TWI477571B - 粘結劑組合物及使用該粘結劑組合物的保護膜 - Google Patents

粘結劑組合物及使用該粘結劑組合物的保護膜 Download PDF

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TWI477571B
TWI477571B TW102121180A TW102121180A TWI477571B TW I477571 B TWI477571 B TW I477571B TW 102121180 A TW102121180 A TW 102121180A TW 102121180 A TW102121180 A TW 102121180A TW I477571 B TWI477571 B TW I477571B
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styrene
binder composition
ultraviolet
rubber
polymer film
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TW201400571A (zh
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Ae-Jung Jang
Jang-Soon Kim
Sle Lee
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Lg Hausys Ltd
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Description

粘結劑組合物及使用該粘結劑組合物的保護膜
本發明涉及一種保護膜用粘結劑組合物,更具體地涉及一種包含紫外線(UV)固化型橡膠的粘結劑組合物及使用該粘結劑組合物的保護膜
包括作為平板顯示裝置(FPD,flat panel display)的一種的偏光膜(polarizer film)或手機的防護窗等的各種顯示裝置的表面,為了保護其表面,始終在附著有保護膜的狀態下,在工作臺等上面進行作業。此時,無論保護膜具有何種層結構,與粘附物面對面的層為粘結劑層,該粘結劑層的性能就是決定著與粘附物的粘結力或粘結劑轉移現象等的非常重要的構成要素。
此時,當去除保護膜時,存在並不是粘結層的一部分均勻地粘結於物件產品表面,而是只有一部分粘結層附著於粘附劑的問題;與此相反,當剝離粘結層時,存在著在粘附劑中殘留污染物或殘渣等而產生殘餘物的問題。
根據以往技術,為了最大限度地賦予粘結劑組合物或粘結劑層的順利剝離及粘結所需的濕潤性(Wetting),利用了矽(Si)高分子,但由於它的價格高,存在無法廣泛使用的問題,在為了還賦予濕潤性(Wetting)而利用矽油(Silicon Oil)的情況下,由於矽油被轉印,導致表面受到污染,因而存在降低適用粘結劑組合物的觸控板的觸摸靈敏度的問題。
並且,在韓國授權專利第10-0826420號中,雖然記載了關於包含橡膠、苯酚類樹脂、硫化劑、填料及有機溶劑等的半導體組裝用粘合膜組合物,但僅僅提到了通過保持粘合性而確保產品的可靠性的粘合膜,仍然存在著確保濕潤性(Wetting)及剝離粘合膜後產生殘渣的問題。
為了解決上述問題,本發明的目的在於,通過確保用作保護膜的粘結劑組合物保持規定水準以上的濕潤性(Wetting),使得在高溫、高濕環境下也能保持規定的粘結力,並在進行剝離後防止產生殘渣。
為了達到上述一目的,本發明的保護膜用粘結劑組合物,其特徵在於,由不飽和度為70%~85%的紫外線(UV)固化型橡膠構成。
並且,為了達到上述再一目的,本發明的保護膜,其特徵在於,包含上述保護膜用粘結劑組合物而形成。
本發明的保護膜用粘結劑組合物通過包含不飽和度被限定的紫外線(UV)固化型橡膠,從而能夠確保規定水準以上的濕潤性(Wetting)。然後,通過在高溫、高濕環境下保持粘結力,能夠顯著減少剝離後在上述保護膜用粘結劑組合物的粘附劑上的殘渣。
並且,通過使用包含在粘結及剝離方面均優異的上述保護膜用 粘結劑組合物的保護膜,從而能在大幅減少工序上的損失方面是有效的。
參照以下詳細說明的實施例,就能夠明確本發明的優點和/或特徵及其實現方法。但是,本發明不局限於以下所公開的實施例,能夠以互不相同的各種方式實施,本實施例只用於使本發明的公開內容更加完整,並向本發明所屬技術領域的普通技術人員準確告知發明的範疇,本發明根據申請專利範圍的範疇而定義。在說明書全文中,相同的附圖標記表示相同的結構部件。
保護膜用粘結劑組合物
本發明提供一種保護膜用粘結劑組合物,其特徵在於,由不飽和度為70%~85%的紫外線(UV)固化型橡膠構成。
