TWI743175B - 用於將聚烯烴膜結合至玻璃纖維之黏著劑 - Google Patents
用於將聚烯烴膜結合至玻璃纖維之黏著劑 Download PDFInfo
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- TWI743175B TWI743175B TW106128312A TW106128312A TWI743175B TW I743175 B TWI743175 B TW I743175B TW 106128312 A TW106128312 A TW 106128312A TW 106128312 A TW106128312 A TW 106128312A TW I743175 B TWI743175 B TW I743175B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本發明提供一種組合物,以所述組合物之重量計,以重量百分比(wt%)為單位,其包括:(A)大於零至39wt%極性烯烴聚合物及苯乙烯類嵌段共聚物中之至少一者;(B)大於零至20wt%環氧基或胺官能化矽烷;(C)60至99wt%(1)所述極性烯烴聚合物及/或苯乙烯類嵌段共聚物與(2)所述環氧基或胺官能化矽烷的混合物之有機溶劑;及(D)零至10wt%聚異氰酸酯交聯劑。
Description
本發明係關於黏著劑。在一個態樣中,本發明係關於一種用於將非極性塗層結合至極性基板之黏著劑,而在另一態樣中,本發明係關於防水屋頂膜、紡織結構膜及其製造。
經塗佈之織物已廣泛用於防水屋頂膜及紡織結構膜。經塗佈之織物存在配置於兩個主要正交方向上之紗線之對稱結構:經紗及緯紗。所述紗線由並行或纏繞在一起的細線組成且可由若干材料製成。儘管結構功能主要由紗線提供,保護免受化學及生物學影響、耐火行為、焊接能力、防水品質及耐UV射線性取決於塗佈層。
歸因於其高彈性模量及拉伸強度,玻璃纖維一般用於永久性重載應用,且因為其具有固有較高的抗火及抗UV降解性。聚氯乙烯(PVC)、聚四氟乙烯(PTFE)、乙基四氟乙烯(ETFE)、聚胺基甲酸酯(PU)、矽及聚烯烴為用作經塗佈之織物之塗佈材料的主要聚合物。對於戶外經塗佈之織物,主要織物為聚酯(PES)、聚乙烯(PE)及纖維玻璃。對於室內及臨時應用,使用纖維,如氨綸(例如SPANDEXTM、 LYCRATM)及耐綸(nylon)。
聚烯烴彈性體(POE),如INFUSETM烯烴嵌段共聚物、VERSIFYTM丙烯基彈性體及ENGAGETM乙烯基聚合物展現多種所需特性,其包含(但不限於)極佳耐候性及耐水性、輕重量、容易處理、可循環性及成本效能平衡,其使其成為防水屋頂膜及紡織結構膜之塗佈層的極佳選擇。然而,歸因於其非極性性質,POE難以結合至極性基板,例如玻璃纖維,且所述工業仍對此問題進展感興趣。
在一個實施例中,本發明為一種組合物,以所述組合物之重量計,以重量百分比(wt%)為單位,其包括:(A)大於零至39wt%極性烯烴聚合物及苯乙烯類嵌段共聚物中之至少一者;(B)大於零至20wt%環氧基或胺官能化矽烷;(C)60至99wt%(1)所述極性烯烴聚合物及/或苯乙烯類嵌段共聚物與(2)所述環氧基或胺官能化矽烷的混合物之有機溶劑;及(D)零至10wt%聚異氰酸酯交聯劑。
