TWI739776B - 不含甲醛之可固化調配物 - Google Patents
不含甲醛之可固化調配物 Download PDFInfo
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Abstract
本發明係關於一種可固化水性調配物,其包括a)具有0.1至20重量%酸單體之乳液聚合物,b)含噁唑啉聚合物及c)具有40至100重量%酸單體且具有在2,000至500,000範圍內之重量平均分子量的水性丙烯酸聚合物分散液。
Description
本發明係關於用於紡織物及非編織應用的黏合劑。
用於紡織物及非編織應用之傳統黏合劑含有N-羥甲基丙烯醯胺(NMA)作為官能性單體,其在固化之後為黏合劑提供極佳的抗水性(濕強度)及抗溶劑性(異丙醇強度)。然而,含NMA黏合劑在加熱時釋放甲醛。一種過去使用之溶液為基於伊康酸之不含甲醛交聯技術。此技術在固化之後具有良好的抗水性及抗溶劑性,但缺乏含NMA黏合劑的極佳特性。因此,期望一種不含甲醛且亦具有相當特性的系統。
本發明之一個態樣為一種可固化水性調配物,其包括以下、由以下組成或基本上由以下組成:a)具有0.1至20重量%酸單體之乳液聚合物b)含噁唑啉聚合物;及c)具有40至100重量%酸單體且具有在2000至500000範圍內之重量平均分子量的水性丙烯酸聚合物分散液。
本發明提供一種形成水性可固化調配物的方法。
如本文所用,「水性」意謂其中連續相為水的組合物,或在替代方案中,主要包含水並且視情況包含水可混溶性溶劑、生物滅除劑、潤滑劑、緩衝劑、螯合劑及界面活性劑及其他成分的混合物。
在本文中「編織」意謂通常呈薄片或網狀物形式的纖維之織物類組裝件,其由長線沿一個方向通過而其他長線與其成直角通過形成。
本文中「非編織」意謂並非編織或針織材料之通常呈薄片或網狀物形式的纖維之織物類組裝件。非編織基材包含紙;非編織織物;毯及墊;或纖維之其他組裝件。非編織基材可包含:纖維素纖維,諸如棉花、嫘縈及木漿;合成纖維,諸如聚酯、玻璃及耐綸(nylon);雙組分纖維;及其混合物。其可由本領域中已知的方法形成,諸如濕式成網、氣流成網、紡黏法、熔紡及水刺網狀物形成。
可固化水性調配物包括以下、由或基本上由以下組成:a)具有0.1至20重量%酸單體之乳液聚合物,b)含噁唑啉聚合物;及c)具有40至100重量%酸單體且具有在2000至500000範圍內之重量平均分子量的水性丙烯酸聚合物分散液。
組分A-乳液聚合物
水性非編織黏合劑包含乳液聚合物;即藉由烯系不飽和單體在水性乳液聚合方法中的自由基聚合而製備的聚合物。乳液聚合物包含作為共聚合單元之以所述乳液聚合物之重量計0.1至20重量%酸單體。在本文中包含且在本文中
揭示在0.1與20重量%之間的所有範圍;例如酸單體之重量%可為下限0.1、5、7或10至上限12、15、18或20。
乳液聚合物亦具有5000至500000之重量平均分子量。在本文中包含且在本文中揭示在5000至500000之間的任何及所有範圍,例如乳液聚合物可具有50000至400000或100000至300000之重量平均分子量。
酸單體可包含一元酸單體及二元酸單體。一元酸單體包含例如羧酸單體,諸如丙烯酸、甲基丙烯酸、丁烯酸、伊康酸單甲酯、反丁烯二酸單甲酯、反丁烯二酸單丁酯。二元酸單體之實例包含(但不限於)伊康酸、反丁烯二酸、順丁烯二酸;包含其酸酐、鹽及其混合物。
