共聚物之重量比介於1.5：1至4：1之間，若第二氧化矽粒子之比例過高，則增加混煉加工的難度。若第二氧化矽粒子之 比例過低，則失去剪切增稠膠體的響應特性。在一實施例中，表面層的第二氧化矽粒子粒徑介於50奈米至1毫米之間。若第二氧化矽粒子的粒徑過大，則難以分散於纖維之中。若第二氧化矽粒子的粒徑過小，則不利於纖維浸潤。在一實施例中，表面層中的纖維可為碳纖維、玻璃纖維、克維拉纖維、聚酯纖維、或上述之組合。
可以理解的是，孔隙層的第一單體組合物與表面層的第二單體組合物可相同或不同。舉例來說，第一單體組合物的DMAA/NVP比例可不同於第二單體組合物的DMAA/NVP比例。第一單體組合物包含的其他單體種類/比例，可與第二單體組合物包含的其他單體種類/比例相同或不同。第一共聚物之重均分子量可與第二共聚物之重均分子量相同或不同。另一方面，孔隙層中的第一共聚物/第一氧化矽粒子比例可與表面層中的第二共聚物/第二氧化矽粒子比例相同或不同。孔隙層的第一氧化矽粒子與表面層的第二氧化矽粒子尺寸可相同或不同。
在一實施例中，表面層更包括均聚物，且第二共聚物與均聚物之重量比介於1：1至7：1之間。若均聚物之比例過高，則容易產生相分離與沉降現象。在一實施例中，均聚物包括聚N-乙烯基吡咯烷酮、聚N,N-二甲基丙烯醯胺、聚N-異丙基丙烯醯胺、聚丙烯酸、聚N,N-二乙基丙烯醯胺、或上述之組合。在一實施例中，均聚物為聚N-乙烯基吡咯烷酮。在一實施例中，均聚物之重均分子量介於20000至100000之間。若均聚物之重均分子量過高，則不利於分散與溶解。若均聚物之重均分子量 過低，則有均聚物滲出的可能性。
在上述防護結構中，孔隙層厚度可介於0.5毫米至1毫米之間，而表面層厚度可介於0.5毫米至1毫米之間。若孔隙層厚度過大，則造成板材厚重。若孔隙層厚度過小，則缺乏足夠的防撞吸能效果。若表面層厚度過大，則造成板材厚重。若表面層厚度過小，則無法有效分散外力衝擊，而造成破裂。
表面層在防護結構中扮演分散衝擊力、抵禦外物穿刺等功能，同時是主要的承力結構，用以提高抗彎強度與表面抗拉強度，提供承受平面內的負載及彎矩。此外，將纖維補強材料導入於表面層之中，可得到輕薄、高強度、高勁度等優點，達成減輕整體結構重量的訴求。孔隙層在防護結構中提供吸能、抗震、防衝擊等功能，在承力方面提供撓曲強度來避免材料內部受到剪切破壞，加上由輕質的剪切增稠膠體材料所構成的孔隙層，更能增進輕量化與吸能效果。其中，孔隙層的製備方法可包括：將單體、起始劑、第一氧化矽粒子與發泡劑所組成的剪切增稠流體(STF)倒入於模具之中，並且進行固化以形成由剪切增稠膠體(STG)所構成的孔隙層，進一步與表面層透過結構膠水或剪切增稠流體進行貼合與固化，成為一防護結構材料；另一實施方式中，將剪切增稠流體倒入於已置放表面層的模具內，再舖上另一塊表面層並進行固化，即可得到由兩塊表面層夾一層孔隙層的防護結構，此方式屬於一體成形的作法，具有簡單、快速、缺陷少等優點。
上述防護結構可置於物體上，使施加至物體的力量消散於防護結構中。上述防護結構主要應用在鋰電池的防護 外殼中，以增加鋰電池受到撞擊後的安全性。除此之外，防護結構亦可用於運動護墊、鞋墊、防彈衣、或其他防護用具中。防護結構可視需求應用於各種物體，並不以上述應用為限。
為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例作詳細說明如下。
實施例
實施例1
將13.5g之二氧化矽(Megasil 550silica，購自Sibelco Asia Pte Ltd.-Bao Lin Branch，粒徑範圍2~3μm)、5.0g之N,N-二甲基丙烯醯胺(DMAA，CAS#：2680-03-7，購自合記化學)、1.0g之N-乙烯基吡咯烷酮(NVP，CAS#：88-12-0，購自Sigma-Aldrich Inc.)、1phr(以DMAA與NVP之總重為基準)之熱起始劑偶氮二異丁腈(AIBN)、與0.03g之發泡劑苯磺酰肼(B3809-25G，CAS#：80-17-1，購自Sigma-Aldrich Inc.)倒入模具中，加熱至90℃後反應1小時，使DMAA與NVP共聚(重均分子量為約14,752g/mol)並發泡，冷卻後形成孔隙層。將孔隙層置於鑽頭上，且鑽頭內含壓力感測器。對孔隙層施加50J的撞擊力，並記錄鑽頭內的壓力感測器量測到的穿透力(越低越好)，即可知孔隙層的吸能效果，而吸能效果之量測標準為EN1621-1。上述孔隙層的密度之量測標準為CNS 7407，而孔隙層的孔隙率之量測標準為ISO-15901。上述孔隙層之起始物及性質如第1表所示。
實施例2
與實施例1類似，差別在於實施例2的發泡劑苯磺酰肼其用量增加至0.06g。二氧化矽、DMAA、與NVP的用量，以及孔隙 層之性質的量測標準均與實施例1相同。上述孔隙層之起始物及性質如第1表所示。