在一個實施例中,本發明為一種多層結構,其包括:(1)織物層,其包括極性紡紗;(2)膜層,其包括非極性烯烴聚合物;及(3)黏著層,其在織物層與膜層之間且與所述織物層及所述膜層接觸,由組合物製成之黏著層,以所述組合物之重量計,以重量百分比(wt%)為單位,其包括: (A)大於零至39wt%極性烯烴聚合物及苯乙烯類嵌段共聚物中之至少一者;(B)大於零至20wt%環氧基或胺官能化矽烷;(C)60至99wt%(1)所述極性烯烴聚合物及/或苯乙烯類嵌段共聚物與(2)所述環氧基或胺官能化矽烷的混合物之有機溶劑;及(D)零至10wt%聚異氰酸酯交聯劑。
定義
除非相反陳述、自上下文暗示或在本領域中慣用,否則所有份數及百分比均按重量計,且截至本發明之申請日為止,所有測試方法均為現行的。出於美國專利實務之目的,任何所參考之專利、專利申請案或公開案之內容均以全文引用之方式併入(或其等效US版本如此以引用之方式併入),尤其在本領域中之定義(在與本發明中特定提供之任何定義不一致的程度上)及常識之揭示方面。
本文所揭示之數值範圍包含來自較低值及較高值之所有值,且包含較低值及較高值。對於含有確切值的範圍(例如,1或2;或3至5;或6;或7),任何兩個確切值之間的任何子範圍包含在內(例如,1至2;2至6;5至7;3至7;5至6等)。
「烯烴」為具有一或多個雙鍵之不飽和脂族或脂環族經取代或未經取代之烴。
「烯烴基聚合物」、「烯烴聚合物」及類似術語意謂含有以聚合形式,以聚合物之總重量計大部分重量百分比烯烴,例如乙烯或丙烯之聚合物。烯烴基聚合物之非限制性實例包含乙烯基聚合物及丙烯基聚合物。
「乙烯基聚合物」、「乙烯聚合物」及類似術語意謂包括以聚合物之重量計大部分量之聚合乙烯且視情況可包括至少一種共聚單體的聚合物。
「丙烯基聚合物」、「丙烯聚合物」及類似術語意謂含有超過50莫耳百分比聚合丙烯單體(以可聚合單體之總量計)且視情況可含有至少一種共聚單體的聚合物。
「極性」、「極性聚合物」及類似術語係指具有永久性偶極子之聚合物分子,亦即,聚合物分子具有正極端及負極端。換言之,極性分子中之電子不同等地共享於分子原子中。相比之下,「非極性」、「非極性聚合物」及類似術語係指並不具有永久性偶極子之聚合物分子,亦即,聚合物不具有正極端及負極端。非極性分子中之電子基本上同等地共享於分子原子中。大部分烴液體及聚合物為非極性的。
「極性基團」為賦予另外基本上非極性烯烴分子之鍵偶極矩的任何基團。例示性極性基團包含羰基、羧酸基、羧酸無水物基團、羧酸酯基、環氧基、磺醯基、腈基、醯胺基、矽烷基及其類似基團,且此等基團可經由接枝或共聚合引入烯烴基聚合物中。組合物之組分(A)
極性烯烴聚合物
實踐本發明中使用之極性烯烴聚合物為包括一或多個極性基團之烯烴聚合物。例示性極性基團包含羰基、 羧酸基、羧酸酐基、羧酸酯基、乙烯酯基、環氧基、磺醯基、腈基、醯胺基、矽烷基及其類似基團,且此等基團可經由接枝或共聚合引入烯烴聚合物中。例示性極性烯烴聚合物包含乙烯/丙烯酸(EAA)、乙烯/甲基丙烯酸(EMA)、乙烯/丙烯酸酯或甲基丙烯酸酯、乙烯/乙酸乙烯酯(EVA)、聚(乙烯-共-乙烯基三甲氧基矽烷)共聚物及順丁烯二酸酐(MAH)或矽烷接枝烯烴聚合物。較佳極性烯烴聚合物包含杜邦(DuPont)ELVAXTM乙烯乙酸乙烯酯(EVA)樹脂、來自陶氏化學公司(The Dow Chemical Company)之AMPLIFYTM EA乙烯丙烯酸乙酯(EEA)共聚物、來自陶氏化學公司之PRIMACORTM乙烯/丙烯酸共聚物及來自陶氏化學公司之SI-LINKTM聚(乙烯-共-乙烯基三甲氧基矽烷)共聚物。在一個實施例中,極性烯烴聚合物為EEA。極性烯烴聚合物可在習知高壓方法中,藉由使乙烯與極性共聚單體(例如乙酸乙烯酯、丙烯酸乙酯等),使用自由基引發劑(諸如有機過氧化物),在150至350℃範圍內之反應溫度及100至300MPa之反應壓力下共聚而產生。