乳液聚合物亦包含至少一種其他共聚合烯系不飽和單體,諸如(甲基)丙烯酸酯單體,包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、脲基官能性(甲基)丙烯酸酯及(甲基)丙烯酸之乙醯乙酸酯、乙醯胺或氰基乙酸酯;苯乙烯或經取代之苯乙烯;乙烯基甲苯;丁二烯;乙酸乙烯酯或其他乙烯酯;乙烯基單體,諸如氯乙烯、偏二氯乙烯;及(甲基)丙烯腈。如貫穿本發明中所使用之諸如(甲基)丙烯酸酯或(甲基)丙烯醯胺之術語「(甲基)」後接另一術語的使用分別係指丙烯酸酯及甲基丙烯酸酯或丙烯醯胺及甲基丙烯醯胺兩者。亦可使用具有不同組成之乳液聚合物的混合物。
乳液聚合物以乾燥固體計以80至99.8重量%之範圍存在於調配物中。乳液聚合物在各種其他實施例中可以
82至99.8重量%之範圍及在各種其他實施例中以85至99.8重量%之範圍存在。
組分B-含噁唑啉聚合物
調配物亦包含至少一種含噁唑啉聚合物作為交聯劑。在各種實施例中,含噁唑啉聚合物可藉由在水性介質中使用本領域中熟習此項技術者已知的任何適合之聚合方法進行加成可聚合噁唑啉及至少一種烯系不飽和單體(諸如上文所列之彼等單體)之溶液聚合反應或乳液聚合加以製備。
在各種實施例中,進行加成聚合反應。
其中R1、R2、R3及R4獨立地代表氫原子、鹵素原子、烷基、芳烷基、苯基、經取代之苯基,且R5代表具有加成可聚合不飽和鍵之非環狀有機基團。
在一些實施例中,含噁唑啉聚合物具有2-噁唑啉基團。
含噁唑啉聚合物之實例包含(但不限於)乙烯基噁唑啉:諸如2-乙烯基-2-噁唑啉、2-乙烯基-4-甲基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-異丙烯基-2-噁唑啉、2-異
丙烯基-4-甲基-2-噁唑啉、2-異丙烯基-5-乙基-2-噁唑啉、2-異丙烯基-4-羥基甲基-4-乙基-2-噁唑啉、2-(I-十六基乙烯基)-4,4-雙硬脂醯基氧甲基)-2-噁唑啉、2-(I-二十基乙烯基)-4,4-雙(羥基甲基)-2-噁唑啉、2-異丙烯基-4,4-雙(羥基甲基)-2-噁唑啉、2-異丙烯基-4,4-雙(甲基)-2-噁唑啉。
含噁唑啉聚合物一般以乾燥固體計以0.1至10重量%之範圍存在於調配物中。含噁唑啉聚合物在各種其他實施例中可以1至8重量%之範圍及在各種其他實施例中以3至7重量%之範圍存在。
組分C-水性丙烯酸聚合物分散液
調配物亦包含水性丙烯酸聚合物分散液。水性丙烯酸聚合物分散液具有40至100重量%酸基。分散液在各種其他實施例中可具有50至95重量%酸基,且在各種其他實施例中具有65至80重量%酸基。水性丙烯酸聚合物分散液亦具有在2000至500000範圍內之重量平均分子量。分散液在各種其他實施例中可具有50000至400000之重量平均分子量,且在各種其他實施例中具有100000至350000之重量平均分子量。
水性丙烯酸聚合物分散液亦可由上文所列之烯系不飽和單體中之任一者形成。
水性丙烯酸聚合物分散液一般以乾燥固體計以0.1至10重量%之範圍存在於調配物中。分散液在各種其他實施例中可以1至8重量%之範圍,且在各種其他實施例中以3至7重量%之範圍存在。
視情況存在之組分
水性非編織黏合劑亦可包含習知處理組分,諸如乳化劑、顏料、填充劑或增效劑、抗遷移助劑、聚結劑、界面活性劑、生物滅除劑、塑化劑、有機矽烷、抗起泡劑、腐蝕抑制劑、著色劑、蠟、其他聚合物及抗氧化劑。
用於製備乳液聚合物之乳液聚合技術為本領域中所熟知,諸如美國專利第4,325,856號、第4,654,397號及第4,814,373號中所揭示。在各種實施例中,乳液聚合在室溫至100℃之反應溫度下執行,視引發方法(例如熱或氧化還原)而定。可以使用習知界面活性劑,諸如陰離子及/或非離子乳化劑,諸如硫酸烷酯鹼金屬鹽或銨鹽、烷基磺酸、脂肪酸、可共聚的界面活性劑及氧乙基化烷基苯酚。較佳為陰離子乳化劑。所用界面活性劑之量通常以總單體之重量計為0.1重量%至6重量%。可使用熱或氧化還原引發方法。