TWI786350B - Optical laminate and organic light emitting device - Google Patents
Optical laminate and organic light emitting device Download PDFInfo
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- TWI786350B TWI786350B TW108143765A TW108143765A TWI786350B TW I786350 B TWI786350 B TW I786350B TW 108143765 A TW108143765 A TW 108143765A TW 108143765 A TW108143765 A TW 108143765A TW I786350 B TWI786350 B TW I786350B
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
本申請案主張在韓國智慧財產局提出申請的韓國專利申請案第10-2018-0152232號的提出申請日期的權益,所述申請案的揭露內容全文併入本案供參考。 This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0152232 filed with the Korea Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.
本申請案是有關於一種光學疊層及其用途。 This application relates to an optical stack and its use.
為保護偏光器,偏光板可藉由施加保護膜來阻擋紫外線。另一方面,如專利文獻1中所揭露的,偏光板的紫外線阻擋功能主要實施在偏光板的保護膜中。此外,偏光板的保護膜被設計成阻擋波長為約380奈米或小於380奈米的光,以保護偏光器免受紫外線照射。
In order to protect the polarizer, the polarizer can block ultraviolet rays by applying a protective film. On the other hand, as disclosed in
另一方面,在有機發光二極體(organic light emitting diode,OLED)中,作為達成RGB(紅、綠、藍)顏色的方法,應用將彩色濾光片應用於白色OLED光源(白色OLED,white OLED,WOLED)的方法或者構成分別發射RGB顏色的元件的方法(RGB方法)等。其中,RGB方法有利於達成其中應用塑膠基板代替有機發光二極體的玻璃基板的塑膠有機發光二極體(plastic OLED,POLED),但存在其較WOLED方法具有更短壽命的問題。 On the other hand, in an organic light emitting diode (OLED), as a method of achieving RGB (red, green, blue) colors, applying a color filter to a white OLED light source (white OLED, white OLED, WOLED) or a method of constituting elements that emit RGB colors respectively (RGB method), etc. Among them, the RGB method is beneficial to achieve plastic organic light-emitting diodes (plastic organic light-emitting diodes) in which plastic substrates are used instead of glass substrates for organic light-emitting diodes. OLED, POLED), but there is a problem that it has a shorter lifetime than the WOLED method.
此種問題的原因之一可包括由於波長為380奈米或大於380奈米的光而導致的尤其構成RGB顏色光源中的藍色光源的有機材料的退化。因此,應用於POLED的偏光板需要對380奈米或大於380奈米的藍色區域中的光具有阻擋功能以保護有機發光二極體的藍色光源進而延長有機發光二極體的壽命。 One of the causes of such a problem may include degradation of an organic material constituting especially a blue light source among RGB color light sources due to light having a wavelength of 380 nm or more. Therefore, the polarizing plate applied to POLED needs to have a blocking function for light in the blue region of 380 nm or greater to protect the blue light source of the OLED and prolong the lifetime of the OLED.
作為表現出上述功能的方法中的一種,應用將各種紫外線吸收劑添加至應用以附著有機發光面板及偏光板的壓敏黏合層的方法。然而,由於存在取決於紫外線吸收劑的類型在壓敏黏合層中發生變黃且因此偏光板的視覺欣賞性質劣化的問題,因此需要對可使偏光板的視覺欣賞性質最小化的紫外線吸收劑的組成進行研究。 As one of the methods of exhibiting the above functions, a method of adding various ultraviolet absorbers to a pressure-sensitive adhesive layer applied to attach an organic light-emitting panel and a polarizing plate is used. However, since there is a problem that yellowing occurs in the pressure-sensitive adhesive layer depending on the type of the ultraviolet absorber and thus the visual appreciation property of the polarizing plate is deteriorated, there is a need for an ultraviolet absorber that can minimize the visual appreciation property of the polarizing plate. Composition for research.
(專利文獻1)韓國註冊專利第10-1042477號 (Patent Document 1) Korean Registered Patent No. 10-1042477
本申請案是有關於一種光學疊層及其用途。 This application relates to an optical stack and its use.