實施例3
與實施例1類似，差別在於實施例3的發泡劑苯磺酰肼其用量增加至0.12g。二氧化矽、DMAA、與NVP的用量，以及孔隙層之性質的量測標準均與實施例1相同。上述孔隙層之起始物及性質如第1表所示。
比較例1
與實施例1類似，差別在於比較例1省略NVP，並將DMAA的用量增加至6.0g，形成之聚合物的重均分子量為約13,125g/mol。二氧化矽用量以及孔隙層之性質的量測標準均與實施例1相同。上述孔隙層之起始物及性質如第1表所示。
比較例2
與實施例1類似，差別在於比較例2的發泡劑苯磺酰肼其用量增加至0.2g。二氧化矽、DMAA、與NVP的用量，以及孔隙層之性質的量測標準均與實施例1相同。上述孔隙層之起始物及性質如第1表所示。
*孔隙層經撞擊後破裂
由第1表可知，缺乏NVP共聚的孔隙層在撞擊測試後破裂。另一方面，過多發泡劑形成的孔隙層厚度偏高且孔隙率過高(密度偏低)，在撞擊後破裂。
實施例4
將13.5g之二氧化矽、5.0g之DMAA、1.0g之NVP、與1phr(以DMAA與NVP之總重為基準)之熱起始劑AIBN倒入模具中，加熱至90℃後反應1小時，使DMAA與NVP共聚，冷卻後形成表面層的膠材(無纖維)。將表面層的膠材置於鑽頭上，且鑽頭內含壓力感測器。對表面層的膠材施加50J的撞擊力，並記錄鑽頭內的壓力感測器量測到的穿透力，即可知表面層的膠材其吸能效果。上述表面層的膠材其撕裂強度之量測標準為ASTM D624。上述表面層之膠材的起始物及性質如第2表所示。
實施例5
與實施例4類似，差別在於實施例5的起始物更包含1.0g的丙烯酸(AA)，形成之聚合物的重均分子量為約11,251g/mol。二氧化矽、DMAA、與NVP的用量，以及表面層的膠材其性質的量測標準均與實施例4相同。上述表面層的膠材之起始物及性質如第2表所示。
比較例3
與實施例4類似，差別在於比較例3省略NVP，並將DMAA的用量增加至6.0g，形成之聚合物的重均分子量為約13,892g/mol。二氧化矽的用量以及表面層的膠材其性質的量測標準均與實施例4相同。上述表面層的膠材之起始物及性質如第2表所示。
比較例4
與實施例4類似，差別在於比較例4將DMAA的用量降低至1.0g，並將NVP的用量增加至5.0g，形成之聚合物的重均分子量為約17,230g/mol。二氧化矽的用量以及表面層的膠材其性質的量測標準均與實施例4相同。上述表面層的膠材之起始物及性質如第2表所示。
比較例5
與比較例4類似，差別在於比較例5將5.0g之NVP置換為5.0g的AA。二氧化矽與DMAA的用量以及表面層的膠材其性質的量測標準均與實施例4相同。上述表面層的膠材之起始物及性質如第2表所示。
比較例6
與比較例4類似，差別在於比較例5將5.0g之NVP置換為5.0g的N-丙烯醯嗎啉(ACMO，CAS#：5117-12-4，購自合記化學)。二氧化矽與DMAA的用量以及表面層的膠材其性質的量測標準均與實施例4相同。上述表面層的膠材之起始物及性質如第2表所示。
第2表
由第2表之比較可知，適當比例的DMAA與NVP可同時兼顧抗撞擊力與撕裂強度。若無NVP(比較例3)，其撕裂強度大幅降低。若DMAA比例過低(比較例4至6)，則穿透力過高。
實施例6
將8層碳纖維層(TC-36 12K，購自台灣塑膠工業股份有限公司)置於模具中，再將13.5g之二氧化矽、5.0g之DMAA、1.0g之NVP、與1phr(以DMAA與NVP之總重為基準)之熱起始劑AIBN倒入模具中，加熱至90℃後反應1小時，使DMAA與NVP共聚，冷卻後形成表面層。上述表面層其剪切強度之量測標準為ASTM D3163。上述表面層之膠材的起始物及性質如第3表所示。
實施例7
與實施例6類似，差別在於實施例7添加1g之均聚物Poly(DMAA)(773638，Sigma-Aldrich Inc.)。二氧化矽、DMAA、與NVP的用量，以及表面層其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
實施例8
與實施例6類似，差別在於實施例8添加1g之均聚物Poly(NVP)(856568-100G，CAS#：9003-39-8，購自Sigma-Aldrich Inc.)。二氧化矽、DMAA、與NVP的用量，以及表面層其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
實施例9
與實施例6類似，差別在於實施例9添加1g之均聚物Poly(AA)(P3981-AA，購自Polymer Source Inc.)。二氧化矽、DMAA、與NVP的用量，以及表面層之膠材其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
比較例7