在本發明之一個實施例中,極性烯烴聚合物用極性基團接枝。極性基團接枝聚合物可含有每100重量份聚合物0.05至5或10重量份接枝極性基團,且較佳含有每100重量份聚合物0.1至2重量份接枝極性基團。用順丁烯二酸酐接枝之POE為較佳極性基團接枝極性烯烴聚合物,例如可購自陶氏化學公司之AMPLIFYTM GR 216。
在一個實施例中,極性烯烴聚合物未經中和。在一個實施例中,極性烯烴聚合物不含有含氮基團,例如胺。在一個實施例中,極性烯烴聚合物不與可中和其極性基團之 化合物,例如與含胺化合物(諸如乙二胺或嗎啉)摻合或以其他方式混合。
在一個實施例中,極性烯烴聚合物,尤其EEA聚合物具有每10分鐘0.5至50克(g/10min)範圍內之熔體流動速率。極性共聚單體含量典型地為以聚合物之重量計5至40重量百分比,更典型地為10至35重量百分比。
苯乙烯類嵌段共聚物
在用極性基團接枝之前,實踐本發明中使用之苯乙烯類嵌段共聚物包含至少兩個單烯基芳烴嵌段,較佳由飽和共軛二烯嵌段間隔開的兩個聚苯乙烯嵌段,較佳飽和聚丁二烯嵌段。較佳苯乙烯類嵌段共聚物具有線性結構,但在一些實施例中,支化或徑向聚合物或官能化嵌段共聚物製得適用的化合物。若共聚物具有線性結構,則苯乙烯類嵌段共聚物之總數目平均分子量較佳為30,000至250,000。此類嵌段共聚物典型地具有6至65,更典型地10至40wt%共聚物之平均聚苯乙烯含量。適用於本發明中之苯乙烯類嵌段共聚物之實例描述於EP 0 712 892、WO 2004/041538、USP 6,582,829、4,789,699、5,093,422及5,332,613及US 2004/0087235、2004/0122408、2004/0122409及2006/0211819中。適合的苯乙烯類嵌段共聚物之非限制性實例包含苯乙烯/丁二烯(SB)共聚物、苯乙烯/乙烯/丁烯/苯乙烯(SEBS)三元共聚物、苯乙烯/丁二烯/苯乙烯(SBS)三元共聚物、氫化或部分氫化SBS、苯乙烯/異戊二烯(SI)及苯乙烯/乙烯/丙烯/苯乙烯(SEPS)三元共聚物。苯乙烯類嵌段共聚物之商業來源包含科騰聚合物(Kraton Polymers)(SEBS G1643M、G1651ES)、旭 化成化學株式會社(Asahi Kasei Chemicals Corporation)及可樂麗美國公司(Kuraray America)。
在本發明之一個實施例中,苯乙烯類嵌段共聚物用極性基團接枝。極性基團接枝苯乙烯類嵌段共聚物可含有每100重量份聚合物0.05至5或10重量份接枝極性基團,且較佳含有每100重量份聚合物0.1至2重量份接枝極性基團。用順丁烯二酸酐接枝之SEBS為較佳極性基團接枝苯乙烯類嵌段共聚物,例如可購自科騰聚合物之KRATONTM FG 1901。
極性基團接枝物
待添加以改質極性烯烴聚合物或苯乙烯類嵌段聚合物之含有極性基團之化合物(例如順丁烯二酸酐)之量典型地在以聚合物之重量計0.05至10重量百分比範圍內。接枝可藉由例如溶液、懸浮液或熔融方法實現。溶液方法藉由混合含有極性基團之化合物、待接枝聚合物、非極性有機溶劑及自由基引發劑(諸如有機過氧化物),且隨後將混合物加熱至100至160℃以進行改質反應來實現。己烷、庚烷、苯、甲苯、二甲苯、氯苯及四氯乙烷為非極性溶劑之實例。2,5-二甲基-2,5-二(第三丁基過氧基)己烷、2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3及過氧化苯甲醯為有機過氧化物之實例。在懸浮方法中,將待接枝聚合物及含有極性基團之化合物與極性溶劑,諸如水混合,且隨後添加自由基引發劑。隨後將混合物加熱至高於100℃之溫度以獲得接枝聚合物。在熔融方法中,將待接枝聚合物、含有極性基團之化合物及自由基引發劑引入熔融捏合機器,諸如擠壓機或BANBURYTM混合器中以獲得接枝聚合物。
