TWI646120B - 化合物 - Google Patents
化合物 Download PDFInfo
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- TWI646120B TWI646120B TW105121763A TW105121763A TWI646120B TW I646120 B TWI646120 B TW I646120B TW 105121763 A TW105121763 A TW 105121763A TW 105121763 A TW105121763 A TW 105121763A TW I646120 B TWI646120 B TW I646120B
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- compound
- sensitive adhesive
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 79
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 105
- 239000010410 layer Substances 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- 230000003287 optical effect Effects 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 26
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 125000005647 linker group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229920005601 base polymer Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 11
- 239000003607 modifier Substances 0.000 abstract description 4
- -1 polyol compound Chemical class 0.000 description 56
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- 238000002329 infrared spectrum Methods 0.000 description 17
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
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- HVZWBVZEZZJOKQ-UHFFFAOYSA-N 2-methylacridine Chemical compound C1=CC=CC2=CC3=CC(C)=CC=C3N=C21 HVZWBVZEZZJOKQ-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
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Abstract
本申請案提出一種可施用於各種用途之化合物。在一個具體實施例中,該化合物可含括於可交聯之組成物中作為交聯速率調整劑。在另一具體實施例中,該化合物可施於可交聯之組成物中,使得藉由可交聯之組成物所形成之膜與另一膜有極佳的界面黏著性,並亦防止藉由該可交聯之組成物所形成之膜發生滲漏的情況。
Description
本申請案係關於化合物,例如,係關於可應用於可交聯之組成物之化合物。此申請案聲明2015年7月10日提出申請的韓國專利申請案第10-2015-0098206號和2016年4月1日提出申請的韓國專利申請案第10-2016-0040353號之優先權和權益,茲將該等案件全文以引用方式納入本文中。
可交聯之組成物被用於各種領域。例如,可用於使保護膜或光學組件接合至元件(如液晶顯示器(LCD))面板以防止光學組件(如偏光板)、其他塑膠產品、家用品、汽車或諸如此類黏附污染物(如塵)或產生刮痕之壓敏性黏著劑或黏著劑,且此處,此壓敏性黏著劑或黏著劑可被製成可交聯之組成物。
藉由使用可交聯之組成物中之壓敏性黏著組成物而具有壓敏性黏著層事先形成於其一表面上之光學元件被稱為壓敏黏著性光學元件。例如,如專利文件1中所
揭示者,此壓敏黏著性光學元件基本上具有包括壓敏性黏著層形成於承載基板(如偏光板、偏光膜或諸如此類)的一表面上之結構。
上述壓敏黏著性光學元件中,須確保介於承載基板(如偏光板)和壓敏性黏著層之間之黏著性,及亦須抑制壓敏性黏合層分離之發生。
(專利文件1)日本專利案第5019552號
本申請案係關於化合物,且更特別地,係關於藉由施用於可交聯之組成物而可進行某些功用之化合物。
本申請案中揭示之化合物可具有下式1之結構。
其中A是包括聚環氧烷單元的核心,B是連接至核心
(A)的鏈並包括聚伸烷氧化單元,m是1或更大的整數,n是0或更大的整數,且m和n的和(m+n)是3或更大。
此處所用“聚環氧烷或聚烷二醇”是指包括二或更多個具有具2至12個碳原子之直鏈或支鏈伸烷基之環氧烷單元之標的。以上描述中,伸烷基可具有2至8、2至4或2或3個碳原子。
本申請案中,聚環氧烷的特定例子包括聚環氧乙烷或聚環氧丙烷,而聚烷二醇的特定例子包括聚乙二醇或聚丙二醇。