可通常以總單體之重量計以0.01重量%至3.0重量%之水準使用習知自由基引發劑,諸如過氧化氫、氫過氧化第三丁基、氫過氧化第三戊基、過硫酸銨及/或過硫酸鹼金屬鹽及可水溶偶氮化合物,諸如偶氮雙氰基戊酸。在一實施例中,引發劑以總單體之重量計以0.5重量%至1.5重量%之範圍存在。使用相同引發劑外加諸如甲醛次硫酸鈉、亞硫酸氫鈉、異抗壞血酸、羥胺硫酸鹽及亞硫酸氫鈉之適合還原劑的氧化還原系統可按類似的水準使用,視情況與諸如鐵及銅之金屬離子組合,視情況進一步包含金屬錯合劑。鏈轉移劑(諸如硫醇)可以用於降低聚合物之分子量。單體混合物可按純淨形式或按水中乳液的形式添加。單體混合物可使用均一或不同組成在反應期間以單次添加形式或以多次添加形式添加或連續地添加。諸如自
由基引發劑、氧化劑、還原劑、鏈轉移劑、中和劑、界面活性劑以及分散劑之附加成分可以在任一階段之前、期間或之後添加。在各種實施例中,乳液聚合物可利用多階乳液聚合方法製備,其中組成不同之至少兩個階段以依序方式聚合。最終聚合物之分子量屬於以上分子量範圍內。在一些實施例中在攪拌或攪動下,含噁唑啉聚合物及水性丙烯酸聚合物分散液可接著添加至乳液聚合物。
乳液聚合物粒子之平均粒徑通常為30奈米至1000奈米,較佳為100奈米至200奈米,如利用由紐約州豪斯維爾(Holtsville,NY.)Brookhaven Instrument Corp.所提供的Brookhaven型號BI-90粒徑分析儀所量測。
使編織或非編織基材與可固化水性調配物接觸。通常以乾重計表示為百分比,亦稱為附加%的調配物與經接觸之基材之比率為1%至40%,較佳為15%至35%,其視基材強度及所期望的最終用途加以選擇。使用習知應用技術,諸如空氣或無空氣噴塗、浸染、浸透、滾塗法、簾式塗佈、凹版印刷及其類似技術使基材與可固化水性調配物接觸。可使基材與可固化水性調配物接觸以使在一或兩個表面處或其附近提供黏合劑,或使該黏合劑在整個結構中均勻地或並非均勻地分佈。亦預期當期望圖案化分佈時,可固化水性調配物可以非均一方式塗覆至一或兩個表面。
在形成含有本發明之可固化水性調配物之基材的方法中,將已與可固化水性調配物接觸之基材加熱至120℃至220℃,較佳為140℃至180℃之溫度持續足以達成固化之時間。
除了紡織物及非編織應用以外,本發明之可固化水性調配物亦可用於製作壓敏黏著劑及層壓黏著劑。
實例
所用縮寫:IPA:異丙醇
DI水:去離子水
CD:橫向
SC:固體含量
BA:丙烯酸丁酯
Sty:苯乙烯
IA:伊康酸
AA:丙烯酸
DS-4:十二烷基苯磺酸鈉,界面活性劑
TR-407:基於利用甲醛(HCHO)之NMA技術的當前市售產品
SWX1116(A):具有49Sty/46BA/3AA/2IA聚合物之乳液,其中SC為45%
EPOCROS WS500(B):來自日本觸媒株式會社(Nippon Shokubai)之具有噁唑啉基團的溶液聚合物,其中SC為40%及噁唑啉含量為4.5mmol/g固體
Leukotan 1084(C1):來自陶氏化學公司(The Dow Chemical Company)之具有100% AA及28% SC的水溶液聚合物
ASE60(C2):來自陶氏化學公司之具有40% AA及28% SC的乳液聚合物
TRITONTM X-100:來自陶氏化學公司之界面活性劑
來自沃特曼有限公司(Whatman Ltd.)之WHATMANTM 4號紙
本發明實例1及2以及比較實例1及2
以上原材料在適當攪動下持續30分鐘調配,獲得如表1及表2中之調配物的可固化水性組合物。
將一片WHATMANTM紙28cm×46cm浸漬至200mL所調配乳液中。經處理基材藉由Mathis壓染機浸染,且隨後乾燥,且在150℃下固化3分鐘。紙上聚合物之量對於表1可控制在28%至32%之間,且對於表2可控制在15%至16%
