TW201819577A - Optically clear adhesive composition, and optically clear adhesive film comprising the same, and flat panel display - Google Patents
Optically clear adhesive composition, and optically clear adhesive film comprising the same, and flat panel display Download PDFInfo
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C09J2301/00—Additional features of adhesives in the form of films or foils
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Abstract
Description
本發明係關於光學透明黏著劑組成物、包括該組成物之光學透明黏著性膜、及平板顯示器。 The present invention relates to an optically clear adhesive composition, an optically transparent adhesive film comprising the composition, and a flat panel display.
平板顯示器的實例包含液晶顯示器(LCD)、電漿顯示器(PDP),有機電場發光顯示器(OLED)等。 Examples of the flat panel display include a liquid crystal display (LCD), a plasma display (PDP), an organic electric field light emitting display (OLED), and the like.
這種平板顯示器包含顯示面板和光學膜。光學膜的實例包含偏振膜、相位差膜、防眩光膜、光學視角補償膜、增亮膜等。當光學膜彼此堆疊或光學膜附接到顯示面板時,使用光學透明黏著劑(OCA)。於是,光學透明黏著劑(OCA)不僅必須表現出典型的光學性能,還要具有優異的抗濕熱性,抗熱性和黏著性。 This flat panel display includes a display panel and an optical film. Examples of the optical film include a polarizing film, a retardation film, an anti-glare film, an optical viewing angle compensation film, a brightness enhancement film, and the like. An optically clear adhesive (OCA) is used when the optical films are stacked on each other or the optical film is attached to the display panel. Thus, optically clear adhesives (OCAs) must not only exhibit typical optical properties, but also have excellent resistance to moist heat, heat and adhesion.
尤其是近來開發可撓性顯示器的激烈競爭正在進行。由於可撓性顯示器係可彎曲的、可捲曲的或可折疊的,顯示面板和含在裝置中的光學膜會受到彎曲應 力。因此,需要進一步改善用於可撓性顯示器的光學透明黏著劑(OCA)的各種性質。 In particular, the recent fierce competition for developing flexible displays is underway. Since the flexible display is bendable, crimpable or foldable, the display panel and the optical film contained in the device are subject to bending stress. Therefore, there is a need to further improve various properties of optically clear adhesives (OCAs) for flexible displays.
例如,用於可撓性顯示器的光學透明黏著劑(OCA)必須具有非常可折疊性的性質,以使得該裝置能夠自由折疊。此外,考慮到可撓性顯示器在戶外低溫下長時間使用的情況,低溫下的折疊性應當優越。 For example, optically clear adhesives (OCAs) for flexible displays must have very foldable properties to enable the device to be freely folded. Further, in consideration of the case where the flexible display is used for a long period of time at an outdoor low temperature, the folding property at a low temperature should be superior.
而且,用於可撓性顯示器的光學透明黏著劑(OCA)必須具有進一步增強的抗濕熱性。這是因為可撓性顯示器在其使用過程中反覆受到大量的折疊和展開過程,因此濕氣穿過折疊和展開部分的可能性可能增加。 Moreover, optically clear adhesives (OCAs) for flexible displays must have further enhanced resistance to moist heat. This is because the flexible display is repeatedly subjected to a large number of folding and unfolding processes during its use, so the possibility of moisture passing through the folded and unfolded portions may increase.
而且,當可撓性顯示器彎曲、捲曲或折疊時,裝置中含有的顯示面板和光學膜受到彎曲應力。因此,由於容易將堆疊的顯示面板和光學膜彼此分離,需要更高的黏著性和更高的耐久性。 Moreover, when the flexible display is bent, curled, or folded, the display panel and the optical film contained in the device are subjected to bending stress. Therefore, since it is easy to separate the stacked display panel and the optical film from each other, higher adhesion and higher durability are required.
然而,迄今習知的光學透明黏著劑(OCA)不能充分提供可撓性顯示器所需的上述性能。 However, conventional optically clear adhesives (OCAs) have hitherto not adequately provide the above-described properties required for flexible displays.
(專利文件1)韓國申請專利公開第10-2016-0085759號 (Patent Document 1) Korean Patent Application No. 10-2016-0085759
於是,考慮到先前技術中遇到的問題,本發明旨在提供一種光學透明黏著劑(OCA)組成物,其能夠充分滿足可撓性顯示器所要求的可折疊性、抗濕熱性、抗 熱性、及黏著性。 Accordingly, in view of the problems encountered in the prior art, the present invention is directed to an optical transparent adhesive (OCA) composition capable of sufficiently satisfying the foldability, moist heat resistance, heat resistance, and the like required for a flexible display. And adhesion.
另外,本發明旨在提供包含光學透明黏著劑(OCA)組成物的光學透明黏著性膜及平板顯示器。 Additionally, the present invention is directed to an optically clear adhesive film and flat panel display comprising an optically clear adhesive (OCA) composition.
因此,本發明提供一種光學透明黏著劑組成物,包括可光固化之(甲基)丙烯酸酯共聚物、丙烯酸酯共聚物、及光聚合起始劑,其中,該可光固化之(甲基)丙烯酸酯共聚物以該共聚物之組成分的總重量為基準計,包含95至99.9wt%的含羥基團之丙烯酸類共聚物和0.1至5wt%的含異氰酸酯基團之(甲基)丙烯酸酯單體,該含羥基團之丙烯酸類共聚物和該含異氰酸酯基團之(甲基)丙烯酸酯單體形成胺基甲酸酯鍵,該含羥基團之丙烯酸類共聚物以共聚物單體的總重量為基準計,具有80至98wt%的玻璃轉化溫度(glass transition temperature)為-70至-50℃的C4-C12直鏈或支鏈之丙烯酸烷基酯單體和2至20wt%的羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體,且該可光固化之(甲基)丙烯酸酯共聚物的重均分子量為500,000至2,000,000;以及,該丙烯酸酯共聚物以該共聚物的單體總重量為基準計,包含80至95wt%的C4-C12直鏈或支鏈之丙烯酸烷基酯單體和5至20wt%的含促黏劑(adhesion-promoter)的可聚合單體,不含光交聯性官能基團,且重均分子量為10,000至100,000,該可光固化之(甲基)丙烯酸酯共聚物及該丙烯酸酯共聚物係以95:5至70:30的重量比範圍包含在內。 Accordingly, the present invention provides an optically clear adhesive composition comprising a photocurable (meth) acrylate copolymer, an acrylate copolymer, and a photopolymerization initiator, wherein the photocurable (methyl) The acrylate copolymer comprises 95 to 99.9% by weight of the hydroxyl group-containing acrylic copolymer and 0.1 to 5% by weight of the isocyanate group-containing (meth) acrylate, based on the total weight of the copolymer component. a monomer, the hydroxyl group-containing acrylic copolymer and the isocyanate group-containing (meth) acrylate monomer form a urethane bond, and the hydroxyl group-containing acrylic copolymer is a copolymer monomer The C 4 -C 12 linear or branched alkyl acrylate monomer having a glass transition temperature of from -70 to -50 ° C and from 2 to 20 wt%, based on the total weight, is from 80 to 98 wt% a hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer, and the photocurable (meth) acrylate copolymer has a weight average molecular weight of 500,000 to 2,000,000; and, the acrylate copolymer Containing 80% based on the total weight of the monomer of the copolymer 95wt% of C 4 -C 12 alkyl acrylate monomer straight or branched chains and containing 5 to 20wt% of the adhesion promoting agent (adhesion-promoter) of the polymerizable monomer containing a photo-crosslinkable functional group And the weight average molecular weight is 10,000 to 100,000, and the photocurable (meth) acrylate copolymer and the acrylate copolymer are included in a weight ratio range of 95:5 to 70:30.
另外,本發明提供了一種光學透明黏著性 膜,該光學透明黏著性膜透過用本發明所述之光學透明黏著劑組成物塗佈轉移膜而形成。 Further, the present invention provides an optically transparent adhesive film formed by coating a transfer film with the optically clear adhesive composition of the present invention.
另外,本發明提供了一種平板顯示器,該平板顯示器包括由本發明所述之光學透明黏著劑組成物形成的黏著劑層。 Additionally, the present invention provides a flat panel display comprising an adhesive layer formed from the optically clear adhesive composition of the present invention.
根據本發明,光學透明黏著劑(OCA)組成物和光學透明黏著性膜能展現平板顯示器和可撓性顯示器所需之足夠的可折疊性,抗濕熱性,抗熱性和黏著性,因此能夠賦予優異的耐久性。 According to the present invention, an optically clear adhesive (OCA) composition and an optically transparent adhesive film can exhibit sufficient foldability, moist heat resistance, heat resistance and adhesion required for a flat panel display and a flexible display, and thus can be imparted Excellent durability.
根據本發明,使用上述黏著劑組成物製造的平板顯示器,因此顯示出優異的可折疊性,抗濕熱性,抗熱性,黏著性、及耐久性。 According to the present invention, a flat panel display manufactured using the above adhesive composition exhibits excellent foldability, moist heat resistance, heat resistance, adhesion, and durability.