典型的酸酐改質可描述如下:藉由將酸酐、有機過氧化物催化劑及有機溶劑之溶液添加至呈顆粒狀形式之待接枝聚合物中來實現接枝。有機過氧化物引發劑可溶於有機溶劑中。可使用對反應物為惰性的各種有機溶劑。適用的有機溶劑之實例為丙酮、甲基乙基酮、甲基丙基酮、3-戊酮及其他酮。可使用允許過氧化物及酸酐溶解且在適當的脫揮發條件下良好洗提出的其他載體溶劑。丙酮為較佳溶劑,因為其充當殘餘物之洗提試劑,諸如非接枝酸酐或酸酐副產物。酸酐溶液可含有以溶液之總重量計10至50重量%酸酐;0.05至5重量%有機過氧化物;及50至90重量%有機溶劑。較佳溶液含有20至40%酸酐;0.1至2%過氧化物;及60至80%溶劑。
組合物中之組分(A)之量
組分(A),亦即,極性烯烴聚合物及苯乙烯類嵌段共聚物中之一者或兩者典型地包括以組合物之重量計大於(>)零,或大於或等於()1或2wt%。組分(A)典型地包括以組合物之重量計小於或等於()39或29,或19wt%。
組分(B),矽烷
將促進組合物之黏著特性之任何矽烷可用於本發明之實踐中。典型地且較佳地,矽烷為環氧基官能化矽烷或胺官能化矽烷。環氧基官能化矽烷包含(但不限於)SILQUESTTM A-187(γ-縮水甘油氧基丙基三甲氧基矽烷)、SILQUESTTM A-1871(γ-縮水甘油氧基丙基三乙氧基矽烷)、SILQUESTTM A-186(β-(3,4-環氧基環己基)-乙基三甲氧基矽烷)及COATOSILTM 2287(二乙氧基(3-縮水甘油基氧基丙基) 甲基矽烷)。胺官能化矽烷包含(但不限於)SILQUESTTM A-1100(γ-胺丙基三乙氧基矽烷)、SILQUESTTM A-1120(N(β-胺基乙基)γ-胺基丙基-三甲氧基矽烷)、SILQUESTTM A-2120(N(β-胺基乙基)γ-胺基丙基甲基-二甲氧基矽烷)。SILQUESTTM A-1170、SILQUESTTM Y-9627及SILQUESTTM Y-11699-為亦可用於當前黏著劑中之二級胺基官能性雙矽烷。
組分(C),溶劑
將溶解(A)極性烯烴聚合物及/或苯乙烯類嵌段共聚物、(B)矽烷及(D)交聯劑之混合物之任何溶劑可用於本發明之實踐中。典型地且較佳地,溶劑為至少一種烴與至少一種極性官能化烴之摻合物。溶劑在環境條件,例如23℃及大氣壓下為液體的。代表性烴包含脂族及芳香族兩者,諸如己烷、環己烷、甲基環己烷、庚烷、石腦油、十氫萘、苯、甲苯、二甲苯、萘等,且代表性極性官能化烴包含四氯化碳、過氯乙烯、環己酮、氯苯及四氯乙烷。包括甲基環己烷(MCH)與環己酮(CYC)之混合物為較佳的,且此等混合物可在5:95至95:5 MCH:CYC,或1:99至99:1 MCH:CYC,或4:96至96:4 MCH:CYC之重量比範圍內變化。
組分(D),交聯劑
在本發明之一個實施例中,所述組合物包括交聯劑。可使用與組合物之其他組分相容且將實現及/或促進組合物之聚合化合物中的一或多者之交聯的任何交聯劑。一個較佳交聯劑為DESMODURTM RFE,其為參(對異氰酸酯基苯基)硫代磷酸酯於乙酸乙酯中之溶液,其可購自科思創(Covestro)。其他交聯劑包含(但不限於)基於二異氰酸己二酯(HDI)之異氰酸酯交聯劑,諸如DESMODURTM N-3300、DESMODURTM N-3900及DESMODURTM N-3600;異佛爾酮二異氰酸酯(IPDI)基交聯劑,諸如DESMODURTM Z-4470及DESMODURTM XP-2565;及基於亞甲基二苯基二異氰酸酯(MDI)或甲苯二異氰酸酯(TDI)之異氰酸酯,諸如SPECFLEXTM NS-540、SPECFLEXTM NE-112、SPECFLEXTM NF-248、ISONATETM M 150、VORNANTETM T80-20。