在一個具體實施例中,式1的核心(A)可為自聚伸烷基多元醇衍生的核心。本申請案中之“聚伸烷基多元醇化合物”是指具有聚環氧烷單元和3或更多個羥基的化合物。以上描述中,羥基可存在於聚伸烷基多元醇化合物的鏈末。例如,式1之化合物可藉由以聚伸烷基多元醇化合物鏈末處的一或多個羥基作為媒介而添加式1的鏈(B)而形成。形成核心(A)之聚伸烷基多元醇化合物可為三醇或高碳多元醇,即,包括3或更多個鏈末羥基之化合物,而鏈(B)可藉由其中的至少一個羥基作為媒介而添加。形成核心(A)之聚伸烷基多元醇化合物可包括3或更多個鏈末羥基。聚伸烷基多元醇化合物中包括的羥基數可為30或更低,25或更低,15或更低,10或更低或5或更低。據此,式1中之n和m的和(n+m)可為3或更高,亦可為30或更低,25或更低,20或更低,15或更低,10或更低,或5或更低。
另一方面,式1之化合物亦可為聚伸烷基多元醇化合物,為包括3或更多個羥基的聚環氧烷單元之化合物。
此外,下文中描述之關於式1中的核心(A)之分子量及聚環氧乙烷和聚環氧丙烷或諸如此類在式1中的核心(A)中之含括形式的細節可為形成核心(A)的聚伸烷基多元醇化合物的分子量,及聚環氧乙烷和聚環氧丙烷在形成核心(A)的聚伸烷基多元醇化合物中之含括形式。
式1之化合物中,核心(A)可具有在1,000至10,000範圍內的重量平均分子量。本申請案中,“重量平均分子量”是指藉凝膠穿透層析法(GPC),相關於聚苯乙烯標準品的轉化值。除非另外特定指明,否則文中所用“分子量”是指重量平均分子量。在另一具體實施例中,核心(A)之分子量可為2,000或更高,3,000或更高,4,000或更高,5,000或更高,或6,000或更高。在另一具體實施例中,核心(A)亦具有約9,000或更低的分子量。
式1之化合物中,核心(A)可包括聚環氧乙烷單元或聚環氧丙烷單元,且在在一個具體實施例中,可包括此二單元。核心(A)包括此二單元時,在式1之化合物的核心中之聚環氧丙烷單元的莫耳數(P)對聚環氧乙烷單元的莫耳數(E)之比(P/E)可在1至10的範圍內。在另一具體實施例中,此比(P/E)可為1.5或更高,2或更高,2.5或更高,3或更高,3.5或更高,或4或更高。在另一具體實施例中,此比(P/E)可為9.5或更低,9或更低,8.5
或更低,8或更低,7.5或更低,7或更低,6.5或更低,6或更低,5.5或更低,或約5或更低。
可形成核心之前述聚伸烷基多元醇化合物的例子可為,例如,被稱為KPX PP-2000、KPX PP-2600、KPX GP-4000、KPX-GP-5000、KPX GP-4000、KPX-HP3753或諸如此類的聚伸烷基多元醇化合物,但本申請案不限於此。
式1中,核心(A)和鏈(B)可各自包括一或多個聚環氧烷單元。
以上描述中,聚環氧烷單元的特定形式如前述者。
此聚環氧烷單元可為,例如,藉以下式3表示者。
其中L是具2至12,2至8或2至4個碳原子的直鏈或支鏈伸烷基、或上述具2或3個碳原子的直鏈或支鏈伸烷基。
式1之化合物中,加至核心(A)的鏈(B)可以,例如,藉以下式2表示。
其中A1至A3各自獨立地代表伸烷基,Q1和Q2代表脂族或芳族二價殘基,L1至L4代表連接基,x是1或更大的整數,y是0或更大的整數,和z是1或更大的整數。
式2中,L1可鍵結至核心(A)。
式2中,伸烷基可為,例如,具2至12,2至8或2至4個碳原子的直鏈或支鏈伸烷基。例如,伸烷基可為伸乙基或伸丙基。伸烷基可任意地經一或多個取代基取代。
式2中,A1或A2和鍵結至彼的氧原子(x或z界定的重複單元)可形成式3的聚環氧烷單元。
式2中,未特別限制L1至L4之連接基的類型,且例如,可為氧原子、硫原子、伸烷基、伸烯基或伸炔基,或可為藉以下式4或5表示的連接基。以上描述中,伸烷基可為具1至20,1至16,1至12,1至8或1至4個碳原子的直鏈或支鏈伸烷基,且伸烯基或伸炔基可為具2至20,2至16,2至12,2至8或2至4個碳原子的直鏈或支鏈伸烯基或伸炔基。
其中R1和R2各自獨立地代表氫原子或烷基。
式4和5中,烷基可為,例如,具1至20,1至16,1至12,1至8或1至4個碳原子的直鏈、支鏈或環狀烷基,且此烷基可經一或多個取代基任意取代。
式2中,脂環族或芳族二價殘基可為自脂環族化合物或芳族化合物衍生的二價殘基。
以上描述中,芳族化合物是指結構中的一個苯或二或更多個苯環藉共享彼的一或兩個碳原子而彼此鍵結之化合物、結構中的二或更多個苯環藉任何連接基彼此鍵結之化合物、或其衍生物。此芳族化合物可為,例如,具6至30,6至25,6至21,6至18或6至13個碳原子的化合物。
以上描述中,脂環狀化合物是指具有環狀烴結構的化合物且不是具有芳環結構的化合物。除非另外特
定指明,否則脂環狀化合物可為,例如,具3至30,3至25,3至21,3至18或3至13個碳原子的化合物。
式2中,-L1-Q1-L2-或-L3-Q2-L4-之結構可為自二異氰酸酯化合物衍生的結構。
以上描述中,二異氰酸酯化合物的例子包括甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、伸己基二異氰酸酯、異佛爾酮二異氰酸酯、四甲基二甲苯二異氰酸酯、萘二異氰酸酯或諸如此類,但不限於此。
在一個具體實施例中,式1之化合物的鏈(B)可藉以下式6表示。
其中A1至A3各自獨立地代表伸烷基,Q1和Q2代表脂族或芳族二價殘基,x是1或更大的整數,y是0或更
大的整數,和z是1或更大的整數。
式6的結構是式2中的連接基L1至L4特定地為式4或5之結構。
因此,式6中之伸烷基、二價殘基或連接基的細節可與式2中者相同。
此外,式2和6中,未特別限制x、y和z的特定範圍,且例如,x、y和z可選自可具有以下描述之分子量的範圍之式1之化合物。
式1之化合物可以,例如,藉由使介於聚烷二醇化合物和二異氰酸酯化合物之間的反應得到的鏈與形成核心(A)並包括三個鏈末羥基的前述聚伸烷基多元醇化合物反應而製得。
例如,作為用於製造鏈之反應,當聚乙二醇與異佛爾酮二異氰酸酯反應時,可得到以下式A表示之結構中的一端是羥基且另一端是異氰酸酯基的鏈之先質。
例如,式A之鏈的先質與以下式B之三醇化合物反應,使得式B之三醇的所有羥基與式A之鏈末的
異氰酸酯基反應以添加該鏈時,可形成具有以下式C中所表示之結構的化合物。此情況中,以下式B和C中的P可為式1之核心(A)。