本發明涉及一種光學透明黏著劑組成物,包括可光固化之(甲基)丙烯酸酯共聚物、丙烯酸酯共聚物、及光聚合起始劑。 The present invention relates to an optically clear adhesive composition comprising a photocurable (meth) acrylate copolymer, an acrylate copolymer, and a photopolymerization initiator.
在此,可光固化之(甲基)丙烯酸酯共聚物以該共聚物之組成分的總重量為基準計,包含95至99.9wt%的含羥基團之丙烯酸類共聚物和0.1至5wt%的含異氰酸酯基團之(甲基)丙烯酸酯單體,該含羥基團之丙烯酸類共聚物和該含異氰酸酯基團之(甲基)丙烯酸酯單體形成胺基甲酸酯鍵,該含羥基團之丙烯酸類共聚物以共聚物單體的總 重量為基準計,具有80至98wt%的玻璃轉化溫度(glass transition temperature)為-70至-50℃的C4-C12直鏈或支鏈之丙烯酸烷基酯單體和2至20wt%的羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體,且該可光固化之(甲基)丙烯酸酯共聚物的重均分子量為500,000至2,000,000。再者,丙烯酸酯共聚物以該共聚物的單體總重量為基準計,包含80至95wt%的C4-C12直鏈或支鏈之丙烯酸烷基酯單體和5至20wt%的含促黏劑的可聚合單體,不含光交聯性官能基團,且重均分子量為10,000至100,000。而且,該可光固化之(甲基)丙烯酸酯共聚物及該丙烯酸酯共聚物係以95:5至70:30的重量比範圍包含在內。 Here, the photocurable (meth) acrylate copolymer comprises 95 to 99.9% by weight of the hydroxyl group-containing acrylic copolymer and 0.1 to 5% by weight based on the total weight of the copolymer component. a (meth) acrylate monomer containing an isocyanate group, the hydroxyl group-containing acrylic copolymer and the isocyanate group-containing (meth) acrylate monomer forming a urethane bond, the hydroxyl group-containing group The acrylic copolymer has a C 4 -C 12 linear or branched chain having a glass transition temperature of -70 to -50 ° C of 80 to 98 wt% based on the total weight of the copolymer monomers. An alkyl acrylate monomer and 2 to 20% by weight of a hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer, and the weight average molecular weight of the photocurable (meth) acrylate copolymer It is 500,000 to 2,000,000. Further, the acrylate copolymer comprises 80 to 95% by weight, based on the total weight of the monomers of the copolymer, of C 4 -C 12 linear or branched alkyl acrylate monomer and 5 to 20% by weight. The polymerizable monomer of the adhesion promoter, which does not contain a photocrosslinkable functional group, and has a weight average molecular weight of 10,000 to 100,000. Moreover, the photocurable (meth) acrylate copolymer and the acrylate copolymer are included in a weight ratio range of 95:5 to 70:30.
在本發明的光學透明黏著劑組成物中,可光固化之(甲基)丙烯酸酯共聚物具有玻璃轉化溫度為-70至-50℃的C4-C12直鏈或支鏈之丙烯酸烷基酯單體,因此表現出優異的可折疊性,由於與透過胺基甲酸酯鍵連接的丙烯醯基官能基團的自由基交聯,所以具有高分子量和高交聯密度,因此可以表現出高抗熱性和耐久性。再者,包含大量羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體,因此獲得高抗濕熱性和黏著性。 In the optically clear adhesive composition of the present invention, the photocurable (meth) acrylate copolymer has a C 4 - C 12 linear or branched alkyl acrylate having a glass transition temperature of -70 to -50 ° C. The ester monomer, thus exhibiting excellent foldability, has high molecular weight and high crosslink density due to free radical crosslinking with the acryloyl functional group linked through the urethane bond, and thus can be expressed High heat resistance and durability. Further, a large amount of a hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer is contained, thereby obtaining high moist heat resistance and adhesion.
在本發明的光學透明黏著劑組成物中,該丙烯酸酯共聚物具有低分子量,並且不含光交聯性官能基團,因此即使在光交聯反應之後也不形成交聯,由此表現出優異的可折疊性。然而,在大量含有低分子量的丙烯酸酯共聚物的情況下,在形成黏著劑層之後,低分子量的丙 烯酸酯共聚物可能從界面滲出,從而使耐久性和黏著性變差。為了解決這些問題,大量包含高極性之含促黏劑的可聚合單體,由此提高抗濕熱性和黏著性。 In the optically clear adhesive composition of the present invention, the acrylate copolymer has a low molecular weight and does not contain a photocrosslinkable functional group, and thus does not form crosslink even after a photocrosslinking reaction, thereby exhibiting Excellent foldability. However, in the case where a large amount of the low molecular weight acrylate copolymer is contained, the low molecular weight acrylate copolymer may bleed out from the interface after the formation of the adhesive layer, thereby deteriorating durability and adhesion. In order to solve these problems, a large amount of a highly polar polymerizable monomer containing an adhesion promoter is contained, thereby improving moist heat resistance and adhesion.
如本文所述,術語「(甲基)丙烯酸酯」係指「丙烯酸酯」或「甲基丙烯酸酯」。 As used herein, the term "(meth)acrylate" means "acrylate" or "methacrylate."
可光固化之(甲基)丙烯酸酯共聚物可以透過共聚合80至98重量份的具有玻璃轉化溫度為-70至-50℃的C4-C12直鏈或支鏈之(甲基)丙烯酸烷基酯單體和2至20重量份的羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體,得到丙烯酸酯共聚物主鏈,使熱固性官能基團(羥基團)引入支鏈或末端,之後使該主鏈與含有異氰酸酯基的(甲基)丙烯酸酯單體,在適當的條件下用該含異氰酸酯基的(甲基)丙烯酸酯單體取代該主鏈的熱固化性官能基團(羥基團)的至少一部分。 The photocurable (meth) acrylate copolymer can be copolymerized by 80 to 98 parts by weight of a C 4 -C 12 linear or branched (meth)acrylic acid having a glass transition temperature of -70 to -50 ° C. An alkyl ester monomer and 2 to 20 parts by weight of a hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer to obtain an acrylate copolymer backbone to introduce a thermosetting functional group (hydroxyl group) Branching or terminating, then subjecting the main chain to a (meth) acrylate monomer containing an isocyanate group, and substituting the isocyanate group-containing (meth) acrylate monomer for thermal curing of the main chain under appropriate conditions At least a portion of a functional group (hydroxyl group).
主鏈可以透過典型的聚合方法製備,例如溶液聚合、光聚合、整體聚合、懸浮聚合、或乳液聚合。 The main chain can be prepared by a typical polymerization method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization, or emulsion polymerization.
以聚合形式包含在可光固化之(甲基)丙烯酸酯共聚物中的具有玻璃轉化溫度為-70至-50℃的C4-C12直鏈或支鏈之(甲基)丙烯酸烷基酯單體之實例可以包含丙烯酸正丁酯、丙烯酸第三丁酯、丙烯酸第二丁酯、丙烯酸戊酯、丙烯酸2-乙基丁酯、丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸異辛酯、及丙烯酸異壬酯,其可以單獨使用或者以兩種或更多種組合使用,且較佳係選自丙烯酸正丁酯和丙烯酸2-乙基己酯中的至少一種單體。 C 4 -C 12 linear or branched alkyl (meth)acrylate having a glass transition temperature of -70 to -50 ° C contained in a photopolymerizable (meth) acrylate copolymer in a polymerized form Examples of the monomer may include n-butyl acrylate, tert-butyl acrylate, second butyl acrylate, amyl acrylate, 2-ethyl butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, acrylic acid The octyl ester, and isodecyl acrylate, which may be used singly or in combination of two or more, is preferably at least one selected from the group consisting of n-butyl acrylate and 2-ethylhexyl acrylate.
如果C4-C12直鏈或支鏈之丙烯酸烷基酯單體的玻璃轉化溫度(Tg)低於-70℃,則其使用在經濟上係不可行的。另一方面,如果其玻璃轉化溫度超過-50℃,則低溫折疊性可能劣化。 If the glass transition temperature (Tg) of a C 4 -C 12 linear or branched alkyl acrylate monomer is lower than -70 ° C, its use is not economically feasible. On the other hand, if the glass transition temperature exceeds -50 ° C, the low-temperature folding property may be deteriorated.