之間。經固化基材切割成1吋×4吋之片段,其中4吋方向為紙之橫向(CD)。樣本之拉伸強度在乾燥(未經處理)、濕潤(浸漬於0.1% Triton X-100/水溶液中30分鐘後)及IPA(於異丙醇中30分鐘後)之處理下進行測試。濕強度反映黏合劑對水之抵抗性,且IPA強度反映黏合劑在溶劑中之抵抗性。資料展示於表3及表4中。
如表3中所指示,愈高的強度值提供愈好的效能。除比較1以外,所有實例為不含HCHO的。比較1係基於利用含有HCHO之NMA技術,且展現最佳總體效能。比較3展示比比較2a更好的IPA強度。比較4具有低分子酸且與比較3相比不改良效能。比較5、比較6具有較高酸聚合物(C)且與無含噁唑啉聚合物之比較2a相比不改良總體效能。
與比較2b相比,本發明實例4及實例5展示濕
潤強度具有大於10%改良及IPA強度具有至少20%改良。與比較2b相比,本發明實例3及實例6展示濕潤強度降低小於15%,但IPA強度增加大於65%。比較本發明實例4及實例6,發現若組分C自0.1%增加至10%,則IPA強度將自2.8增加至3.81。
Claims (10)
- 一種可固化水性調配物,所述可固化水性調配物包括:a)乳液聚合物,其具有以該乳液聚合物重量計5至20重量%之酸單體;b)含噁唑啉聚合物;及c)水性丙烯酸聚合物分散液,其具有40至100重量%酸單體且具有在2,000至500,000範圍內之重量平均分子量。
- 如請求項1所述的可固化水性調配物,其中以乾燥固體計,所述乳液聚合物以80至99.8重量%範圍內之量存在,所述含噁唑啉聚合物以0.1至10重量%範圍內之量存在,且所述水性丙烯酸聚合物分散液以0.1至10重量%範圍內之量存在。
- 如請求項1所述的可固化水性調配物,其中所述乳液聚合物包括苯乙烯、丙烯酸丁酯、丙烯酸及伊康酸。
- 如請求項1所述的可固化水性調配物,其中所述含噁唑啉聚合物具有至少一個2-噁唑啉基團。
- 如請求項1所述的可固化水性調配物,其中所述含噁唑啉聚合物係選自由以下組成之群:2-乙烯基-2-噁唑啉、2-乙烯基-4-甲基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-異丙烯基-2-噁唑啉、2-異丙烯基-4-甲基-2-噁唑啉、2-異丙烯基-5-乙基-2-噁唑啉、2-異丙烯基-4-羥基甲基-4-乙基-2-噁唑啉、2-(I-十六基乙烯基)-4,4-雙硬脂醯基氧甲基)-2-噁唑啉、2-(I-二十基乙烯基)-4,4-雙(羥基甲基)-2-噁唑啉、2-異丙烯基-4,4-雙(羥基甲基)-2-噁唑啉、2-異丙烯基-4,4-雙(甲基)-2-噁唑啉及其混合物。
- 一種形成如請求項1所述的可固化水性調配物之方法,所述方法包括以下步驟:a)在水溶液中乳液聚合至少一種單烯系不飽和單體及至少一種酸單體,形成所述乳液聚合物;及b)將所述含噁唑啉聚合物及所述水性丙烯酸聚合物分散液添加至所述乳液聚合物,形成所述可固化水性調配物。
- 一種利用如請求項1所述的可固化水性調配物形成固化基材之方法,所述方法包括:a)使編織或非編織基材與所述可固化水性調配物接觸,形成經接觸之基材;及b)將所述經接觸之非編織基材加熱至120℃至220℃之溫度,形成所述固化基材。
- 一種產物,所述產物包括:a)編織或非編織基材;及b)包括如請求項1所述的可固化水性調配物之黏合劑。
- 一種壓敏黏合劑,其包括如請求項1所述的可固化水性調配物。
- 一種層壓黏著劑,其包括如請求項1所述的可固化水性調配物。
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