混配組合物
本發明之黏著劑組合物使用已知技術及已知設備製備。組合物之各種組分可彼此混合以形成組合物之順序對於本發明而言並不關鍵且可因此根據便利性而變化。在一個實施例中,極性烯烴聚合物及苯乙烯類嵌段共聚物各自單獨地與溶劑混合,兩種混合物隨後彼此混合,且隨後將矽烷與極性烯烴聚合物、苯乙烯類嵌段共聚物及溶劑之混合物混合。在一個實施例中,矽烷首先與溶劑混合,且隨後單獨地 與極性烯烴共聚物及苯乙烯類嵌段共聚物中之一者或兩者摻合。攪拌或以其他方式攪動極性烯烴聚合物、苯乙烯類嵌段共聚物、矽烷及溶劑之混合物直至獲得均勻混合物為止。在混合物準備好使用時,交聯劑(若存在)典型地添加至均勻混合物中。
屋頂及建築模
以與用於製造屋頂、建築及其他此類膜之已知黏著劑相同之方式使用本發明之組合物。藉由任何技術,例如噴塗、刷塗、滾塗等,使極性織物(例如纖維玻璃墊)及非極性膜(例如聚烯烴膜)中之任一者或兩者塗佈有本發明組合物,且隨後典型地在熱及壓力下接合至其他物。
以下實例說明本發明之某些實施例。
特定實施例
材料
玻璃纖維基板包括未經處理之(藉由FTIR分析確證)玻璃纖維。
聚烯烴彈性體(POE)防水屋頂膜包括:(A)每一百樹脂(phr)70份VERSIFYTM 2300(具有0.866g/cc之密度及2g/10min(230℃/2.16Kg)之MFR之丙烯-乙烯共聚物,其可購自陶氏化學公司);(B)8phr ENGAGETM 7387 HM(具有0.872g/cc之密度及0.5g/10min(190℃/2.16Kg)之MI(I2)之乙烯-丁烯共聚物,其可購自陶氏化學公司);(C)22phr S-T B1530(具有0.91g/cc之密度及10g/10min(230℃/2.16Kg)之MFR之嵌段共聚物聚丙烯樹脂,其 可購自三星道達爾石化有限公司(Samsung-Total Petrochemicals Co.,Ltd.));(D)55phr ATIMAGTM 16 ZA碳酸鈣,其可購自Atimag;(E)6phr TI-PURETM 105(藉由氯化物法製造之金紅石二氧化鈦顏料),其可購自杜邦;(F)0.35phr IRGANOXTM B225(50%參(2,4-二第三丁基苯基)亞磷酸酯與50%異戊四醇肆[3-[3,5-二第三丁基-4-羥基苯基]丙酸酯之摻合物),其可購自巴斯夫(BASF);及(G)0.75phr CHIMASSORBTM 2020(高分子量受阻胺光穩定劑(HALS)),其可購自巴斯夫。
AMPLIFYTM GR 216為MAH-g-POE(含有0.5-1wt% MAH之MAH-g-聚烯烴彈性體(POE)共聚物)且可購自陶氏化學公司。
KRATONTM FG 1901為MAH-g-SEBS(1.7wt% MAH,30wt%苯乙烯)且可購自科騰聚合物。
SILQUESTTM A-187矽烷為γ-縮水甘油氧基丙基三甲氧基矽烷且可購自邁圖(Momentive)。
溶劑為甲基環己烷(MCH)與環己酮(CYC)重量比95:5之摻合物。
DESMODURTM RFE為包括參(對異氰酸酯基苯基)硫代磷酸酯於乙酸乙酯中之溶液的交聯劑且可購自科思創。
黏著劑製備