以聚合形式包含在可光固化之(甲基)丙烯酸酯共聚物中的羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體之實例可以包含丙烯酸2-羥乙酯、丙烯酸3-羥丙酯、丙烯酸4-羥丁酯、丙烯酸5-羥基戊酯、及丙烯酸6-羥基己酯等,其可以單獨使用或者以兩種或更多種組合使用。以聚合形式包含在可光固化之(甲基)丙烯酸酯共聚物中的羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體較佳係選自丙烯酸2-羥乙酯和丙烯酸4-羥丁酯中的至少一種單體。 Examples of the hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer contained in the photocurable (meth) acrylate copolymer in a polymerized form may comprise 2-hydroxyethyl acrylate, acrylic acid. 3-hydroxypropyl ester, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate, etc., which may be used singly or in combination of two or more. The hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer contained in a polymerizable form in the photocurable (meth) acrylate copolymer is preferably selected from the group consisting of 2-hydroxyethyl acrylate and At least one monomer in 4-hydroxybutyl acrylate.
可光固化之(甲基)丙烯酸酯共聚物的結構可以由以下的化學式A表示。 The structure of the photocurable (meth) acrylate copolymer can be represented by the following chemical formula A.
在化學式A中,R1係C4-C12直鏈或支鏈烷基,R2係C1-C10直鏈或支鏈伸烷基,R3係氫或甲基,o係2至6的自然數,且l、m、n各自具有取決於上述單體的 數值範圍而決定的值。 In Chemical Formula A, R 1 is a C 4 -C 12 linear or branched alkyl group, R 2 is a C 1 -C 10 linear or branched alkylene group, R 3 is a hydrogen or a methyl group, and o is 2 to 2 A natural number of 6, and each of l, m, and n has a value determined depending on the numerical range of the above monomer.
含羥基的丙烯酸類共聚物較佳具有80至98wt%的玻璃轉化溫度(Tg)為-70至-50℃的C4-C12直鏈或支鏈之丙烯酸烷基酯單體和2至20wt%的羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體。如果羥基-C2-C6直鏈或支鏈之丙烯酸烷基酯單體的量小於2重量份,則黏著劑中作為親水性基團的羥基的量可能減少,因此黏著劑層可能不會捕捉水分,而是可能被排放到界面,在耐濕熱條件下不希望地使黏著性劣化,並且可能不希望地發生界面分層。另一方面,如果其量超過20重量份,則黏著劑可能會過量地吸收水分,因此黏著劑的體積可能增加,並且黏著性可能降低,不希望地引起界面分層和起泡。 The hydroxyl group-containing acrylic copolymer preferably has 80 to 98% by weight of a C 4 -C 12 linear or branched alkyl acrylate monomer having a glass transition temperature (Tg) of -70 to -50 ° C and 2 to 20 wt% % hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer. If the amount of the hydroxy-C 2 -C 6 linear or branched alkyl acrylate monomer is less than 2 parts by weight, the amount of the hydroxyl group as a hydrophilic group in the adhesive may be reduced, and thus the adhesive layer may not The moisture is captured, but may be discharged to the interface, undesirably deteriorating the adhesion under moist heat and humidity conditions, and interface delamination may undesirably occur. On the other hand, if the amount exceeds 20 parts by weight, the adhesive may excessively absorb moisture, so the volume of the adhesive may increase, and the adhesion may be lowered, undesirably causing interfacial delamination and foaming.
可光固化之(甲基)丙烯酸酯共聚物可以進一步包含本領域習知另外的可共聚單體並且係能夠聚合的形式。作為另外的可共聚單體的種類沒有特別限定,例如可以包含含氮單體如(甲基)丙烯腈、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、或N-丁氧基甲基(甲基)丙烯醯胺;苯乙烯類單體如苯乙烯或甲基苯乙烯;(甲基)丙烯酸縮水甘油酯;以及羧酸乙烯酯如乙酸乙烯酯。 The photocurable (meth) acrylate copolymer may further comprise additional copolymerizable monomers and are capable of being polymerized in the art. The kind of the other copolymerizable monomer is not particularly limited, and for example, may include a nitrogen-containing monomer such as (meth)acrylonitrile, (meth)acrylamide, N-methyl(meth)acrylamide, or N. - Butoxymethyl (meth) acrylamide; styrenic monomers such as styrene or methyl styrene; glycidyl (meth)acrylate; and vinyl carboxylates such as vinyl acetate.
當包含另外的可共聚單體時,考慮到可撓性和剝離強度,其量較佳調整至基於上述單體總計100重量份之基準計的20重量份或以下。 When another copolymerizable monomer is contained, the amount thereof is preferably adjusted to 20 parts by weight or less based on 100 parts by weight based on the total of the above monomers in consideration of flexibility and peel strength.
該可光固化之(甲基)丙烯酸酯共聚物的重均分子量係指使用聚苯乙烯標準品,經GPC(Gel Permeation Chromatography,凝膠滲透層析)測定的值。 The weight average molecular weight of the photocurable (meth) acrylate copolymer refers to a value measured by GPC (Gel Permeation Chromatography) using a polystyrene standard.
含異氰酸酯基團的(甲基)丙烯酸酯單體可以例舉如異氰酸酯基-C1-C10直鏈或支鏈之(甲基)丙烯酸烷基酯。在此,C1-C10直鏈或支鏈之烷基可以包括甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、己基、庚基、辛基、2-乙基己基、及癸基。上述中,較佳使用乙基或丙基。 The isocyanate group-containing (meth) acrylate monomer may, for example, be an isocyanate group-C 1 -C 10 linear or branched alkyl (meth) acrylate. Here, the C 1 -C 10 linear or branched alkyl group may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl. , hexyl, heptyl, octyl, 2-ethylhexyl, and fluorenyl. Among the above, ethyl or propyl is preferably used.
例如,含異氰酸酯基團的(甲基)丙烯酸酯單體可以係以下化學式B的化合物。 For example, the isocyanate group-containing (meth) acrylate monomer may be a compound of the following chemical formula B.
在化學式B中,R係氫或甲基,並且n係1至10的整數。 In Chemical Formula B, R is hydrogen or methyl, and n is an integer of 1 to 10.
含異氰酸酯基團的(甲基)丙烯酸酯單體可以為其中R係甲基且n係2的化學式B化合物,即甲基丙烯酸2-異氰酸基乙酯。 The isocyanate group-containing (meth) acrylate monomer may be a compound of the formula B wherein R is a methyl group and n is 2, that is, 2-isocyanatoethyl methacrylate.
基於可光固化之(甲基)丙烯酸酯共聚物成分的總重量,含異氰酸酯基團的(甲基)丙烯酸酯單體的用量可以為0.1至5.0wt%。如果該含異氰酸酯基團的(甲基)丙烯酸酯單體的量小於0.1wt%,則黏著劑組成物的內聚力和抗熱性可能降低。另一方面,如果其量超過5.0wt%,則黏著劑的內聚力可能變得過強,不希望地使折疊性惡化。 The isocyanate group-containing (meth) acrylate monomer may be used in an amount of from 0.1 to 5.0% by weight based on the total mass of the photocurable (meth) acrylate copolymer component. If the amount of the isocyanate group-containing (meth) acrylate monomer is less than 0.1% by weight, the cohesive force and heat resistance of the adhesive composition may be lowered. On the other hand, if the amount thereof exceeds 5.0% by weight, the cohesive force of the adhesive may become too strong, and the foldability is undesirably deteriorated.
含促黏劑的可聚合單體係含有極性基團或 反應性官能基團的可聚合單體。 The polymerizable monomer containing an adhesion promoter contains a polymerizable monomer having a polar group or a reactive functional group.
含促黏劑的可聚合單體係選自由以下化學式1的化合物、以下化學式2的化合物,以下化學式3的化合物、以下化學式4的化合物、以下化學式5的化合物、以下化學式6的化合物、以下化學式7的化合物、及以下化學式8的化合物所組成群組之至少一者:
在化學式7中,X係具有pKa小於-3之強酸的共軛鹼,並且X可以係選自由PF5、SbF6、甲磺酸鹽(OMs)、甲苯磺酸鹽(OTs)、三氟甲磺酸鹽(OTf)、雙(氟磺醯基)醯亞胺(FSI)、及雙(三氟甲基磺醯基)醯亞胺(TFSI)所組成群組之一者。 In Chemical Formula 7, X is a conjugate base having a strong acid having a pKa of less than -3, and X may be selected from PF5, SbF6, methanesulfonate (OMs), tosylate (OTs), trifluoromethanesulfonic acid. One of a group consisting of salt (OTf), bis(fluorosulfonyl) quinone imine (FSI), and bis(trifluoromethylsulfonyl) quinone imine (TFSI).
以聚合形式包含在丙烯酸酯共聚物中的C4-C12直鏈或支鏈之(甲基)丙烯酸烷基酯單體之實例可以包括丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基丁酯、丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、及(甲基)丙烯酸異壬酯等,其可以單獨使用或者以兩種或更多種組合使用,且較佳係選自丙烯酸正丁酯和丙烯酸2-乙基己酯中的至少一種單體。 Examples of the C 4 -C 12 linear or branched alkyl (meth) acrylate monomer contained in the acrylate copolymer in a polymerized form may include n-butyl acrylate and tert-butyl (meth) acrylate. , (butyl) (meth) acrylate, amyl (meth) acrylate, 2-ethyl butyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, (A) Isooctyl acrylate, isodecyl (meth) acrylate or the like, which may be used singly or in combination of two or more, and is preferably selected from n-butyl acrylate and 2-ethyl acrylate At least one monomer in the ester.