此式1之化合物可包括3莫耳或更多的羥基。在另一具體實施例中,式1之化合物中含括的羥基的莫耳數可為30或更低,25或更低,20或更低,15或更低,10或更低,或5或更低。
在另一具體實施例中,式1之化合物可具有4mgKOH/g或更高的羥值。在另一具體實施例中,羥值可為30mgKOH/g或更低,25mgKOH/g或更低,20mgKOH/g或更低,或15mgKOH/g或更低。
以上描述中,羥值可根據ASTM E222-10(使
用乙酸酐,用於羥基的標準試驗方法)計算。
式1之化合物可為具有10,000或更高的分子量之化合物。在另一具體實施例中,分子量可為100,000或更低,90,000或更低,80,000或更低,70,000或更低,60,000或更低,50,000或更低,或40,000或更低。
前述式1之化合物可用於各種用途。在一個具體實施例中,式1之化合物可含括於可交聯之組成物中以改良介於藉可交聯組成物所形成的膜和另一膜之間的界面黏著性。特定言之,式1之化合物藉由含括於可交聯之組成物中以將介於組成物中的交聯組份之間的交聯反應延遲或抑制至適當程度而用以提高界面黏著性。結果,在另一具體實施例中,此式1之化合物可被視為交聯速率調整劑。前述式1之化合物的結構、羥值、分子量或諸如此類可經控制以使得式1之化合物可作為交聯速率調整劑。
如前述者,可交聯之組成物可以,例如,用以在承載基板(如壓敏黏著性光學組件)的一表面上形成黏著層或壓敏性黏合層,且式1之化合物可用於此可交聯之組成物以增進介於承載基板和壓敏性黏著層或黏著層之間的界面黏著性,並抑制滲漏現象或諸如此類。
本發明之發明者預測藉前述可交聯組成物所形成之壓敏性黏著層、黏著層或諸如此類與承載基板具有低界面黏著性的原因之一是因為介於可交聯之組成物中之可交聯組份之間的反應之發生過於迅速。但是,預期式1之化合物適當地延遲或抑制介於可交聯之組成物中之可交
聯組份之間的反應,藉此形成與承載基板具有極佳界面黏著性的膜。
因此,本申請案係關於包括式1之化合物之可交聯之組成物。
未特別限制可交聯之組成物中含括的其他組份。
例如,可交聯之組成物可包括丙烯酸系壓敏黏著性樹脂和就壓敏黏著性樹脂作為交聯組份之交聯劑。
本申請案中,“丙烯酸系壓敏黏著性樹脂”是指聚合物,其包括丙烯酸系單體作為主要組份且其於交聯之前或之後展現壓敏黏著性。以上描述中,丙烯酸系單體可為丙烯酸或甲基丙烯酸、丙烯酸或甲基丙烯酸的衍生物,且例如,可為丙烯酸酯或甲基丙烯酸酯。此外,在本申請案中,含括作為主要組份是指對應組份的重量比為55%或更高,60%或更高,65%或更高,70%或更高,75%或更高,80%或更高,85%或更高,或90%或更高。在另一具體實施例中,含括作為主要組份之重量比可為100%或更低或低於100%。
可含括丙烯酸系壓敏黏著性樹脂作為可交聯之組成物中之主要組份。即,基於可交聯之組成物的固體總含量,丙烯酸系壓敏黏著性樹脂的重量比可為55%或更高,60%或更高,65%或更高,70%或更高,75%或更高,80%或更高,85%或更高,或90%或更高。在另一具體實施例中,基於可交聯之組成物的固體總含量,樹脂的重量
比亦可為100%或更低,或低於100%。
作為丙烯酸系壓敏黏著性樹脂,例如,可以使用具有羧基的丙烯酸系壓敏黏著性樹脂。本發明之發明者確認使用具有羧基的壓敏黏著性樹脂作為可交聯組份時,式1之化合物能夠更有效地延遲交聯反應。
此外,此丙烯酸系壓敏黏著性樹脂可改良可交聯之組成物在耐熱和耐濕熱條件下的耐久性,且在添加以下描述的離子性化合物的情況中,因為形成化合物,所以膜的表面耐受性的長時間變化極微。
藉由使用丙烯酸系壓敏黏著性樹脂,壓敏黏著性光學組件特別施用至所謂的LCD之直立對準(VA)模式能夠得到良好的效果。
在一個具體實施例中,該丙烯酸系壓敏黏著性樹脂可具有20或更高的酸值。以上描述中,酸值代表中和1g樣品中所含游離脂肪酸或樹脂酸所須之氫氧化鉀的毫克數。在另一具體實施例中,樹脂的酸值可為約25或更高或約30或更高。此外,在另一具體實施例中,樹脂的酸值可為約50或更低,約45或更低,約40或更低,或約35或更低。藉由施用具有上述酸值的樹脂可進一步增進含括羧酸的效果。
例如,可以使用具有(甲基)丙烯酸酯單體之聚合單元和酸性單體之聚合單元之聚合物作為丙烯酸系壓敏黏著性樹脂。本說明書中,“聚合單元”是指對應的單體藉聚合反應形成聚合物主鏈的狀態。
以上描述中,可以使用,例如,(甲基)丙烯酸烷酯作為(甲基)丙烯酸酯化合物,考慮控制黏著力、玻璃轉變溫度、壓敏黏著性等,可以使用具有具2至12個碳原子的烷基之(甲基)丙烯酸烷酯。此單體的例子包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-乙基丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸月桂酯或諸如此類,且其中的一或二或更多者可含括於聚合物中。
例如,該丙烯酸系壓敏黏著性樹脂可包括酸性單體作為聚合單元。“酸性單體”是指具有酸性基團的可聚合單體,且例如,可使用具有羧基的單體。以上描述中,具有羧基的單體的例子包括(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙酸、3-(甲基)丙烯醯氧基丙酸、4-(甲基)丙烯醯氧基丁酸、丙烯酸二聚物、衣康酸、順丁烯二酸、順丁烯二酸酐或諸如此類,但不限於此。
該丙烯酸系壓敏黏著性樹脂可包括酸性單體作為聚合單元,以100重量份的(甲基)丙烯酸酯化合物計,其量為約5重量份或更高,5.5重量份或更高,或6重量份或更高。除非另外指明,否則本說明書中,“重量份”是指組份之間的重量比。在另一具體實施例中,所含
酸性單體的比是約20重量份或更低,約15重量份或更低,或約10重量份或更低。