通過限定上述紫外線(UV)固化型橡膠所包含的雙鍵的含量,能夠提高固化度,通過包含規定水準以上的雙鍵,能夠確保粘結劑組合物的濕潤性(Wetting)。此時,以不飽和度表示上述紫外線(UV)固化型橡膠的雙鍵含量,上述不飽和度是將上述紫外線(UV)固化型橡膠的整體組合中的雙鍵的含量以%表示的。在本發明中,以不飽和度為70%~85%為特徵,更具體地,在上述紫外線(UV)固化型橡膠的不飽和度小於70%的情況下,存在著在高溫下將導致耐久性下降的憂慮,而在大於85%的情況下,存在隨著雙鍵的固化度的增加,粘結劑的硬度提高並粘結力下降的問題。
根據以往技術,為了向粘結劑組合物賦予濕潤性(Wetting), 使用矽類粘結劑組合物或者使用矽油並通過熱固化方式進行應用,而與此相反,本發明表示橡膠類粘結劑組合物,通過限定表示雙鍵的含量的不飽和度,由此克服了橡膠的固化度低的缺點,在高溫、高濕環境下也能夠確保粘結劑組合物的濕潤性(Wetting),因而保持了良好的粘結力,並剝離時也不會產生殘渣。
並且,為與一同包含矽油等各種添加劑的以往的粘結劑組合物相反,本發明的保護膜用粘結劑組合物為了賦予昂貴的矽類樹脂或濕潤性(Wetting),在限定紫外線(UV)固化型橡膠的不飽和度的情況下,不經過單獨的熟成及處理步驟等,並不包含額外的添加劑。
上述紫外線(UV)固化型橡膠,其類型並不受到限制,但能夠包含選自包括異戊二烯橡膠(isoprene rubber)、苯乙烯橡膠(Styrene rubber)、聚丁二烯橡膠(polybutadiene rubber)、丁腈橡膠(acrylonitrile-butadiene rubber)、丁基橡膠(butyl rubber)、氯丁橡膠(polychloroprene rubber)、聚氨酯橡膠(urethane rubber)及丙烯酸酯橡膠(acrylic rubber)的組中的一種以上。
由於上述紫外線(UV)固化型橡膠形成有雙鍵的環,優選地使用硬度高的苯乙烯橡膠(Styrene rubber),上述苯乙烯橡膠(Styrene rubber)可以是選自包含苯乙烯-異戊二烯-苯乙烯(styrene-isoprene-styrene)嵌段共聚物、苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene)嵌段共聚物、苯乙烯-丁烯-苯乙烯(styrene-butylene-styrene)嵌段共聚物、苯乙烯-丙烯-苯乙烯(styrene-propylene-styrene)嵌段共聚物、丙烯腈-丁烯-苯乙烯(acrylonitrile-butylene-styrene)共聚物及它們的羧酸(carboxylic acid)衍生物的組中的一種以上。
更具體地,上述苯乙烯橡膠(Styrene rubber)中可包含含量小 於15%~30%的苯乙烯(styrene)。當苯乙烯(styrene)的含量超過30%時,存在因硬度高而導致粘結力下降的問題,優選地,粘結劑的耐久性方面,苯乙烯(styrene)的含量為15%以上。
本發明的保護膜用粘結劑組合物,其特徵在於,其主要成分是限定不飽和度的紫外線(UV)固化型橡膠,並上述紫外線(UV)固化型橡膠的重均分子量為30000~60000。當紫外線(UV)固化型橡膠的重均分子量小於30000時,存在紫外線(UV)固化時,耐久性降低的問題;當紫外線(UV)固化型橡膠的重均分子量大於60000時,存在因高分子的長度大而導致固化度增加,從而剝離強度下降的憂慮。
本發明的特徵在於,上述紫外線(UV)固化型橡膠的玻璃轉移溫度(Tg)為-60℃~-40℃。本發明的粘結劑組合物包含橡膠,相比於現有的丙烯(acryl)類樹脂,玻璃轉移溫度(Tg)的測定值低(與以往的丙烯(acryl)類樹脂相比,測定出低璃化轉變溫度(Tg)),由於低玻璃轉移溫度(Tg),從而對於耐熱性及耐寒性表現更良好的物理性質。更具體地,當上述紫外線(UV)固化型橡膠的玻璃轉移溫度小於-60℃時,很難確保耐久性;當上述紫外線(UV)固化型橡膠的玻璃轉移溫度大於-40℃時,低溫特性方面將存在問題。
並且,上述紫外線(UV)固化型橡膠的表面能源可以為30mN/m-40mN/m。表面能源作為影響濕潤性(Wetting)的最大的因素,並紫外線(UV)固化型橡膠保持保持低表面能源,從而對於大部分基材或粘附劑的濕潤性(Wetting)良好。更具體地,當上述紫外線(UV)固化型橡膠的表面能源可小於30mN/m時,存在對於表面能源相對低的基材或粘附劑的剝離強度低的憂慮;當上述紫外線(UV)固化型橡膠的表面能源大於40mN/m時,有可能對表面能源相對高的基材或粘附劑的物性存在問題。
本發明的粘結劑組合物通過還包含光聚合引發劑,能夠根據非常短時間的紫外線(UV)等活性能量射線的照射,固化保護膜用粘結劑組合物,調節粘結劑組合物的重均分子量。在使用熱聚合引發劑的情況下,是通過加熱對粘結劑組合物進行固化,其固化速度慢,很難調節粘結劑組合物的分子量,根據需要,能夠並用光固化或熱固化。