丙烯酸酯共聚物較佳包含80至95wt%的C4-C12直鏈或支鏈之丙烯酸烷基酯單體和5至20wt%的含 促黏劑的可聚合單體。如果含促黏劑的可聚合單體的量小於5wt%,則難以解決由於界面上具有低分子量的丙烯酸酯共聚物滲出而引起的低耐久性和低黏著性的問題。另一方面,如果其量超過20wt%,則黏著劑層具有差的可撓性,因此折疊性可能劣化。 The acrylate copolymer preferably comprises 80 to 95% by weight of a C 4 -C 12 linear or branched alkyl acrylate monomer and 5 to 20% by weight of an adhesion promoter-containing polymerizable monomer. If the amount of the adhesion-promoting polymerizable monomer is less than 5% by weight, it is difficult to solve the problem of low durability and low adhesion due to bleed out of the acrylate copolymer having a low molecular weight at the interface. On the other hand, if the amount exceeds 20% by weight, the adhesive layer has poor flexibility, and thus the foldability may be deteriorated.
如果丙烯酸酯共聚物的重均分子量小於10,000,滲出可能變得嚴重,因此耐久性可能劣化。另一方面,如果其重均分子量超過100,000,由於滲出低,黏著性的改善程度可能變得不足。 If the weight average molecular weight of the acrylate copolymer is less than 10,000, bleed out may become severe, and thus durability may be deteriorated. On the other hand, if the weight average molecular weight exceeds 100,000, the degree of improvement in adhesion may become insufficient due to low bleeding.
在光學透明黏著劑組成物中,可光固化之(甲基)丙烯酸酯共聚物和該丙烯酸酯共聚物較佳係以95:5至70:30的重量比範圍包含在內。基於該可光固化之(甲基)丙烯酸酯共聚物和該丙烯酸酯共聚物的總計為100重量份之基準計,如果該丙烯酸酯共聚物的量小於5重量份,則黏著性的改善程度可能變得不足。另一方面,基於該可光固化之(甲基)丙烯酸酯共聚物和該丙烯酸酯共聚物的總計為100重量份之基準計,如果丙烯酸酯共聚物的量超過30重量份,則可能導致折疊性差。 In the optically clear adhesive composition, the photocurable (meth) acrylate copolymer and the acrylate copolymer are preferably included in a weight ratio range of from 95:5 to 70:30. Based on the total of 100 parts by weight of the photocurable (meth) acrylate copolymer and the acrylate copolymer, if the amount of the acrylate copolymer is less than 5 parts by weight, the degree of improvement in adhesion may be Become insufficient. On the other hand, based on the total amount of the photocurable (meth) acrylate copolymer and the acrylate copolymer of 100 parts by weight, if the amount of the acrylate copolymer exceeds 30 parts by weight, it may cause folding Poor sex.
本發明的光學透明黏著劑組成物包含光聚合起始劑以有效地誘導可聚合自由基基團的反應。該光聚合起始劑可以在含羥基丙烯酸共聚物的聚合中使用,也可以與可光固化之(甲基)丙烯酸酯共聚物一起含在光學透明黏著劑組成物中。 The optically clear adhesive composition of the present invention contains a photopolymerization initiator to effectively induce a reaction of a polymerizable radical group. The photopolymerization initiator may be used in the polymerization of the hydroxyl group-containing acrylic copolymer or may be contained in the optically clear adhesive composition together with the photocurable (meth)acrylate copolymer.
該光聚合起始劑沒有特別限制,只要係本 領域習知的,可以使用任何光聚合起始劑。起始劑的實例可以包括例如安息香系起始劑、羥基酮系起始劑、胺基酮系起始劑、及氧化膦系起始劑等能夠藉由UV照射產生自由基從而引發光聚合的典型起始劑。 The photopolymerization initiator is not particularly limited as long as it is conventional in the art, any photopolymerization initiator can be used. Examples of the initiator may include, for example, a benzoin-based initiator, a hydroxyketone-based initiator, an aminoketone-based initiator, and a phosphine oxide-based initiator, which are capable of generating a radical by UV irradiation to initiate photopolymerization. Typical starter.
如果光聚合起始劑的量太低,其添加效果可能變得不顯著。另一方面,如果其量太高,則耐久性或透明度的一致性等性質可能劣化。因此,其量可以被適當地決定。 If the amount of the photopolymerization initiator is too low, the effect of addition may become insignificant. On the other hand, if the amount thereof is too high, properties such as durability or uniformity of transparency may deteriorate. Therefore, the amount thereof can be appropriately determined.
基於可光固化之(甲基)丙烯酸酯共聚物和丙烯酸酯共聚物的總計為100重量份之基準計,光聚合起始劑的含量較佳為0.1至5重量份,更佳為0.5至2重量份。 The photopolymerization initiator is preferably contained in an amount of from 0.1 to 5 parts by weight, more preferably from 0.5 to 2, based on 100 parts by weight based on the total of the photocurable (meth) acrylate copolymer and the acrylate copolymer. Parts by weight.
本發明的光學透明黏著劑組成物可以進一步包括多官能交聯劑。該多功能交聯劑沒有特別限制,可以包括本領域所習知者。其具體實例可以包含熱固性多官能異氰酸酯交聯劑,多官能(甲基)丙烯酸酯交聯劑等。 The optically clear adhesive composition of the present invention may further comprise a multifunctional crosslinking agent. The multifunctional crosslinking agent is not particularly limited and may include those well known in the art. Specific examples thereof may include a thermosetting polyfunctional isocyanate crosslinking agent, a polyfunctional (meth) acrylate crosslinking agent, and the like.
基於可光固化之(甲基)丙烯酸酯共聚物和丙烯酸酯共聚物的總計為100重量份之基準計,多官能交聯劑的含量可以為0.02至5重量份。 The content of the polyfunctional crosslinking agent may be 0.02 to 5 parts by weight based on 100 parts by weight of the total of the photocurable (meth) acrylate copolymer and the acrylate copolymer.
本發明的光學透明黏著劑組成物可以進一步包括矽烷偶合劑。偶合劑的種類沒有特別限定,可以使用製備黏著劑領域所習知的任何偶合劑。矽烷偶合劑的例子包含γ-環丙氧基丙基三乙氧基矽烷、γ-環丙氧基丙基三甲氧基矽烷、γ-環丙氧基丙基甲基二乙氧基矽烷、γ-環丙 氧基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、及3-異氰酸基丙基三乙氧基矽烷。 The optically clear adhesive composition of the present invention may further comprise a decane coupling agent. The kind of the coupling agent is not particularly limited, and any coupling agent known in the field of preparing an adhesive can be used. Examples of the decane coupling agent include γ-cyclopropoxypropyltriethoxydecane, γ-cyclopropoxypropyltrimethoxydecane, γ-cyclopropoxypropylmethyldiethoxydecane, γ. - cyclopropoxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, gamma-methacryloxypropyltrimethoxy Baseline, γ-methacryloxypropyltriethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and 3-isocyanatopropyl Triethoxy decane.
基於可光固化之(甲基)丙烯酸酯共聚物和丙烯酸酯共聚物的總計為100重量份之基準計,矽烷偶合劑的含量為0.01重量份至5重量份,較佳係0.01重量份至1重量份。 The content of the decane coupling agent is from 0.01 part by weight to 5 parts by weight, based on 100 parts by weight of the total of the photocurable (meth) acrylate copolymer and the acrylate copolymer, preferably from 0.01 part by weight to 1 Parts by weight.
本發明的光學透明黏著劑組成物可以進一步包括增黏劑(tackifier)以調節黏著性能。 The optically clear adhesive composition of the present invention may further include a tackifier to adjust the adhesive properties.
而且,可以進一步包含至少一種添加劑,係選自由環氧樹脂、固化劑、UV穩定劑、抗氧化劑、著色劑、增強劑、填充劑、消泡劑、表面活性劑、及增塑劑所組成群組之一者。 Furthermore, it may further comprise at least one additive selected from the group consisting of an epoxy resin, a curing agent, a UV stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, and a plasticizer. One of the groups.
本發明的光學透明黏著劑組成物可以進一步包括溶劑。本領域習知的任何溶劑都可以使用而沒有限制,只要它能夠溶解光學透明黏著劑組成物中使用的單體和共聚物即可。 The optically clear adhesive composition of the present invention may further comprise a solvent. Any solvent conventionally known in the art can be used without limitation as long as it can dissolve the monomers and copolymers used in the optically clear adhesive composition.
溶劑的典型例子可以包含乙酸乙酯、甲乙酮、甲苯、及乙腈 Typical examples of the solvent may include ethyl acetate, methyl ethyl ketone, toluene, and acetonitrile.