必要時,該丙烯酸系壓敏黏著性樹脂可包括額外的單體之聚合單元,額外的單體如:含羥基的單體,如(甲基)丙烯酸羥烷酯(如,(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯或諸如此類)或(甲基)丙烯酸羥基烷二醇酯,如,(甲基)丙烯酸2-羥基乙二醇酯、(甲基)丙烯酸2-羥基丙二醇酯或諸如此類;含氮的單體,如,(甲基)丙烯晴、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-乙烯基吡咯烷酮、N-乙烯基己內醯胺或諸如此類;含環氧烷基的單體,如,烷氧基烷二醇(甲基)丙烯酸酯、烷氧基二烷二醇(甲基)丙烯酸酯、烷氧基三烷二醇(甲基)丙烯酸酯、烷氧基四烷二醇(甲基)丙烯酸酯、烷氧基聚乙二醇(甲基)丙烯酸酯、苯氧基烷二醇(甲基)丙烯酸酯、苯氧基二烷二醇(甲基)丙烯酸酯、苯氧基三烷二醇(甲基)丙烯酸酯、苯氧基四烷二醇(甲基)丙烯酸酯、苯氧基聚烷二醇(甲基)丙烯酸酯或諸如此類;以苯乙烯為基礎的單體,如,苯乙烯或甲基苯乙烯;含環氧丙基的單體,如,(甲基)丙烯酸環氧丙酯;羧酸乙烯酯,如,乙酸乙烯酯等。
此丙烯酸系壓敏黏著性樹脂可使用典型的聚合法製得,例如,藉由將根據所欲單體組成之適當單體加以混合而製得的單體混合物施用於溶液聚合法。此程序
中,必要時,可以一併使用適當的聚合反應引發劑、分子量調整劑、鏈轉移劑或諸如此類。
可交聯之組成物可以另包括交聯劑,特定言之,有助於壓敏黏著性樹脂交聯之交聯劑。交聯劑的例子包括具有二或更多個能夠與丙烯酸系壓敏黏著性樹脂中所含括的羧基反應之官能基的化合物。可以使用此技術中常用的交聯劑(如以環氧基為基礎的交聯劑或以吖啶為基礎的交聯劑)作為此交聯劑。特定言之,例如,選自由以下所組成之群組中之一或多者:乙二醇二環氧丙醚、三環氧丙醚、三羥甲基丙烷三環氧丙醚、N,N,N’,N’-四環氧丙基乙二胺、甘油二環氧丙醚、N,N’-甲苯-2,4-雙(1-吖啶羧醯胺)、N,N’-二苯基甲烷-4,4’-雙(1-吖啶羧醯胺)、三伸乙基三聚氰胺、雙isoprothaloyl-1-(2-甲基吖啶)和三-1-吖啶基膦化氧,但本申請案不限於此。以100重量份在可交聯之組成物中之丙烯酸系壓敏黏著性樹脂計,此交聯劑含量可為0.0001至15重量份,但不限於此。在另一具體實施例中,交聯劑的比可為約0.0005重量份或更高,或約0.001重量份或更高。在另一具體實施例中,交聯劑的比可為13重量份或更低,11重量份或更低,9重量份或更低,7重量份或更低,5重量份或更低,3重量份或更低,1重量份或更低,0.5重量份或更低,0.1重量份或更低,或0.05重量份或更低。
未特別限制前述可交聯之組成物中之式1之化合物的比,且可考慮所欲界面黏著改良效果或諸如此類
而適當地調整。例如,以100重量份的丙烯酸系壓敏黏著性樹脂計,式1之化合物含量可為0.01重量份或更高。在另一具體實施例中,式1之化合物的比可為約0.02重量份或更高,約0.03重量份或更高,或約0.04重量份或更高。此外,在另一具體實施例中,式1之化合物的比可為約10重量份或更低,約9重量份或更低,約8重量份或更低,約7重量份或更低,約6重量份或更低,約5重量份或更低,約4重量份或更低,約3重量份或更低,約2重量份或更低,約1重量份或更低,約0.5重量份或更低,約0.4重量份或更低,約0.3重量份或更低,約0.2重量份或更低,或約0.1重量份或更低。
除了前述組份以外,該可交聯之組成物可以根據用途而進一步包括其他組份。
例如,該可交聯之組成物可另外包括異氰酸酯化合物。例如,當該可交聯之組成物施用於以下將描述的光學組件時,此化合物可用以提高與光學組件之黏著性。以異氰酸酯為基礎的化合物的例子包括選自由以下所組成之群組中之一或多者:甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、伸己基二異氰酸酯、異佛爾酮二異氰酸酯、四甲基二甲苯二異氰酸酯、萘二異氰酸酯及彼等與多元醇(如三羥甲基丙烷)之反應物,但不限於此。以100重量份的丙烯酸系壓敏黏著性樹脂計,此以異氰酸酯為基礎的化合物含量可為0.01至10重量份,但不在此限。在另一具體實施例中,異氰酸酯化合物的比可
為約0.05重量份或更高,0.01重量份或更高,0.1重量份或更高,0.5重量份或更高,或約1重量份或更高。在另一具體實施例中,交聯劑的比可為8重量份或更低,6重量份或更低,4重量份或更低,或3.5重量份或更低。
必要時,該可交聯之組成物可以另包括離子性化合物。以上描述中,可選擇具有4或更高的辛烷-水分配係數(LogP)之離子性化合物作為該離子性化合物。辛烷-水分配係數是代表溶質在兩種不互溶的辛烷和水相中之分佈的係數。當辛烷-水分配係數為4或更高的離子性化合物與可交聯之組成物混合時,可提供在高濕度條件或高溫和高濕度條件下長時間維持安定的抗靜電性且表面電阻未改變之可交聯之組成物。在另一具體實施例中,辛烷-水分配係數可為4.5或更高,5或更高,或5.5或更高。辛烷-水分配係數越高,確保離子性化合物在高濕度或高濕度條件下的安定性越高,並因此而未特別限制其上限。在一個具體實施例中,辛烷-水分配係數可為30或更低,25或更低,20或更低,或15或更低。
該離子性化合物亦包括陽離子-水結合能在0至0.6Kcal/mol範圍內的陽離子。在此範圍內的結合能有利於確保離子性化合物在高濕度條件或高溫度和高濕度條件下的安定性。在另一具體實施例中,陽離子-水結合能可約略在0至0.55Kcal/mol,0.1至0.55Kcal/mol,0.2至0.55Kcal/mol或0.3至0.55Kcal/mol的範圍內。
無特別限制地,可以使用任何已知化合物作
為離子性化合物,只要該化合物的辛烷-水分配係數在上述範圍內,且陽離子-水結合能如所須地在上述範圍內即可。
在一個具體實施例中,包括以下式7之陽離子的離子性化合物可作為該離子性化合物。
其中R1代表具1至3個碳原子的烷基,R2至R4各自獨立地代表具4至20個碳原子的烷基。
式7中,R1至R4可代表直鏈、支鏈或環狀烷基,且較佳地為直鏈烷基。該烷基亦可任意地經另一取代基(如烷基或諸如此類)取代。
在另一具體實施例中,式7中,R2至R4各自獨立地代表具4至16,4至12或4至8個碳原子的烷基。