與實施例6類似，差別在於比較例7省略NVP，並將DMAA的用量增加至6.0g。二氧化矽的用量，以及表面層其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
比較例8
與比較例7類似，差別在於比較例8添加1g之均聚物Poly(DMAA)(773638，Sigma-Aldrich Inc.)。二氧化矽的用量， 以及表面層其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
比較例9
與比較例7類似，差別在於比較例9添加1g之均聚物Poly(NVP)(856568-100G，CAS#：9003-39-8，購自Sigma-Aldrich Inc.)。二氧化矽的用量，以及表面層其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
比較例10
與比較例7類似，差別在於比較例10添加1g之均聚物Poly(AA)(323667-100G，CAS#：9003-01-4，購自Sigma-Aldrich Inc.)。二氧化矽的用量，以及表面層其性質的量測標準均與實施例6相同。上述表面層之膠材的起始物及性質如第3表所示。
由第3表之比較可知，均聚物可進一步增加表面層的剪切強度。然而共聚物若缺乏NVP，即使添加均聚物也無法使表面層達到足夠的剪切強度。
實施例10
將8層碳纖維層(TC-36 12K，購自台灣塑膠工業股份有限公司)置於模具中，再將13.5g之二氧化矽、5.0g之DMAA、1.0g之NVP、1phr(以DMAA與NVP之總重為基準)之熱起始劑AIBN、與1g之均聚物Poly(NVP)倒入模具中，加熱至90℃後反應1小時，使DMAA與NVP共聚，冷卻後形成表面層。重複上述步驟，以得另一表面層。
接著將將13.5g之二氧化矽、5.0g之DMAA、1.0g之NVP、1phr(以DMAA與NVP之總重為基準)之熱起始劑AIBN、與0.06g之發泡劑苯磺酰肼(B3809-25G，CAS#：80-17-1，購自Sigma-Aldrich Inc.)倒入模具中的表面層上作為孔隙層配方，再將另一表面層放置在上述孔隙層配方上。將孔隙層配方加熱至90℃後反應1小時，使DMAA與NVP共聚發泡，冷卻後形成孔隙層夾設於兩個表面層之間的三層結構(防護結構)。在表面層上黏貼黏土(厚度30mm)，再於另一表面層上設置鋼製圓頭(110.4g，圓頭體積14.29cm3)，即防護結構位於黏土與鋼製圓頭之間。接著以48m/s球速之高爾夫球(直徑42.67mm)撞擊鋼製圓頭，使鋼製圓頭以25m/s速度撞擊防護結構。接著量測黏 土凹陷程度與體積、量測防護結構凹陷深度、並觀察防護結構外觀如第4表所示。
實施例11
與實施例10類似，差別在於實施例11將表面層中8層碳纖維置換為8層玻璃纖維(E-glass 2116，購自金財興股份有限公司)。表面層中的其他組成、孔隙層的組成，與防護結構性質的量測方法均與實施例10類似。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
實施例12
與實施例10類似，差別在於實施例12省略一表面層，即防護結構為表面層與孔隙層的雙層結構。表面層的組成、孔隙層的組成，與防護結構性質的量測方法均與實施例10類似。在此實施例的撞擊測試中，黏土接觸孔隙層，而鋼製圓頭接觸表面層。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
實施例13
與實施例11類似，差別在於實施例13省略一表面層，即防護結構為表面層與孔隙層的雙層結構。表面層中的其他組成、孔隙層的組成，與防護結構性質的量測方法均與實施例10類似。在此實施例的撞擊測試中，黏土接觸孔隙層，而鋼製圓頭接觸表面層。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例11(空白試驗)
無防護結構的情況下，直接進行撞擊測試。撞擊測試後的黏土凹陷程度與體積如第4表所示。
比較例12
取市售之SS41鋼板作為防護結構，進行撞擊測試。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例13
將實施例10之表面層改為中間層，並將實施例10之孔隙層改為上層與下層。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例14
將實施例11之表面層改為中間層，並將實施例11之孔隙層改為上層與下層。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例15
取實施例10之孔隙層直接進行撞擊測試。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例16