基於可光固化之(甲基)丙烯酸酯共聚物和丙烯酸酯共聚物的總計為100重量份之基準計,溶劑的含量可以為40至85重量份。 The solvent may be contained in an amount of from 40 to 85 parts by weight based on 100 parts by weight of the total of the photocurable (meth) acrylate copolymer and the acrylate copolymer.
本發明的光學透明黏著劑組成物較佳在23℃下具有500釐泊(cP)至2,500釐泊的黏度。 The optically clear adhesive composition of the present invention preferably has a viscosity of from 500 centipoise (cP) to 2,500 centipoise at 23 °C.
除了上面所描述之外,製備本發明光學透明黏著劑組成物的方法可以透過本領域中通常習知的任何方法進行。在此,可以使用本領域中典型的分子量控制劑、催化劑等而沒有限制。 In addition to the above, the method of preparing the optically clear adhesive composition of the present invention can be carried out by any method generally known in the art. Here, a molecular weight controlling agent, a catalyst, or the like which is typical in the art can be used without limitation.
使用本發明光學透明黏著劑組成物的塗佈方法沒有特別限制,其實例可以包含典型方法如棒塗、旋塗、刮刀塗佈(comma coating)、及凹版塗佈。在塗佈過程中,必須控制黏著劑組成物中所含涉及多官能交聯劑的官能基團,從而防止交聯反應發生以實現均勻塗佈。由此,交聯劑才能在塗佈製程後的固化和老化製程中形成交聯結構,從而增加了黏著性能和可切割性以及黏著劑的內聚力。 The coating method using the optically clear adhesive composition of the present invention is not particularly limited, and examples thereof may include typical methods such as bar coating, spin coating, comma coating, and gravure coating. During the coating process, it is necessary to control the functional groups involved in the adhesive composition involving the polyfunctional crosslinking agent, thereby preventing the crosslinking reaction from occurring to achieve uniform coating. Thereby, the crosslinking agent can form a crosslinked structure in the curing and aging process after the coating process, thereby increasing the adhesion property and the cuttability and the cohesive force of the adhesive.
而且,較佳係在從黏著劑組成物中充分除去揮發性成分或發泡成分,如反應殘餘物之後進行塗覆製程。由此,可以防止由於黏著劑的交聯密度或分子量過低而導致彈性模量下降,並且防止在高溫下由於玻璃板和黏著劑層之間氣泡的尺寸增大而形成內部散射體。 Further, it is preferred to carry out a coating process after sufficiently removing volatile components or foaming components, such as reaction residues, from the adhesive composition. Thereby, it is possible to prevent the elastic modulus from being lowered due to the crosslinking density or the molecular weight of the adhesive being too low, and to prevent the internal scatter body from being formed at a high temperature due to an increase in the size of the bubble between the glass plate and the adhesive layer.
在形成光學透明黏著劑組成物的塗層之後,透過光照射使其固化。在此,當進行UV照射時,可以使用高壓汞燈、無電極燈、或氙燈。 After the coating of the optically clear adhesive composition is formed, it is cured by light irradiation. Here, when UV irradiation is performed, a high pressure mercury lamp, an electrodeless lamp, or a xenon lamp can be used.
在光照之前或之後,可以誘導組成物中交聯劑的官能基團與其聚合物的熱固性官能基團之間的反應,進行適當的老化過程,其條件沒有特別的限制,只要 交聯反應可以適當地發生。 Before or after the irradiation, the reaction between the functional group of the crosslinking agent in the composition and the thermosetting functional group of the polymer may be induced, and an appropriate aging process may be carried out, and the conditions are not particularly limited as long as the crosslinking reaction is appropriate. Occurs.
根據本發明用於光學膜的黏著劑組成物可以用於堆疊光學膜,如偏振膜、相位差膜、防眩光膜、光學視角補償膜、或增亮膜,可以互相堆疊,或者將光學膜或其層壓體附著到如顯示面板的目標上。 The adhesive composition for an optical film according to the present invention can be used for stacking optical films such as a polarizing film, a retardation film, an anti-glare film, an optical viewing angle compensation film, or a brightness enhancement film, which can be stacked on each other, or an optical film or The laminate is attached to a target such as a display panel.
特別地,根據本發明用於光學膜的黏著劑組成物較佳用於可撓性顯示器。 In particular, the adhesive composition for an optical film according to the present invention is preferably used for a flexible display.
另外,本發明提出了透過用本發明光學透明黏著劑組成物塗佈轉移膜而形成的光學透明黏著性膜。 Further, the present invention proposes an optically transparent adhesive film formed by coating a transfer film with the optically clear adhesive composition of the present invention.
作為用於光學透明黏著性膜的轉移膜,可以使用本領域習知的任何膜而沒有限制。此外,在製造光學透明黏著性膜的方法中,可以進行本領域習知的任何方法而沒有限制。 As the transfer film for the optically transparent adhesive film, any film known in the art can be used without limitation. Further, in the method of producing an optically transparent adhesive film, any method known in the art can be carried out without limitation.
另外,本發明提出了一種平板顯示器,其包括由本發明的光學透明黏著劑組成物形成的黏著劑層。 Further, the present invention proposes a flat panel display comprising an adhesive layer formed of the optically clear adhesive composition of the present invention.
在此,平板顯示器較佳係可撓性顯示器。 Here, the flat panel display is preferably a flexible display.
本發明透過以下實施例和比較例來說明,這些實施例和比較例僅僅係為了說明本發明而提出的,但是本發明不限於這些實施例,並且可以進行各種修飾和改變。 The invention is illustrated by the following examples and comparative examples, which are merely intended to illustrate the invention, but the invention is not limited thereto, and various modifications and changes can be made.
製備實施例1-1:丙烯酸酯共聚物A1的製備Preparation Example 1-1: Preparation of Acrylate Copolymer A1
將80重量份的丙烯酸正丁酯(n-BA)和20重量份的丙烯酸4-羥丁酯(4-HBA)放入配有冷凝器的1公 升反應器中,以便在氮氣回流的同時促進其溫度控制。向其中加入120重量份乙酸乙酯(EAc)溶劑,並將所得反應混合物用氮氣吹掃60分鐘以除去氧氣。之後,將溫度保持在70℃,向其中加入0.5重量份反應起始劑AIBN(偶氮二異丁腈),反應12小時,由此製備重均分子量為1,200,000的丙烯酸酯共聚物A1。 80 parts by weight of n-butyl acrylate (n-BA) and 20 parts by weight of 4-hydroxybutyl acrylate (4-HBA) were placed in a 1 liter reactor equipped with a condenser to promote nitrogen reflux Its temperature control. 120 parts by weight of ethyl acetate (EAc) solvent was added thereto, and the resulting reaction mixture was purged with nitrogen for 60 minutes to remove oxygen. Thereafter, the temperature was maintained at 70 ° C, and 0.5 part by weight of a reaction initiator AIBN (azobisisobutyronitrile) was added thereto, and reacted for 12 hours, thereby preparing an acrylate copolymer A1 having a weight average molecular weight of 1,200,000.
製備實施例1-2:丙烯酸酯共聚物A2的製備Preparation Example 1-2: Preparation of Acrylate Copolymer A2
使用與製備實施例1-1中相同的聚合技術製備重均分子量為1,280,000的丙烯酸酯共聚物A2,不同之處在於,使用90重量份的丙烯酸正丁酯(n-BA)和10重量份的丙烯酸4-羥丁酯(4-HBA)。 An acrylate copolymer A2 having a weight average molecular weight of 1,280,000 was prepared using the same polymerization technique as in Preparation Example 1-1, except that 90 parts by weight of n-butyl acrylate (n-BA) and 10 parts by weight were used. 4-hydroxybutyl acrylate (4-HBA).
製備實施例1-3:丙烯酸酯共聚物A3的製備Preparation Example 1-3: Preparation of Acrylate Copolymer A3
使用與製備實施例1-1中相同的聚合技術製備重均分子量為1,390,000的丙烯酸酯共聚物A3,不同之處在於,使用98重量份丙烯酸正丁酯(n-BA)和2重量份的丙烯酸4-羥丁酯(4-HBA)。 An acrylate copolymer A3 having a weight average molecular weight of 1,390,000 was prepared using the same polymerization technique as in Preparation Example 1-1, except that 98 parts by weight of n-butyl acrylate (n-BA) and 2 parts by weight of acrylic acid were used. 4-hydroxybutyl ester (4-HBA).
製備實施例1-4:丙烯酸酯共聚物A4的製備Preparation Examples 1-4: Preparation of Acrylate Copolymer A4
使用與製備實施例1-1中相同的聚合技術製備重均分子量為1,450,000的丙烯酸酯共聚物A4,不同之處在於,使用99.5重量份丙烯酸正丁酯(n-BA)和0.5重量份的丙烯酸2-羥乙酯(2-HEA)。 An acrylate copolymer A4 having a weight average molecular weight of 1,450,000 was prepared using the same polymerization technique as in Preparation Example 1-1, except that 99.5 parts by weight of n-butyl acrylate (n-BA) and 0.5 part by weight of acrylic acid were used. 2-Hydroxyethyl ester (2-HEA).