上述陽離子具有氮原子鍵結至4個烷基且其中的3個烷基是具4或更多個碳原子的長鏈烷基之結構,且具此結構之陽離子有利於確保辛烷-水分配係數和陽離子-水結合能在上述範圍內。
式7之陽離子的例子包括N-甲基-N,N,N-三丁基銨、N-乙基-N,N,N-三丁基銨、N-甲基-N,N,N-三己基
銨、N-乙基-N,N,N-三己基銨、N-甲基-N,N,N-三辛基銨、N-乙基-N,N,N-三辛基銨或諸如此類,但不限於此。
該離子性化合物中所含陰離子的例子包括氟(F-)、氯(Cl-)、溴(Br-)、碘(I-)、過氯酸(ClO4-)、羥基(OH-)、碳酸根(CO3 2-)、硝酸根(NO3 -)、三氟甲磺酸根(CF3SO3 -)、磺酸根(SO4 -)、六氟磷酸根(PF6 -)、甲基苯磺酸根(CH3(C6H4)SO3 -)、對-甲苯磺酸根(CH3C6H4SO3-)、四硼酸根(B4O7 2-)、羧基苯磺酸根(COOH(C6H4)SO3 -)、三氟甲磺酸根(CF3SO2 -)、苯甲酸根(C6H5COO-)、醋酸根(CH3COO-)、三氟醋酸根(CF3COO-)、四氟硼酸根(BF4 -)、四苄基硼酸根(B(C6H5)4 -)、參(五氟乙基)三氟磷酸根(P(C2F5)3F3 -)等。
在一個具體實施例中,該離子性化合物包括藉以下式8表示的陰離子或雙(氟磺醯基)醯亞胺。
[式8][X(YOmRf)n]-
其中X代表氮原子或碳原子,Y代表碳原子或硫原子,Rf代表全氟烷基,m是1或2和n是2或3。
式8中,當Y是碳時,m可為1,當Y是硫時,m可為2,當X是氮時,n可為2,而當X是碳時,n可為3。
式8之陰離子或雙(氟磺醯基)醯亞胺因為全氟烷基(Rf)或氟基而展現高陰電性,並包括獨特的共振結構
(其與陽離子形成弱鍵結),藉此具有疏水性。據此,該離子性化合物展現與組成物的另一組份(如聚合物)之極佳的相容性,並可以小量提供高抗靜電能力。
式8的Rf可為具1至20,1至12,1至8或1至4個碳原子的全氟烷基。此情況中,該全氟烷基具有直鏈、支鏈或環狀結構。式8之陰離子可為以磺醯基甲基化物為基礎、以磺醯基醯亞胺為基礎、以羰基甲基化物為基礎或以羰基醯亞胺為基礎的陰離子,且特定言之,參三氟甲磺醯基甲基化物、雙三氟甲磺醯基醯亞胺、雙全氟丁磺醯基醯亞胺、雙五氟乙磺醯基醯亞胺、參三氟甲羰基甲氧化物、雙全氟丁羰基醯亞胺、雙五氟乙羰基醯亞胺等中之一者或二或更多者之混合物。
未特別限制在該可交聯之組成物中之離子性化合物的比,且可考慮所欲抗靜電性或諸如此類而調整至適當範圍。
該離子性化合物實質上未與該可交聯之組成物中的式1之化合物形成鉗合物。此外,式1之化合物對於丙烯酸系壓敏黏著性樹脂的親和性高於對於該可交聯之組成物中之離子性化合物的親和性。
除了上述組份以外,該可交聯之組成物可另以包括一或多種添加劑,例如,選自由以下所組成之群組:矽烷偶合劑、賦黏劑、環氧樹脂、交聯劑、UV光安定劑、抗氧化劑、著色劑、強化劑、填料、抗起泡劑、界面活性劑和塑化劑。
本申請案亦係關於壓敏黏著性光學組件,其包括光學組件;形成於該光學組件的一表面上的壓敏性黏著層。以上描述中,“可交聯之組成物的壓敏性黏著層”是指由可交聯組成物所形成的壓敏性黏著層,且例如,該壓敏性黏著層可藉由自上述可交聯之組成物揮發有機溶劑及交聯丙烯酸系壓敏黏著性樹脂而形成。以上描述中,壓敏黏著性光學組件亦是指藉壓敏性黏著層接合至黏著物而形成的光學組件。
以上描述中,光學組件的例子無特別限制地包括偏光膜、亮光增進膜、阻滯膜或諸如此類,可使用偏光膜作為代表。
以上描述中,未特別限制偏光膜的類型,且例如,可以無限制地施用此技術中已知之一般類型的偏光膜,如以聚乙烯醇為基礎的偏光膜或諸如此類。
該偏光膜係能夠自在各方向振動的入射光僅萃出在一個方向振動的光之功能膜。此偏光膜中,例如,以聚乙烯醇為基礎的樹脂可吸附和對準二向色染料。形成該偏光膜之該以聚乙烯醇為基礎的樹脂可以,例如,藉由使以聚乙酸乙烯酯為基礎的樹脂膠凝而得。此情況中,所用之以聚乙酸乙烯酯為基礎的樹脂亦可包括乙酸乙烯酯和能夠與乙酸乙烯酯共聚之單體的共聚物及乙酸乙烯酯的均聚物。能夠與乙酸乙烯酯共聚之單體可為,但不限於,不飽和碳酸酯、烯烴、乙烯醚、不飽和磺酸酯和具有銨基的丙烯醯胺中之一或至少二者之混合物。通常,以聚乙烯醇
為基礎的樹脂的膠凝程度可為約85至100mol%,且較佳地為98mol%或更高。該以聚乙烯醇為基礎的樹脂可經進一步改質,且例如,可為經醛改質的聚乙烯甲醛或聚乙烯乙醛。該以聚乙烯醇為基礎的樹脂之聚合程度可為約1,000至10,000,或1,500至5,000。
該偏光膜可經由定向該以聚乙烯醇為基礎的樹脂(如單軸定向),以二向色染料將該以聚乙烯醇為基礎的樹脂加以染色,吸附該二向色染料,以硼酸水溶液處理已吸附二向色染料之該以聚乙烯醇為基礎的樹脂,及之後清洗該聚乙烯醇樹脂膜而製得。此處,可以使用碘或二向色有機顏料作為二向色染料。
當光學組件是偏光膜時,該偏光膜可進一步包括接合至該偏光膜的一或兩表面的保護膜,且在此情況中,壓敏性黏著層可形成於該保護膜的一表面。未特別限制該保護膜的類型,且其例子包括以纖維素為基礎的膜,如三乙醯基纖維素(TAC)膜;以聚酯為基礎的膜,如聚碳酸酯或聚(伸乙基對酞酸酯)(PET)膜;丙烯酸系膜;以聚醚碸為基礎的膜;和具有聚乙烯膜、聚丙烯膜和以聚烯烴為基礎的膜(使用具有以環為基礎的結構或降莰烯結構或乙烯-丙烯共聚物製得)中之一或至少二者之堆疊結構的膜。
本申請案中,未特別限制在前述光學組件上形成壓敏性黏著層之方法,例如,可施用製造壓敏性黏著劑之方法,也可以使用將壓敏性黏著組成物直接塗覆和固化於偏光板上的方法,或將壓敏性黏著組成物塗覆和固化
在脫模膜之經脫模處理的表面上並將所得組成物轉移至偏光板之方法。
有壓敏性黏著層接合至彼的光學組件表面可另包括表面經處理的層,如經電暈處理的層或經電漿處理的層。表面經處理的層具有羥基,其可藉由與異氰酸酯化合物反應或諸如此類而提高界面黏著性。