參考US20170174930之實施例3，將13.5g之二氧化矽、6.0g之DMAA、與1phr(以DMAA之重量為基準)的AIBN加入模具中，加熱至90℃後反應1小時，使DMAA聚合，冷卻後即形成防護 結構並進行撞擊測試。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例17
參考TW201722734A之實施例22，將立體編織物置入模具中，並將13.5g之二氧化矽、6.0g之DMAA、與1phr(以DMAA之重量為基準)的AIBN加入模具中，加熱至90℃後反應1小時，使DMAA聚合，冷卻後即形成防護結構並進行撞擊測試。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
比較例18
與實施例10類似，差別在於比較例18將中間層置換為PU發泡層(百事隆®二液型PU發泡劑UR-370，購自廣隆興股份有限公司)。表面層的組成與防護結構性質的量測方法均與實施例10類似。防護結構的組成，以及撞擊測試後的黏土凹陷程度與體積、防護結構凹陷深度、與防護結構外觀如第4表所示。
由第4表之比較可知，孔隙層與表面層的組合具有抗撞擊效果，但位於外側的孔隙層會有表面破裂的問題。只有孔隙層而無表面層的抗撞擊效果不佳。若表面層未搭配本申請案實施例之孔隙層，而是搭配其他孔隙層如常見之PU發泡層，其抗撞擊的效果亦不佳。可以理解的是，若只有表面層而無孔隙層，則其抗撞擊效果應更差。
雖然本揭露已以數個實施例揭露如上，然其並非用以限定本揭露，任何本技術領域中具有通常知識者，在不脫離本揭露之精神和範圍內，當可作任意之更動與潤飾，因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。

Claims (12)

  1. 一種防護結構，包括：一孔隙層；以及一表面層，位於該孔隙層上，其中該孔隙層包括一第一共聚物、多個孔洞、與多個第一氧化矽粒子，該第一共聚物係由一第一單體組合物聚合而成，且該第一單體組合物包括N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮；其中該表面層包括一第二共聚物、多個纖維、與多個第二氧化矽粒子，該第二共聚物係由一第二單體組合物聚合而成，且該第二單體組合物包括N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮。
  2. 如申請專利範圍第1項所述之防護結構，其中該孔隙層包含35體積%至80體積%的該些孔洞，且該些孔洞之粒徑介於50奈米至500微米之間。
  3. 如申請專利範圍第1項所述之防護結構，其中該第一單體組合物中的N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮之重量比介於3：1至7：1之間，且該第二單體組合物中的N,N-二甲基丙烯醯胺與N-乙烯基吡咯烷酮之重量比介於3：1至7：1之間。
  4. 如申請專利範圍第1項所述之防護結構，其中該些第一氧化矽粒子與該第一共聚物之重量比介於1.5：1至4：1之間，且該些第二氧化矽粒子與該第二共聚物之重量比介於1.5：1至4：1之間。
  5. 如申請專利範圍第1項所述之防護結構，其中該第一單體組合物更包括丙烯酸、N-丙烯醯嗎啉、N,N-二乙基丙烯醯胺、或上述之組合；及/或該第二單體組合物更包括丙烯酸、N-丙烯醯嗎啉、N,N-二乙基丙烯醯胺、或上述之組合。
  6. 如申請專利範圍第1項所述之防護結構，其中該第一共聚物之重均分子量介於1000至50000之間，及/或該第二共聚物之重均分子量介於1000至50000之間。
  7. 如申請專利範圍第1項所述之防護結構，其中該表面層更包括一均聚物，且該第二共聚物與該均聚物之重量比介於1：1至7：1之間。
  8. 如申請專利範圍第7項所述之防護結構，其中該均聚物包括聚N-乙烯基吡咯烷酮、聚N,N-二甲基丙烯醯胺、聚N-異丙基丙烯醯胺、聚丙烯酸、聚N,N-二乙基丙烯醯胺、或上述之組合。
  9. 如申請專利範圍第7項所述之防護結構，其中該均聚物之重均分子量介於20000至100000之間。
  10. 如申請專利範圍第1項所述之防護結構，其中該些第一氧化矽粒子與該些第二氧化矽粒子的粒徑介於50奈米至1毫米之間。
  11. 如申請專利範圍第1項所述之防護結構，其中該些纖維包括碳纖維、玻璃纖維、克維拉纖維、聚酯纖維、或上述之組合。
  12. 如申請專利範圍第1項所述之防護結構，其中該孔隙層之厚度介於0.5毫米至1毫米之間，且該表面層之厚度介於0.5毫米至1毫米之間。
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