製備實施例2-1:可光固化之(甲基)丙烯酸酯共聚物B1的製備Preparation Example 2-1: Preparation of photocurable (meth) acrylate copolymer B1
將100重量份的丙烯酸酯共聚物A1固體成分、1重量份的甲基丙烯酸2-異氰酸基乙酯和0.1重量份的DBTDL(二月桂酸二丁基錫)放入配有冷凝器的1公升反應器中,以便在氮氣回流的同時促進其溫度控制。隨後,在40℃、大氣壓力下進行4小時或以上的反應,得到可光固化之(甲基)丙烯酸酯共聚物B1。 100 parts by weight of acrylate copolymer A1 solid content, 1 part by weight of 2-isocyanatoethyl methacrylate, and 0.1 part by weight of DBTDL (dibutyltin dilaurate) were placed in 1 liter equipped with a condenser In the reactor, to promote temperature control while refluxing with nitrogen. Subsequently, the reaction was carried out at 40 ° C under atmospheric pressure for 4 hours or more to obtain a photocurable (meth) acrylate copolymer B1.
製備實施例2-2:可光固化之(甲基)丙烯酸酯共聚物B2的製備Preparation Example 2-2: Preparation of photocurable (meth) acrylate copolymer B2
使用與製備實施例2-1中相同的方式製備可光固化之(甲基)丙烯酸酯共聚物B2,不同之處在於,使用丙烯酸酯共聚物A2。 The photocurable (meth) acrylate copolymer B2 was prepared in the same manner as in the preparation of Example 2-1, except that the acrylate copolymer A2 was used.
製備實施例2-3:可光固化之(甲基)丙烯酸酯共聚物B3的製備Preparation Example 2-3: Preparation of photocurable (meth) acrylate copolymer B3
使用與製備實施例2-1中相同的方式製備可光固化之(甲基)丙烯酸酯共聚物B3,不同之處在於,使用丙烯酸酯共聚物A3。 The photocurable (meth) acrylate copolymer B3 was prepared in the same manner as in the preparation of Example 2-1 except that the acrylate copolymer A3 was used.
製備實施例2-4:可光固化之(甲基)丙烯酸酯共聚物B4的製備Preparation Example 2-4: Preparation of photocurable (meth) acrylate copolymer B4
將100重量份的丙烯酸酯共聚物A4固體成分、0.1重量份的甲基丙烯酸2-異氰酸基乙酯和0.1重量份的DBTDL(二月桂酸二丁基錫)放入配有冷凝器的1公升反應器中,以便在氮氣回流的同時促進其溫度控制。隨後, 在40℃、大氣壓力下進行4小時或以上的反應,得到可光固化之(甲基)丙烯酸酯共聚物B4。 100 parts by weight of acrylate copolymer A4 solid content, 0.1 part by weight of 2-isocyanatoethyl methacrylate, and 0.1 part by weight of DBTDL (dibutyltin dilaurate) were placed in 1 liter equipped with a condenser In the reactor, to promote temperature control while refluxing with nitrogen. Subsequently, the reaction was carried out at 40 ° C under atmospheric pressure for 4 hours or more to obtain a photocurable (meth) acrylate copolymer B4.
製備實施例3-1:丙烯酸酯共聚物C1的製備Preparation Example 3-1: Preparation of Acrylate Copolymer C1
將90.9重量份的丙烯酸正丁酯(n-BA)和9.1重量份的下述化學式2單體放入配有冷凝器的1公升反應器中,以便在氮氣回流的同時促進其溫度控制。向其中加入120重量份乙酸乙酯(EAc)溶劑,並將所得反應混合物用氮氣吹掃60分鐘以除去氧氣。之後,將溫度保持在70℃,向其中加入0.5重量份反應起始劑AIBN(偶氮二異丁腈),反應12小時,由此製備重均分子量為55,000的丙烯酸酯共聚物C1。 90.9 parts by weight of n-butyl acrylate (n-BA) and 9.1 parts by weight of the following Chemical Formula 2 monomer were placed in a 1 liter reactor equipped with a condenser to promote temperature control while refluxing with nitrogen. 120 parts by weight of ethyl acetate (EAc) solvent was added thereto, and the resulting reaction mixture was purged with nitrogen for 60 minutes to remove oxygen. Thereafter, the temperature was maintained at 70 ° C, and 0.5 part by weight of a reaction initiator AIBN (azobisisobutyronitrile) was added thereto, and reacted for 12 hours, thereby preparing an acrylate copolymer C1 having a weight average molecular weight of 55,000.
製備實施例3-2:丙烯酸酯共聚物C2的製備Preparation Example 3-2: Preparation of Acrylate Copolymer C2
使用與製備實施例3-1中相同的方式製備重均分子量為69,000的丙烯酸酯共聚物C2,不同之處在於,使用下面的化學式3的單體代替化學式2的單體。 An acrylate copolymer C2 having a weight average molecular weight of 69,000 was prepared in the same manner as in the production of Example 3-1, except that the monomer of the following Chemical Formula 3 was used instead of the monomer of Chemical Formula 2.
製備實施例3-3:丙烯酸酯共聚物C3的製備Preparation Example 3-3: Preparation of Acrylate Copolymer C3
使用與製備實施例3-1中相同的方式製備重均分子量為51,000的丙烯酸酯共聚物C3,不同之處在於,使用下面的化學式4的單體代替化學式2的單體。 An acrylate copolymer C3 having a weight average molecular weight of 51,000 was prepared in the same manner as in the production of Example 3-1, except that the monomer of the following Chemical Formula 4 was used instead of the monomer of Chemical Formula 2.
製備實施例3-4:丙烯酸酯共聚物C4的製備Preparation Example 3-4: Preparation of Acrylate Copolymer C4
使用與製備實施例3-1中相同的方式製備重均分子量為51,000的丙烯酸酯共聚物C4,不同之處在於,使用下面的化學式6的單體代替化學式2的單體。 An acrylate copolymer C4 having a weight average molecular weight of 51,000 was prepared in the same manner as in the preparation of Example 3-1, except that the monomer of the following Chemical Formula 6 was used instead of the monomer of Chemical Formula 2.
製備實施例3-5:丙烯酸酯共聚物C5的製備Preparation Example 3-5: Preparation of Acrylate Copolymer C5
使用與製備實施例3-1中相同的方式製備重均分子量為78,000的丙烯酸酯共聚物C5,不同之處在於,使用下面的化學式7的單體代替化學式2的單體。 An acrylate copolymer C5 having a weight average molecular weight of 78,000 was prepared in the same manner as in the preparation of Example 3-1, except that the monomer of the following Chemical Formula 7 was used instead of the monomer of Chemical Formula 2.
<化學式7>
在化學式7中,X係三氟甲磺酸鹽(OTf)。 In Chemical Formula 7, X-based triflate (OTf).
製備實施例4:形成用於彎曲性評估的硬塗膜Preparation Example 4: Formation of a hard coat film for flexibility evaluation
<環氧矽氧烷樹脂的製備><Preparation of epoxy oxirane resin>
將3-環丙氧基丙基三甲氧基矽烷(GPTS,取自Gelest公司)和水以23.63公克比2.70公克(0.1莫耳:0.15莫耳)的比例混合,然後置於100毫升雙頸燒瓶中。之後,向該混合物中加入0.05毫升作為催化劑的氨,並在60℃下攪拌6小時,由此製備矽氧烷溶膠。 3-Cyclopropoxypropyltrimethoxydecane (GPTS, taken from Gelest) and water were mixed at a ratio of 23.63 grams to 2.70 grams (0.1 mole: 0.15 mole) and then placed in a 100 ml two-necked flask in. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 ° C for 6 hours, thereby preparing a oxime sol.
<硬塗(hard coating)組成物的製備><Preparation of hard coating composition>
將矽氧烷溶膠和二縮水甘油醚以100比10的重量比混合,且將100重量份的所得混合物與2重量份的三芳基锍六氟銻酸鹽(triarylsulfonium hexafluoroantimonate)混合,由此得到硬塗組成物。 The oxirane sol and the diglycidyl ether are mixed in a weight ratio of 100 to 10, and 100 parts by weight of the obtained mixture is mixed with 2 parts by weight of triarylsulfonium hexafluoroantimonate, thereby obtaining a hard Apply the composition.