在一個具體實施例中,本申請案係關於用於影像顯示裝置之壓敏黏著性光學組件,其包括壓敏性黏著層,該層含有形成於用於影像顯示裝置之該壓敏黏著性光學組件的一或兩表面上之壓敏性黏著劑組成物。以上描述中,該壓敏性黏著劑組成物可為可交聯之組成物的例子。
該壓敏性黏著劑組成物可包括離子性液體和作為基底聚合物之具有玻璃轉變溫度為0℃或更低的聚合物。以上描述中,該離子性液體可為前述離子性化合物中之於室溫為液相的離子性化合物,且該基底聚合物可為丙烯酸系壓敏黏著性樹脂。該基底聚合物具有約-200℃或約-100℃或更高的玻璃轉變溫度。
此外,該具有玻璃轉變溫度為0℃或更低的聚合物可為丙烯酸系聚合物(該丙烯酸系聚合物具有50至100重量%之包括一或多種具有具1至14個碳原子的烷基的(甲基)丙烯酸酯之單體作為主要組份),並具有29或更低的酸值。該聚合物可具有0或更高的酸值。
該壓敏性黏著劑組成物可以另包括前述聚伸烷基多元醇化合物。
本申請案亦係關於前述壓敏黏著性光學組件接合至彼的顯示裝置或影像顯示裝置。例如,該裝置可包括液晶面板和接合至液晶面板的一或兩表面的光學組件。
可以使用已知面板,如被動基質型面板(如扭曲向列(TN)、超扭曲向列(STN)、鐵電(F)或聚合物分散(PD)面板)、活性基質型面板(如二或三端點面板、同平面切換(IPS)面板或直立對準(VA)面板)作為液晶面板。特別地,當施用前述壓敏性黏著劑時,VA模式液晶面板可以有效地作為液晶面板。
此外,未特別限制液晶顯示器的其他組件的類型,例如,濾色基板或上和下基板(如陣列基板),且可以無限制地施用此技術已知的任何組件。
本申請案提供可用於各種用途之化合物。在一個具體實施例中,該化合物可含括於可交聯之組成物中作為交聯速率調整劑。在另一具體實施例中,該化合物可用於可交聯之組成物,使得藉該可交聯組成物所形成之膜具有與另一膜之極佳的界面黏著性,且亦防止藉該可交聯之組成物所形成的膜發生滲漏的情況。
圖1至4出示製備例2至5中製得的化合物的紅外光(IR)光譜結果。
下文中,將對照實例和比較例,詳細解釋本發明,但壓敏性黏著組成物之範圍不限於以下實例。
1.紅外光(IR)光譜術
本說明書中所用之測定IR光譜的條件如下。測定期間內,光譜基線是空氣。
測定儀器:Agilent Cary 660 FTIR Spectrometer
ATR:PIKE Technologies 025-2018 Miracle ZnSe performance crystal plate
測定波長:400至4000nm
測定溫度:25℃
2.分子量之評估
重量平均分子量(Mn)係在以下條件下使用GPC測定。製作校正曲線時,在Agilent系統中,使用聚苯乙烯標準品轉換測定結果。
測定儀器:Agilent GPC(Agilent 1200 series,U.S.)
管柱:連接的兩個PL Mixed B
管柱溫度:40℃
沖提液:四氫呋喃(THF)
流率:1.0mL/min
濃度:~1mg/mL(100μL注射)
3.酸值之測定
使用自動滴定裝置測定(COM-550,HIRANUMA SANGYO Co.,Ltd.製造)測定酸值,並藉以下式計算:
A={(Y-X)×f×5.611}/M
A;酸值
Y;樣品溶液的滴定量(ml)
X;含有50g混合溶劑之溶液的滴定量(ml)
f;滴定液的因子
M;聚合物樣品的重量(g)
測定條件如下。
樣品溶液:將約0.5g的聚合物樣品溶於50g混合溶劑(甲苯/2-丙醇/蒸餾水=50/49.5/0.5,重量比)中而製得
滴定液:0.1N,2-丙醇型氫氧化鉀溶液(Wako Junyaku Kogyo Co.,Ltd.,製造,測定石油產品的中和值)
電極:玻璃電極,GE-101,比較電極:RE-201
測定模式:測定石油產品的中和值
4.辛醇-水分配係數之測定
辛醇-水分配係數(LogP)係使用COSMOtherm(版本C30_1301,COSMOlogic)(其為市售熱動力程式)計算。使用此程式計算各化合物的表面電荷分佈及水和辛醇的化學電位差異,並藉此得到分配係數(LogP)。此程序中,施用BP_TZVP_C30_1301參數化處理。
5.陽離子-水結合能之測定
使用市售密度函數理論(DFT)程式,所謂的TURBOMOLE(6.5版,COSMOlogic GmbH & Co.KG製造),藉由計算各模型的能量及計算水和相關化合物維持分離之情況及水和相關化合物形成水-陽離子錯合物之情況的能量差異,得到結合能。此程序中,施用B-P函數,def-TZVP基礎組,COSMO及ε=無限大。
6.耐久性之測定
實例或比較例之偏光板切成約262mm×約465mm(寬×長)的尺寸以製得兩片試樣,藉此製得的兩片試樣以各偏光板的光學吸收軸交錯的方式接合至玻璃基板的兩表面,藉此製得樣品。約5Kg/cm2壓力施於接合處,此操作於無塵室中進行,以免引入氣泡或外來物質。
藉耐熱耐久性和耐濕熱耐久性評估樣品的耐久性。樣品留置於60℃的溫度和90%的相對濕度中約500小時之後評估耐濕熱耐久性,樣品留置於80℃的溫度中500小時之後評估耐熱耐久性。
耐久性的評估標準如下。
○:評估耐熱和耐濕熱耐久性時,沒觀察到氣泡和剝離
△:評估耐熱和/或耐濕熱耐久性時,觀察到少許氣泡和/或剝離
X:評估耐熱和/或耐濕熱耐久性時,觀察到許多氣泡
和/或剝離
7.壓敏性黏著層的表面電阻之測定
實例或比較例中製得的偏光板留置於25℃和50%RH的室溫條件下7天並測定表面電阻(初始表面電阻)。自偏光板移除脫模膜之後,測定表面電阻,在23℃和50%RH的環境下,使用HIRESTA-UP(MCP-HT450;Mitsubishi Chemical Corporation製造)施以500V的電壓達1分鐘。樣品(壓敏黏著性偏光板)留置於80℃達1,000小時以測定樣品在耐熱條件下的表面電阻,及樣品(壓敏黏著性偏光板)留置於60℃和90%RH達1,000小時以測定樣品在耐濕熱條件下的表面電阻。留置於以上耐熱和耐濕熱條件下的樣品在各試樣留置於室溫達24小時之後接受評估。
8.濁度之評估
在剛塗覆實例或比較例中製得的壓敏性黏著組成物之後,藉由以肉眼觀察塗覆溶液的狀態而評估濁度。根據以下標準進行此評估。