上述光聚合引發劑不受特殊限制,例如可以是二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯甲基丙酮、4-(2-羥乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基苯基甲酮、2-甲基-2-嗎啉代(4-甲硫基苯)丙烷-1-酮、2-苯甲醯基-2-二甲氨基-1-(4-嗎啉代苯基)丁酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯)苯基]丙酮低聚物等的苯乙酮類;苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻異丁基醚等的苯偶姻類;二苯甲酮、o-苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲酯-二苯硫醚、3,3',4,4'-四(叔丁過氧化碳酸基)二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯甲醯基-N,N-二甲基-N-[2-(1-氧-2-丙烯基氧)乙基]苯甲烷溴化銨(4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzene methane Aminium bromide)、(4-苯甲醯基苄基)三甲基氯化銨等的二苯甲酮類;2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯代-4-丙氧基噻噸酮、2-(3-二甲氨基-2-羥基)-3,4-二甲基-9H-噻噸酮-9-1-中-氯化物等的噻噸酮類;2,4,6-三甲酯苯甲醯基-二苯基氧化膦、二(2,6-二甲氧基苯甲醯)-2,4,4-三甲基-戊基氧化膦、二(2,4,6-三甲基苯)-苯基氧化膦等的醯基磷氧化物類等。並且,在這些光聚合引發劑中,能夠獨立使用其中的一種,也能夠並用其中的一種以上。
並且,作為它們的調劑,能夠並用三乙醇胺、三異丙醇胺、4,4'-二甲氨基二苯酮(米蚩酮)、4,4'-二乙氨基二苯酮、2-二甲氨基苯甲酸乙 酯、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸(n-丁氧基)乙酯、4-二甲氨基苯甲酸異戊酯、4-二甲氨基苯酸2-乙基己基、2,4-二乙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮等。
其中,優選地,使用苄基甲基酮、1-羥基環己基苯基酮、苯偶姻異丙醚、4-(2-羥乙氧基)苯基-(2-羥基-2-丙基)酮、2-羥基-2-甲基-1-苯基丙烷-1-1。
關於上述光聚合引發劑的含量,本發明的粘結劑組合物,相對於100重量份的紫外線(UV)固化型橡膠,還可包含0.1重量份~1重量份的光聚合引發劑。當上述光聚合引發劑不足0.1重量份時,固化度低,固化後粘結劑組合物的耐久性將出現問題;當超過1重量份時,硬度高,固化後將存在粘結劑組合物的剝離強度低的憂慮。
保護膜 實施例1
添加由苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene)嵌段共聚物構成的不飽和度為82%的苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene,SBS)樹脂、相對於上述苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene,SBS)樹脂100重量份為0.5重量份的作為光聚合引發劑的豔佳固(Irgacure)651、1重量份的作為固化劑的己二醇二丙烯酸(HDDA),對溶劑甲苯進行乾燥後進行紫外線(UV)固化,來製備出粘結劑組合物。
實施例2
添加由苯乙烯-異戊二烯-苯乙烯(styrene-isoprene-styrene)嵌段共聚物構成的不飽和度為76%的苯乙烯-異戊二烯-苯乙烯(styrene-isoprene-styrene,SIS)樹脂、相對於上述苯乙烯-異戊二烯-苯乙 烯(styrene-isoprene-styrene,SIS)樹脂100重量份為0.5重量份的作為光聚合引發劑的豔佳固(Irgacure)651、1重量份的作為固化劑的己二醇二丙烯酸(HDDA),對溶劑甲苯進行乾燥後進行紫外線(UV)固化,來製備出粘結劑組合物。
比較例1
相對於矽類粘結劑組合物100重量份,混合乙烯基矽氧烷(vinyl siloxane)類矽聚合物(道康寧公司)60重量份、聚二甲基矽氧烷(PDMS,polydimethylsiloxane)類矽粘結劑(道康寧公司)40重量份、氫聚矽氧烷(Hydrogen polysiloxane)類樹脂(道康寧公司)7重量份、鉑催化劑1重量份,並賦予熱風進行乾燥,製備出矽類粘結劑組合物。
比較例2
除了相對於上述比較例1的矽類粘結劑組合物100重量份添加5重量份的矽油之外,如同上述比較例1,形成了矽類粘結劑組合物。
比較例3
除了上述實施例1中的苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene,SBS)樹脂的不飽和度為90%的之外,如同上述實施例1,形成了保護膜用粘結劑組合物。