<硬塗膜的形成><Formation of hard coat film>
在具有厚度為40微米的COP(環烯烴聚合物,ZF-16,可從Zeon公司取得)膜上施加厚度為50微米的硬塗組成物,並進行表面電暈處理,由此製造膜。將該膜在汞UV燈(20毫瓦特/平方公分)下暴露5分鐘,並使用三芳基鋶六氟銻酸鹽起始反應以產生酸,然後在50℃和50%RH(相對濕度)下水熱處理60分鐘,從而形成硬塗膜。 A hard coat composition having a thickness of 50 μm was applied to a film having a thickness of 40 μm (cycloolefin polymer, ZF-16, available from Zeon Corporation), and subjected to surface corona treatment, thereby producing a film. The film was exposed to a mercury UV lamp (20 mW/cm 2 ) for 5 minutes, and the reaction was initiated using triarylsulfonium hexafluoroantimonate to produce an acid, which was then water at 50 ° C and 50% RH (relative humidity). The heat treatment was performed for 60 minutes to form a hard coat film.
實施例1:光學透明黏著劑組成物的製備Example 1: Preparation of optically clear adhesive composition
透過混合80重量份的製備實施例2-1可光固化之(甲基)丙烯酸酯共聚物B1和20重量份的製備實施例3-1(甲基)丙烯酸酯共聚物C1,亦即,將總計100重量份的該可光固化之(甲基)丙烯酸酯共聚物B1和該丙烯酸酯共聚物C1、0.5重量份的多官能異氰酸酯系交聯劑(Coronate L,取自日本NPU公司)、及0.2重量份的光聚合起始劑(羥基環己基苯基酮,Irgacure 184,取自瑞士汽巴精化公司),製備光學透明黏著劑組成物。 By mixing 80 parts by weight of Preparation Example 2-1 photocurable (meth) acrylate copolymer B1 and 20 parts by weight of Preparation Example 3-1 (meth) acrylate copolymer C1, that is, 100 parts by weight of the photocurable (meth) acrylate copolymer B1 and the acrylate copolymer C1, 0.5 parts by weight of a polyfunctional isocyanate crosslinking agent (Coronate L, available from NPU, Japan), and 0.2 parts by weight of a photopolymerization initiator (hydroxycyclohexyl phenyl ketone, Irgacure 184, obtained from Ciba Specialty Chemicals, Switzerland) was used to prepare an optically clear adhesive composition.
實施例2:光學透明黏著劑組成物的製備Example 2: Preparation of optically clear adhesive composition
使用與實施例1中相同的方式製備光學透明黏著劑組成物,不同之處在於,使用70重量份的製備實施例2-1可光固化之(甲基)丙烯酸酯共聚物B2和30重量份的製備實施例3-2(甲基)丙烯酸酯共聚物C2。 An optically clear adhesive composition was prepared in the same manner as in Example 1, except that 70 parts by weight of the photocurable (meth) acrylate copolymer B2 and 30 parts by weight of Preparation Example 2-1 were used. Preparation Example 3-2 (meth) acrylate copolymer C2.
實施例3:光學透明黏著劑組成物的製備Example 3: Preparation of optically clear adhesive composition
使用與實施例1中相同的方式製備光學透明黏著劑組成物,不同之處在於,使用75重量份的製備實施例2-1可光固化之(甲基)丙烯酸酯共聚物B2和25重量份的製備實施例3-3(甲基)丙烯酸酯共聚物C3。 An optically clear adhesive composition was prepared in the same manner as in Example 1, except that 75 parts by weight of the photocurable (meth) acrylate copolymer B2 and 25 parts by weight of Preparation Example 2-1 were used. Preparation Example 3-3 (meth) acrylate copolymer C3.
實施例4:光學透明黏著劑組成物的製備Example 4: Preparation of optically clear adhesive composition
使用與實施例1中相同的方式製備光學透明黏著劑組成物,不同之處在於,使用85重量份的製備實施例2-1可光固化之(甲基)丙烯酸酯共聚物B2和15重量份的製備實施例3-4(甲基)丙烯酸酯共聚物C4。 An optically clear adhesive composition was prepared in the same manner as in Example 1, except that 85 parts by weight of the photocurable (meth) acrylate copolymer B2 and 15 parts by weight of Preparation Example 2-1 were used. Preparation Example 3-4 (meth) acrylate copolymer C4.
實施例5:光學透明黏著劑組成物的製備Example 5: Preparation of optically clear adhesive composition
使用與實施例1中相同的方式製備光學透明黏著劑組成物,不同之處在於,使用95重量份的製備實施例2-1可光固化之(甲基)丙烯酸酯共聚物B2和5重量份的製備實施例3-5(甲基)丙烯酸酯共聚物C5。 An optically clear adhesive composition was prepared in the same manner as in Example 1, except that 95 parts by weight of the photocurable (meth) acrylate copolymer B2 and 5 parts by weight of Preparation Example 2-1 were used. Preparation Example 3-5 (meth) acrylate copolymer C5.
比較例1:光學透明黏著劑組成物的製備Comparative Example 1: Preparation of optically clear adhesive composition
透過混合100重量份的製備實施例2-4可光固化之(甲基)丙烯酸酯共聚物B4、0.5重量份的多官能異氰酸酯交聯劑(Coronate L,取自日本NPU公司)、及0.2重量份的光聚合起始劑(羥基環己基苯基酮,Irgacure 184,取自瑞士汽巴精化公司),製備光學透明黏著劑組成物。 By mixing 100 parts by weight of Preparation Example 2-4 photocurable (meth) acrylate copolymer B4, 0.5 part by weight of a polyfunctional isocyanate crosslinking agent (Coronate L, available from NPU, Japan), and 0.2 weight A photopolymerization initiator (hydroxycyclohexyl phenyl ketone, Irgacure 184, obtained from Ciba Specialty Chemicals, Switzerland) was used to prepare an optically clear adhesive composition.
比較例2:光學透明黏著劑組成物的製備Comparative Example 2: Preparation of optically clear adhesive composition
透過混合100重量份的製備實施例3-1丙烯酸酯共聚物C1和0.5重量份的多官能異氰酸酯交聯劑(Coronate L,取自日本NPU獲得),製備光學透明黏著劑組成物。 An optically clear adhesive composition was prepared by mixing 100 parts by weight of Preparation Example 3-1 acrylate copolymer C1 and 0.5 part by weight of a polyfunctional isocyanate crosslinking agent (Coronate L, available from NPU, Japan).
實施例6:光學透明黏著性膜的形成Example 6: Formation of an optically transparent adhesive film
將實施例1至5和比較例1及2中的各個光學透明黏著劑組成物塗佈在具有厚度為50微米的PET膜上,並塗佈有機矽剝離劑,以使固化後厚度達到100微米,然後在100℃下乾燥5分鐘,由此製造實施例6-1(使用實施例1的光學透明黏著劑組成物)、實施例6-2(使用實施例2的光學透明黏著劑組成物)、實施例6-3(使用實施例3的光學透明黏著劑組成物)、實施例6-4(使用實施例4的 光學透明黏著劑組成物)、實施例6-5(使用實施例5的光學透明黏著劑組成物)、比較例3-1(使用比較例1的光學透明黏著劑組成物)、及比較例3-2(使用比較例2的光學透明黏著劑組成物)。 Each of the optically clear adhesive compositions of Examples 1 to 5 and Comparative Examples 1 and 2 was coated on a PET film having a thickness of 50 μm, and an organic tantalum release agent was applied so as to have a thickness of 100 μm after curing. Then, it was dried at 100 ° C for 5 minutes, thereby producing Example 6-1 (using the optically clear adhesive composition of Example 1), and Example 6-2 (using the optically clear adhesive composition of Example 2) Example 6-3 (using the optically clear adhesive composition of Example 3), Example 6-4 (using the optically clear adhesive composition of Example 4), and Examples 6-5 (using the use of Example 5) Optically clear adhesive composition), Comparative Example 3-1 (using the optically clear adhesive composition of Comparative Example 1), and Comparative Example 3-2 (using the optically clear adhesive composition of Comparative Example 2).
實施例7:具有黏著劑層之層壓板的形成Example 7: Formation of a laminate with an adhesive layer
使用實施例6-1、實施例6-2、實施例6-3、實施例6-4、實施例6-5、比較例3-1、及比較例3-2中的各個光學透明黏著性膜,在100微米厚的PET膜(取自三菱公司)上形成黏著劑層,並且使用UV燈(取自Fusion公司)以1000毫焦耳/平方公分的光照射形成剝離膜的方向,由此製造具有實施例7-1、實施例7-2、實施例7-3、實施例7-4、實施例7-5、比較例4-1、及比較例4-2中的各個的黏著劑層的層壓板。 The optical transparency of each of Example 6-1, Example 6-2, Example 6-3, Example 6-4, Example 6-5, Comparative Example 3-1, and Comparative Example 3-2 was used. Film, an adhesive layer was formed on a 100 μm thick PET film (taken from Mitsubishi Corporation), and a UV lamp (taken from Fusion Corporation) was used to irradiate light of 1000 mJ/cm 2 to form a release film, thereby manufacturing The adhesive layer of each of Example 7-1, Example 7-2, Example 7-3, Example 7-4, Example 7-5, Comparative Example 4-1, and Comparative Example 4-2 Laminate.