○:未觀察到混濁
△:觀察到輕微混濁
X:觀察到嚴重混濁
9.剝離強度之評估
實例或比較例中製得的壓敏黏著性偏光板切成25mm×120mm(寬×長)的尺寸並藉壓敏性黏著層媒介
接合至玻璃基板。
接合4小時之後,以180度的剝離角度和300mm/min的剝離速率自玻璃基板逐漸剝離偏光板以測定剝離強度(初始剝離強度)。進一步地,在接合之後,使偏光板留置於50℃ 4小時,並以相同方式測定剝離強度(50℃剝離強度)。
10.基板黏著性之評估
藉以下方法評估壓敏黏著性偏光板的基板黏著性(介於壓敏性黏著層和偏光板保護膜(TAC膜)之間的黏著性)。先將強力黏著膠帶接合至形成於壓敏黏著性偏光板的一表面上之壓敏性黏著層的表面上。積層之後的1分鐘內,自壓敏黏著性偏光板剝離此強力黏著膠帶,測定剝離之後殘留在偏光板表面上的壓敏性黏著層的量並基於以下標準分類。
○:偏光板總面積的90%或以上有壓敏性黏著層殘留
△:偏光板總面積的50%或以上且低於90%有壓敏性黏著層殘留
X:偏光板總面積之低於50%有壓敏性黏著層殘留
11.於室溫的脫模剝離強度
實例或比較例中製得的壓敏黏著性偏光板切成50mm×120mm(寬×長)的尺寸。之後,經切割之壓敏黏著性偏光板之沒有壓敏性黏著層的表面使用雙面膠帶接合至玻璃基板。之後,於180度的剝離角度和300
mm/min的剝離速率剝離在壓敏性黏著層上的脫模膜以測定剝離強度(初始剝離強度)。
製備例1. 丙烯酸系壓敏性黏著樹脂溶液之製備
在經氮氣回流及裝設冷卻裝置以易於調整溫度的1L反應器中,引入丙烯酸正丁酯(BA)和丙烯酸(AA),其重量比(BA:AA)為94:6,亦將乙酸乙酯引至其中作為溶劑。之後,藉由通以氮氣1小時而移除氧,引入反應引發劑(AIBN:偶氮基雙異丁腈)並反應約8小時。之後,反應物以乙酸乙酯稀釋以製得酸值範圍約32至34且重量平均分子量約1,800,000的丙烯酸系壓敏性黏著樹脂溶液。
製備例2. 式1之化合物(A)之製備
在經氮氣回流並裝設加熱器、冷卻裝置和溫度計以易於調整溫度的反應器中,引入重量平均分子量約400的聚乙二醇(PEG)和異佛爾酮二異氰酸酯(IPDI),其引入的重量比(PEG:IPDI)為約5:2.8,溫度緩慢升至約50℃並維持。在此狀態,混合物均勻混合並反應約1小時。藉IR光譜定出反應時間,持續反應直到在IR光譜中之2,270cm-1處的NCO峰的面積降為反應之前的50%。
之後,反應物與多元醇反應以製得式1之化合物(A)。以上描述中,使用重量平均分子量約7,000的多元醇化合物(HP-3753,KPX CHEMICAL CO.,LTD.製造),其為具有三個鏈末羥基的三醇化合物,包括85重量%的聚環氧丙烷單元和15重量%的聚環氧乙烷單元,作為
多元醇。
此多元醇化合物、反應物和觸媒(二丁基二月桂酸錫)以92.1:7.8:0.003的重量比(多元醇化合物:反應物:觸媒)混合,混合物緩慢地逐滴加至溫度維持於約60℃的反應器中並進一步反應,藉此製得式1之化合物(A)。持續反應直到IR光譜中的NCO峰完全消失。
藉此製得的化合物(A)具有約15,200的分子量(Mw)和約11.2mgKOH/g的羥值(OHv)。製得之化合物的IR光譜示於圖1。
製備例3. 式1之化合物(B)之製備
在經氮氣回流並裝設加熱器、冷卻裝置和溫度計以易於調整溫度的反應器中,引入重量平均分子量約400的聚乙二醇(PEG)和異佛爾酮二異氰酸酯(IPDI),其引入的重量比(PEG:IPDI)約13.6:7.6,溫度緩慢升至約50℃並維持。在此狀態,混合物均勻混合並反應約1小時。藉IR光譜定出反應時間,持續反應直到在IR光譜中之2,270cm-1處的NCO峰的面積降為反應之前的50%。
之後,反應物與多元醇反應以製得式1之化合物(A)。以上描述中,使用重量平均分子量約7,000的多元醇化合物(HP-3753,KPX CHEMICAL CO.,LTD.製造),其為具有三個鏈末羥基的三醇化合物,包括85重量%的聚環氧丙烷單元和15重量%的聚環氧乙烷單元,作為多元醇。
此多元醇化合物、反應物和觸媒(二丁基二月
桂酸錫)以78.9:21.2:0.009的重量比(多元醇化合物:反應物:觸媒)混合,混合物緩慢地逐滴加至溫度維持於約60℃的反應器中並進一步反應,藉此製得式1之化合物(B)。持續反應直到IR光譜中的NCO峰完全消失。
藉此製得的化合物(B)具有約28,900的分子量(Mw)和約5.61mgKOH/g的羥值(OHv)。製得之化合物的IR光譜示於圖2。
製備例4. 式1之化合物(D)之製備
在經氮氣回流並裝設加熱器、冷卻裝置和溫度計以易於調整溫度的反應器中,引入重量平均分子量約400的聚乙二醇(PEG)和異佛爾酮二異氰酸酯(IPDI),其引入的重量比(PEG:IPDI)約17.3:9.7,溫度緩慢升至約50℃並維持。在此狀態,混合物均勻混合並反應約1小時。藉IR光譜定出反應時間,持續反應直到在IR光譜中之2,270cm-1處的NCO峰的面積降為反應之前的50%。
之後,反應物與多元醇反應。以上描述中,使用重量平均分子量約5,000的多元醇化合物(GP-5000,KPX CHEMICAL CO.,LTD.製造),其為具有三個鏈末羥基的三醇化合物,包括聚環氧丙烷單元,作為多元醇。
此多元醇化合物、反應物和觸媒(二丁基二月桂酸錫)以73.1:27:0.011的重量比(多元醇化合物:反應物:觸媒)混合,混合物緩慢地逐滴加至溫度維持於約60℃的反應器中並進一步反應,藉此製得式1之化合物(D)。持續反應直到IR光譜中的NCO峰完全消失。
藉此製得的化合物(D)具有約13,500的分子量(Mw)和約12.2mgKOH/g的羥值(OHv)。製得之化合物的IR光譜示於圖3。
製備例5. 式1之化合物(E)之製備
在經氮氣回流並裝設加熱器、冷卻裝置和溫度計以易於調整溫度的反應器中,引入重量平均分子量約2000的聚乙二醇(PEG)和異佛爾酮二異氰酸酯(IPDI),其引入的重量比(PEG:IPDI)約17.3:9.7,溫度緩慢升至約45℃並維持。在此狀態,混合物均勻混合並反應約1小時。藉IR光譜定出反應時間,持續反應直到在IR光譜中之2,270cm-1處的NCO峰的面積降為反應之前的50%。