使十(10)重量%(wt%)AMPLIFYTM GR 216 MAH-g-POE溶解於甲基環己烷與環己酮之按重量計85.5/4.5 溶劑摻合物中。使十(10)wt% KRATONTM FG 1901 MAH-g-SEBS溶解於甲基環己烷中。將0.99wt% SILQUESTTM A-187矽烷引入AMPLIFYTM GR 216 MAH-g-POE溶液或KRATONTM FG 1901 MAH-g-SEBS溶液任一者中,且在充分混合後,添加其他溶液,亦即,不具有SILQUESTTM A-187矽烷之溶液,且隨後在室溫(23℃)下以每分鐘500-2000轉(rpm)攪拌所得混合物直至獲得均勻摻合物為止(通常在15分鐘攪拌之後)。隨後將黏著劑轉移至玻璃瓶子,密封且儲存在環境條件(例如23℃及大氣壓)下直至需要為止。
層壓
使玻璃織物塗佈有黏著劑,且隨後在120℃下放置於烘箱中3分鐘以移除有機溶劑。使用壓縮模製器,在170℃下,以4千牛頓(kN)之壓縮力將經塗佈之織物與POE化合物薄片一起層壓6秒。
剝離強度測試
剝離強度測試根據ASTM D1876(黏著劑之剝離耐性,T-剝離測試)進行。將層壓織物及POE薄片樣品切割成3cm×15cm矩形樣本,使用180度剝離測試,用300mm/min之十字頭速度,在INSTRONTM機器上量測剝離強度。記錄平均負荷(以公斤-力或kgf為單位量測)且由至少3個樣品計算平均剝離強度(kgf/3cm)。
結果及論述
製備四個比較實例及六個本發明實例且在以下表1中報導其組合物及平均剝離強度數據。比較實例1(CE-1)為空白樣品(亦即,在玻璃織物上未塗佈黏著劑,且將玻璃 織物與聚烯烴膜直接層壓在一起)。所有剝離強度數據之標準差均低於0.15kgf/3cm。
空白樣品CE-1具有低剝離強度(0.3kgf/3cm),其係因為剝離強度僅由經塗佈之玻璃纖維紗布基板中之機械互鎖作用貢獻。其指示僅機械互鎖力自身可能無法在玻璃纖維基板與POE化合物膜之間提供足夠的黏著力。
具有MAH-g-POE或MAH-g-SEBS黏著劑之層壓玻璃纖維織物展示高於空白樣品的改良黏著力。MAH-g-SEBS基黏著劑之剝離強度可達到2kgf/3cm,且MAH-g-POE基黏著劑甚至可達到4kgf/3cm。
在將矽烷SILQUESTTM A 187引入調配物中之情況下,IE-1之剝離強度(7kgf/3cm)高於不包括矽烷之其對應的比較實例CE-2之剝離強度(4.2kgf/3cm)。IE-2之剝離強度(4kgf/3cm)高於其對應的比較實例CE-3之剝離強度(2.6kgf/3cm),此意謂引入矽烷可進一步改良MAH-g-SEBS或MAH-g-POE基黏著劑之剝離強度,且兩種黏著劑摻合物之剝離強度在引入矽烷之後亦具有明顯的改良,其為4.1至5.8kgf/3cm。
在將矽烷SILQUESTTM A 1100引入調配物中之情況下,IE-7之剝離強度(7.5kgf/3cm)高於不包括矽烷之其對應的比較實例CE-2之剝離強度(4.2kgf/3cm)。
若需要更主動的結合力,則交聯劑可引入上述樣品中以製得2k黏著劑。將交聯劑引入彼等含有矽烷之黏著劑中可進一步改良剝離強度,且所有黏著劑之剝離強度均能夠增至約9至11kgf/3cm。
Claims (7)
- 一種組合物,以所述組合物之重量計,以重量百分比(wt%)為單位,其包括:(A)大於零至39wt%順丁烯二酸酐接枝的極性乙烯基共聚物及順丁烯二酸酐接枝的苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物(SEBS)中之至少一者;(B)大於零至20wt%環氧基或胺官能化矽烷;(C)60至99wt%(1)所述極性烯烴聚合物及/或苯乙烯類嵌段共聚物與(2)所述環氧基或胺官能化矽烷的混合物之有機溶劑;及(D)零至10wt%聚異氰酸酯交聯劑。