實施例8:彎曲性評價用硬塗膜/黏著劑層/PET層壓板的形成Example 8: Formation of a hard coat film/adhesive layer/PET laminate for evaluation of flexibility
將實施例7-1、實施例7-2、實施例7-3、實施例7-4、實施例7-5、比較例4-1、及比較例4-2中的各個層壓板切割成50毫米×100毫米的尺寸。隨後,將PET膜從該經切割之層壓板的黏著劑層剝離,然後將所得層壓板黏貼到尺寸為50毫米×100毫米的製備實施例3中製造的彎曲性評價用硬塗膜上,在壓力鍋內加壓(50℃,5大氣壓)約20分鐘,然後在恆溫恆濕條件(23℃和50%RH)下老化24小時,由此製造實施例8-1、實施例8-2、實施例8-3、實施例8-4、實施例8-5、比較例5-1、及比較例5-2中的 各個用於彎曲性評價之硬塗膜/黏著劑層/PET(100微米)層壓板。 Each of the laminates of Example 7-1, Example 7-2, Example 7-3, Example 7-4, Example 7-5, Comparative Example 4-1, and Comparative Example 4-2 was cut into 50 mm x 100 mm size. Subsequently, the PET film was peeled off from the adhesive layer of the cut laminate, and then the resulting laminate was adhered to a hard coating film for bending evaluation manufactured in Preparation Example 3 having a size of 50 mm × 100 mm. The pressure cooker was pressurized (50 ° C, 5 atm) for about 20 minutes, and then aged under constant temperature and humidity conditions (23 ° C and 50% RH) for 24 hours, thereby producing Example 8-1, Example 8-2, and carrying out Each of Example 8-3, Example 8-4, Example 8-5, Comparative Example 5-1, and Comparative Example 5-2, Hard Coating Film/Adhesive Layer/PET (100 μm for Flexibility Evaluation) ) Laminate.
測試實施例:光學透明黏著劑組成物性質的評估Test Example: Evaluation of the Properties of Optically Clear Adhesive Compositions
1.可折疊性的評估1. Evaluation of foldability
<評估方法><Evaluation method>
評估標準:IEC 62715 Evaluation criteria: IEC 62715
評估裝置:無張力U形折疊測試機(DLDMLH-FS) Evaluation device: tension-free U-fold tester (DLDMLH-FS)
裝置製造商:YUASA SYSTEM(日本) Device manufacturer: YUASA SYSTEM (Japan)
評估條件:-20℃/10,000次(彎曲使得硬塗層位於內側) Evaluation conditions: -20 ° C / 10,000 times (bending so that the hard coat is on the inside)
將實施例8中製造的實施例8-1、實施例8-2、實施例8-3、實施例8-4、實施例8-5、比較例5-1、及比較例5-2中的各個用於彎曲性評價之硬塗膜/黏著劑層/PET層壓板,透過上述評估方法測量以決定其可折疊性。結果如下表1所示。 In Example 8-1, Example 8-2, Example 8-3, Example 8-4, Example 8-5, Comparative Example 5-1, and Comparative Example 5-2 produced in Example 8, Each of the hard coat film/adhesive layer/PET laminate for bending evaluation was measured by the above evaluation method to determine its foldability. The results are shown in Table 1 below.
<評估標準> <Evaluation criteria>
○:在層壓板上未觀察到發泡、剝離和裂紋等缺陷 ○: No defects such as foaming, peeling, and cracking were observed on the laminate.
△:用肉眼在層壓板上觀察到細小的缺陷 △: Small defects were observed on the laminate with the naked eye.
×:用肉眼在層壓板的折疊部分上清楚地觀察到缺陷 ×: The defect was clearly observed on the folded portion of the laminate with the naked eye.
2.耐久性的評估2. Evaluation of durability
(1)抗熱性的評估(1) Evaluation of heat resistance
將實施例8中製造的實施例8-1、實施例8-2、實施例8-3、實施例8-4、實施例8-5、比較例5-1、及比較例5-2中的各個用於彎曲性評價之硬塗膜/黏著劑層/PET層壓板,在80℃下放置1,000小時,然後觀察是否發生發泡或剝離,以評估其抗熱性。結果如下表1所示。 In Example 8-1, Example 8-2, Example 8-3, Example 8-4, Example 8-5, Comparative Example 5-1, and Comparative Example 5-2 produced in Example 8, Each of the hard coat film/adhesive layer/PET laminate for bending evaluation was allowed to stand at 80 ° C for 1,000 hours, and then it was observed whether foaming or peeling occurred to evaluate the heat resistance. The results are shown in Table 1 below.
<評估標準> <Evaluation criteria>
◎:不發生發泡或剝離 ◎: no foaming or peeling occurs
○:發泡或剝離缺陷數<5 ○: Number of foaming or peeling defects <5
△:5發泡或剝離缺陷數<10 △: 5 Number of foaming or peeling defects <10
×:10發泡或剝離缺陷數 ×:10 Number of foaming or peeling defects
(2)評估抗濕熱性(2) Evaluation of resistance to heat and humidity
將實施例8中製造的實施例8-1、實施例8-2、實施例8-3、實施例8-4、實施例8-5、比較例5-1、及比較例5-2中的各個用於彎曲性評價之硬塗膜/黏著劑層/PET層壓板,在60℃和90%RH下放置1,000小時,然後觀察是否發生發泡或剝離。在即將進行樣品評估之前,將樣品在室溫下靜置24小時,然後觀察以評估其抗濕熱性。結果如下表1所示。 In Example 8-1, Example 8-2, Example 8-3, Example 8-4, Example 8-5, Comparative Example 5-1, and Comparative Example 5-2 produced in Example 8, Each of the hard coat film/adhesive layer/PET laminate for bending evaluation was allowed to stand at 60 ° C and 90% RH for 1,000 hours, and then it was observed whether foaming or peeling occurred. The sample was allowed to stand at room temperature for 24 hours immediately before sample evaluation, and then observed to evaluate its resistance to moist heat. The results are shown in Table 1 below.
<評估標準> <Evaluation criteria>
◎:不發生發泡或剝離 ◎: no foaming or peeling occurs
○:發泡或剝離缺陷數<5 ○: Number of foaming or peeling defects <5
△:5發泡或剝離缺陷數<10 △: 5 Number of foaming or peeling defects <10
×:10發泡或剝離缺陷數 ×:10 Number of foaming or peeling defects
3.黏著性的評估3. Adhesion assessment
將實施例7中製造具有實施例7-1、實施例7-2、實施例7-3、實施例7-4、實施例7-5、比較例4-1、及比較例4-2中的各個的黏著劑層的層壓板,切成25毫米×100毫米的尺寸。隨後,將PET膜從該經切割之層壓板的黏著劑層剝離,然後根據JIS Z 0237使用2公斤滾筒將具有黏著劑層的層壓板附著到無鹼玻璃上。將該貼有層壓板的無鹼玻璃在壓力鍋內加壓(50℃,5大氣壓)約20分鐘,並在恆溫恆濕條件(23℃和50%RH)下儲存24小時。之後,使用TA(Texture Analyzer,取自英國Stable Micro Systems公司)以300毫米/分的剝離速率和180°的剝離角從該無鹼玻璃上剝離層壓板,以測量黏著性。結果如下表2所示。 The production of Example 7 was carried out in the same manner as in Example 7-1, Example 7-2, Example 7-3, Example 7-4, Example 7-5, Comparative Example 4-1, and Comparative Example 4-2. The laminate of each adhesive layer was cut into a size of 25 mm x 100 mm. Subsequently, the PET film was peeled off from the adhesive layer of the cut laminate, and then the laminate having the adhesive layer was attached to the alkali-free glass using a 2 kg roller according to JIS Z 0237. The laminate-attached alkali-free glass was pressurized in a pressure cooker (50 ° C, 5 atm) for about 20 minutes, and stored under constant temperature and humidity conditions (23 ° C and 50% RH) for 24 hours. Thereafter, the laminate was peeled off from the alkali-free glass using TA (Texture Analyzer, available from Stable Micro Systems, UK) at a peel rate of 300 mm/min and a peel angle of 180° to measure adhesion. The results are shown in Table 2 below.
從表1和2的測試結果可明顯看出,本發明實施例的光學透明黏著劑組成物在可折疊性、抗濕熱性、抗熱性、及黏著性均較優異。特別地,與比較例的光學透明黏著劑組成物相比,可折疊性顯著地高。 As is apparent from the test results of Tables 1 and 2, the optically clear adhesive composition of the examples of the present invention is excellent in foldability, moisture resistance, heat resistance, and adhesion. In particular, the foldability was remarkably high as compared with the optically clear adhesive composition of the comparative example.
儘管為了說明的目的已經揭露了本發明的較佳實施例,但是本領域的技術人員將會理解,在不違背所屬申請專利範圍揭露之本發明的範圍和精神的情況下,可以進行各種修改、添加及替換。 While the preferred embodiment of the present invention has been disclosed for the purposes of illustration, it will be understood that Add and replace.
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