之後,反應物與多元醇反應。以上描述中,使用重量平均分子量約5,000的多元醇化合物(GP-5000,KPX CHEMICAL CO.,LTD.製造),其為具有三個鏈末羥基的三醇化合物,包括聚環氧丙烷單元,作為多元醇。
此多元醇化合物、反應物和觸媒(二丁基二月桂酸錫)以73.1:27:0.011的重量比(多元醇化合物:反應物:觸媒)混合,混合物緩慢地逐滴加至溫度維持於約60℃的反應器中並進一步反應,藉此製得式1之化合物(E)。持續反應直到IR光譜中的NCO峰完全消失。
藉此製得的化合物(E)具有約20,200的分子量(Mw)和約8.27mgKOH/g的羥值(OHv)。製得之化合物的IR光譜示於圖4。
實例1
使用具有甲基三丁基銨作為陽離子和三氟甲磺醯基醯亞胺作為陰離子之離子性化合物(辛醇-水分配係數:約5.65,陽離子-水結合能:0.45Kcal/mol)作為離子性化合物。此離子性化合物、製備例1的丙烯酸系壓敏性黏著樹脂、交聯劑、製備例2的化合物(A)和異氰酸酯化合物經混合以製得可交聯的組成物。以上描述中,使用環氧基交聯劑(T-743L,Nippon Soken Inc.製造)作為交聯劑,藉甲苯二異氰酸酯和三羥甲基丙烷之加成聚合反應製得的化合物(T-760B)作為異氰酸酯化合物。基於100重量份丙烯酸系壓敏性黏著樹脂溶液中之固體含量,混合0.0052重量份的交聯劑、約0.0793重量份的製備例2之化合物(A)、約4重量份的離子性化合物和約2重量份的異氰酸酯化合物。藉此製得之可交聯之組成物施用於經脫模處理的聚(伸乙基對酞酸酯)(PET,MRF-38,Mitsubishi Chemical Corporation製造)膜之經脫模處理的表面上並在適當條件下乾燥以形成壓敏性黏著層。藉此形成的壓敏性黏著層積層於以碘為基礎並具有以三乙醯基纖維素(TAC)為基礎的保護膜接合於其兩表面上的偏光板的一個表面上,藉此製得壓敏黏著性偏光板。此壓敏黏著性偏光板具有壓敏性黏著層和脫模層連續形成於偏光板的一表面上的TAC膜上之結構(TAC膜/以碘為基礎的偏光板/TAC膜)。
實例2
以與實例1相同的方式製得可交聯之組成
物、壓敏性黏著層和壓敏黏著性偏光板,但使用製備例3的化合物(B)代替製備例2的化合物(A)。
實例3
以與實例1相同的方式製得可交聯之組成物、壓敏性黏著層和壓敏黏著性偏光板,但使用製備例4的化合物(D)代替製備例2的化合物(A)。
實例4
以與實例1相同的方式製得可交聯之組成物、壓敏性黏著層和壓敏黏著性偏光板,但使用製備例5的化合物(E)代替製備例2的化合物(A)。
比較例1
以與實例1相同的方式製得可交聯之組成物、壓敏性黏著層和壓敏黏著性偏光板,但未使用製備例2的化合物(A)。
實例和比較例的結果彙整於以下的表1。
Claims (10)
- 一種下式1之化合物,其中A是包含聚環氧烷單元的核心,B是藉以下式2表示的鏈,m是1或更大的整數,n是0或更大的整數,且m和n的和(m+n)是3或更大,及該核心(A)包括聚環氧乙烷單元和聚環氧丙烷單元:其中A1至A3各自獨立地代表伸烷基,Q1和Q2代表脂族或芳族二價殘基,L1至L4代表連接基,x是1或更大的整數,y是0或更大的整數,和z是1或更大的整數。
- 如申請專利範圍第1項之化合物,其中該式1之聚環氧烷單元藉以下式3表示:其中L是具2至12個碳原子的直鏈或支鏈伸烷基。
- 如申請專利範圍第1項之化合物,其中該核心具有在1,000至10,000範圍內的重量平均分子量。
- 如申請專利範圍第1項之化合物,其中該核心中之該聚環氧丙烷單元的莫耳數(P)對該聚環氧乙烷單元的莫耳數(E)之比(P/E)在1至10的範圍內。
- 如申請專利範圍第1項之化合物,其中該式2之連接基是氧原子、硫原子、伸烷基、伸烯基或伸炔基,或是藉以下式4或5表示: 其中R1和R2各自獨立地代表氫原子或烷基。
- 如申請專利範圍第1項之化合物,其中式1之B藉以下式6表示:其中A1至A3各自獨立地代表伸烷基,Q1和Q2代表脂族或芳族二價殘基,x是1或更大的整數,y是0或更大的整數,和z是1或更大的整數。
- 如申請專利範圍第1項之化合物,其中羥值是4mgKOH/g或更高。
- 如申請專利範圍第1項之化合物,其中重量平均分子量是10,000或更高。
- 一種用於影像顯示裝置之壓敏黏著性光學組件,包括壓敏性黏著層,該層含有形成於用於影像顯示裝置之該壓敏黏著性光學組件的一或兩表面上之壓敏性黏著劑組成物,其中該壓敏性黏著劑組成物包括離子性液體和作為基礎聚合物之具有玻璃轉變溫度為0℃或更低的聚合物,該具有玻璃轉變溫度為0℃或更低的聚合物是丙烯酸系聚合物(該丙烯酸系聚合物具有50至100重量%之包括一或多種具有具1至14個碳原子的烷基的(甲基)丙烯酸酯之單體作為主要組份),並具有29或更低的酸值,且該壓敏性黏著劑組成物另包括下式1之化合物:其中A是包括聚環氧烷單元的核心,B是藉以下式2表示的鏈,m是1或更大的整數,n是0或更大的整數,而m和n的和(m+n)是3或更大:其中A1至A3各自獨立地代表伸烷基,Q1和Q2代表脂族或芳族二價殘基,L1至L4代表連接基,x是1或更大的整數,y是0或更大的整數,和z是1或更大的整數。
- 一種影像顯示裝置,包含如申請專利範圍第9項之壓敏黏著性光學組件。
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| KR20230054705A (ko) * | 2020-09-02 | 2023-04-25 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | 화상 표시 장치용 적층체 및 화상 표시 장치 |
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