- 如申請專利範圍第1項所述之組合物,其中所述有機溶劑為甲基環己烷與環己酮之混合物。
- 如申請專利範圍第1或2項所述之組合物,其中所述聚異氰酸酯交聯劑包括(i)參(對異氰酸酯基苯基)硫代磷酸酯於乙酸乙酯中之溶液、(ii)基於二異氰酸己二酯(HDI)之異氰酸酯、(iii)異佛爾酮二異氰酸酯(IPDI)及(iv)基於亞甲基二苯基二異氰酸酯(MDI)或甲苯二異氰酸酯(TDI)之異氰酸酯中之至少一者。
- 一種多層結構,其包括:(a)織物層,其包括極性紡紗;(b)膜層,其包括非極性烯烴聚合物;及(c)黏著層,其在所述織物層與所述膜層之間且與所述織物層及所述膜層接觸,所述連接層由如申請專利範圍第1項所述之組合物製成。
- 如申請專利範圍第4項所述之多層結構,其中所述紡紗包括玻璃纖維。
- 如申請專利範圍第5項所述之多層結構,其中所述膜層包括非極性丙烯基彈性體及非極性乙烯基彈性體。
- 如申請專利範圍第4項至第6項中任一項所述之多層結構,其呈防水屋頂膜或紡織建築膜形式。
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- 2016-08-23 EP EP16913736.1A patent/EP3504287B1/en active Active
- 2016-08-23 WO PCT/CN2016/096359 patent/WO2018035712A1/en not_active Ceased
- 2016-08-23 US US16/326,770 patent/US11015092B2/en active Active
- 2016-08-23 CN CN201680089847.9A patent/CN109804032B/zh active Active
- 2016-08-23 KR KR1020197007562A patent/KR102601946B1/ko active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3504287A1 (en) | 2019-07-03 |
| US20190203084A1 (en) | 2019-07-04 |
| JP2019533031A (ja) | 2019-11-14 |
| KR102601946B1 (ko) | 2023-11-15 |
| WO2018035712A1 (en) | 2018-03-01 |
| CN109804032A (zh) | 2019-05-24 |
| EP3504287B1 (en) | 2023-01-25 |
| US11015092B2 (en) | 2021-05-25 |
| CN109804032B (zh) | 2022-01-14 |
| EP3504287A4 (en) | 2020-04-15 |
| TW201829702A (zh) | 2018-08-16 |
| KR20190042032A (ko) | 2019-04-23 |
| BR112019003728B1 (pt) | 2022-06-14 |
| BR112019003728A2 (pt) | 2019-07-16 |
| JP7129968B2 (ja) | 2022-09-02 |
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