比較例4
除了上述實施例2的苯乙烯-異戊二烯-苯乙烯(styrene-isoprene-styrene,SIS)樹脂的不飽和度為60%的之外,如同上述實施例1,形成了保護膜用粘結劑組合物。
實驗例--保護膜的物理特性
由上述實施例及比較例的保護膜用粘結劑組合物形成粘結劑層,將粘結劑層的厚度以20μm進行乾燥後,塗敷在無處理聚對苯二甲酸乙二醇酯膜(PET)上並形成了保護膜,以下實驗的測定結果由以下表2表示。
1)測定聚對苯二甲酸乙二醇酯膜(PET)剝離時是否發生殘渣:將上述保護膜附著於玻璃面,在80℃的高溫烤箱中放置1天后剝離聚對苯二甲酸乙二醇酯膜(PET),此時,觀察在粘結劑層是否發生殘渣。
2)濕潤速度:將上述保護膜沿著橫向X豎向(10cmX2.5cm)切割並放在玻璃上,用手按上3個點後,觀察整體保護膜附著的時間。
參考上述表2,不包含紫外線(UV)固化型橡膠的比較例1,在剝離後未發生殘渣,但濕潤(Wetting)速度為6秒鐘,相比於實施例1及實施例2,速度表現慢。並且,在比較例3的情況下,濕潤(Wetting)速度減小到2秒鐘,但發生了殘渣,仍然無法克服以往的粘結劑組合物所存在的問題。
並且,在比較例3及比較例4的情況下,雖然包含含有苯乙烯橡膠(Styrene rubber)的紫外線(UV)固化型橡膠,但不飽和度的含量超過本發明的範圍。在這種情況下,剝離時發生殘渣,並且濕潤(Wetting)速度也慢,即便是包含紫外線(UV)固化型橡膠的粘結劑組合物,不飽和度的含量未被限定的情況下,很難達到本發明的目的。

Claims (8)

  1. 一種粘結劑組合物,其特徵在於,由不飽和度為70%~85%的紫外線(UV)固化型橡膠構成,其中該紫外線固化型橡膠係為苯乙烯橡膠,該苯乙烯橡膠中的苯乙烯含量為15%~30%。
  2. 根據申請專利範圍第1項所述的粘結劑組合物,其中,該苯乙烯橡膠(styrene rubber)是選自包含苯乙烯-異戊二烯-苯乙烯(styrene-isoprene-styrene)嵌段共聚物、苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene)嵌段共聚物、苯乙烯-丁烯-苯乙烯嵌段共聚物(styrene-butylene-styrene)、苯乙烯-丙烯-苯乙烯(styrene-propylene-styrene)嵌段共聚物、丙烯腈-丁烯-苯乙烯(acrylonitrile-butylene-styrene)共聚物及它們的羧酸(carboxylic acid)衍生物(derivative)的組中的一種以上。
  3. 根據申請專利範圍第1項所述的粘結劑組合物,其中,該紫外線(UV)固化型橡膠的重均分子量為30000~60000。
  4. 根據申請專利範圍第1項所述的粘結劑組合物,其中,該紫外線(UV)固化型橡膠的玻璃轉移溫度為-60℃~-40℃。
  5. 根據申請專利範圍第1項所述的粘結劑組合物,其中,該紫外線(UV)固化型橡膠的表面能量為30mN/m~40mN/m。
  6. 根據申請專利範圍第1項所述的粘結劑組合物,其中,相對於100重量份的該紫外線(UV)固化型橡膠,還包含0.1重量份~1重量份的光聚合引發劑。
  7. 一種保護膜,其特徵在於,由申請專利範圍第1項至第6項中的任一項所述的粘結劑組合物形成。
  8. 根據申請專利範圍第7項所述的保護膜,其中,該粘結劑組合物被塗敷的基材是選自包括包含聚對苯二甲酸乙二醇酯(polyethylene terephthalate)的酯(ester)類高分子膜、包含聚苯乙烯(polystyrene)的苯乙烯(styrene)類高分子膜、包含環烯烴(cyclic olefin)高分子的烯烴(olefin)類高分子膜、包含聚碳酸酯(polycarbonate)的碳酸酯(carbonate)類高分子膜、包含聚醯亞胺(polyimide)的醯亞胺(imide)類高分子膜、包含聚醚碸(polyether sulphone)的碸(sulphone)類高分子膜、包含三乙醯纖維素(triacetyl cellulose)的纖維素(cellulose)類高分子膜或包含聚甲基丙烯酸甲酯(poly(methyl methacrylate))的丙烯(acryl)類高分子膜的組中的一種以上。
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TW201400571A (zh) 2014-01-01
CN104411793B (zh) 2017-12-22
US20150166855A1 (en) 2015-06-18
KR20130143304A (ko) 2013-12-31
WO2013191340A1 (ko) 2013-12-27
CN104411793A (zh) 2015-03-11
JP2015523437A (ja) 2015-08-13

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