本申請案是有關於一種光學疊層。本申請案的光學疊層包括光學膜;及存在於光學膜的一側或兩側上的壓敏黏合層。 This application relates to an optical stack. The optical stack of the present application includes an optical film; and a pressure sensitive adhesive layer present on one or both sides of the optical film.
壓敏黏合層由例如壓敏黏合劑組成物形成。具體而言, 壓敏黏合劑組成物被固化以產生壓敏黏合層。此處,固化壓敏黏合劑組成物的方法沒有特別限制,其中壓敏黏合劑組成物可藉由例如熱固性固化;光固化,例如紫外線照射;熱及光的雙重固化;或濕固化等已知固化方法來固化。因此,壓敏黏合層包含壓敏黏合劑組成物的至少一種固化產物。 The pressure-sensitive adhesive layer is formed of, for example, a pressure-sensitive adhesive composition. in particular, The pressure sensitive adhesive composition is cured to produce a pressure sensitive adhesive layer. Here, the method of curing the pressure-sensitive adhesive composition is not particularly limited, wherein the pressure-sensitive adhesive composition can be cured by, for example, thermosetting; photocuring, such as ultraviolet radiation; dual curing of heat and light; or moisture curing, etc. Curing method to cure. Therefore, the pressure-sensitive adhesive layer contains at least one cured product of the pressure-sensitive adhesive composition.
在本申請案中,術語「壓敏黏合劑組成物」指能夠在組成物固化之前及/或之後表現出壓敏黏合劑性質的組成物,且術語「壓敏黏合劑」的含義為眾所習知的。 In this application, the term "pressure-sensitive adhesive composition" refers to a composition capable of exhibiting properties of a pressure-sensitive adhesive before and/or after the composition is cured, and the meaning of the term "pressure-sensitive adhesive" is well known Known.
壓敏黏合劑組成物包含能夠表現出至少壓敏黏合劑性質的至少一種聚合物。此處,「壓敏黏合劑聚合物」指能夠在其固化及/或交聯之前及/或之後達成壓敏黏合劑性質的聚合物。 The pressure sensitive adhesive composition comprises at least one polymer capable of exhibiting at least pressure sensitive adhesive properties. Here, "pressure-sensitive adhesive polymer" refers to a polymer capable of achieving pressure-sensitive adhesive properties before and/or after its curing and/or crosslinking.
此外,壓敏黏合劑組成物可包含壓敏黏合劑聚合物作為主要組分。亦即,壓敏黏合劑組成物可包含比率為約50重量%或大於50重量%、55重量%或大於55重量%、60重量%或大於60重量%、65重量%或大於65重量%、70重量%或大於70重量%、75重量%或大於75重量%、80重量%或大於80重量%、85重量%或大於85重量%、90重量%或大於90重量%或者95重量%或大於95重量%的壓敏黏合劑聚合物。在另一實例中,所述比率可為約100重量%或小於100重量%或者約99重量%或小於99重量%左右。 In addition, the pressure-sensitive adhesive composition may contain a pressure-sensitive adhesive polymer as a main component. That is, the pressure-sensitive adhesive composition may contain a ratio of about 50% by weight or more, 55% by weight or more than 55% by weight, 60% by weight or more than 60% by weight, 65% by weight or more than 65% by weight, 70% by weight or more, 75% by weight or more than 75% by weight, 80% by weight or more than 80% by weight, 85% by weight or more than 85% by weight, 90% by weight or more than 90% by weight, or 95% by weight or more 95% by weight pressure sensitive adhesive polymer. In another example, the ratio may be about 100% by weight or less, or about 99% by weight or less.
壓敏黏合劑聚合物的類型沒有特別限制,其在本申請案中可無限制地應用,只要其為能夠表現出已知壓敏黏合劑功能的 聚合物(聚合物或類似物)即可。另一方面,由於本申請案是有關於光學疊層,因此選擇不顯著影響光學疊層的光學性質的聚合物作為壓敏黏合劑聚合物可為適宜的。例如,壓敏黏合劑聚合物可為丙烯酸聚合物。 The type of pressure-sensitive adhesive polymer is not particularly limited, and it can be used without limitation in this application as long as it is capable of exhibiting known pressure-sensitive adhesive functions. A polymer (polymer or the like) will suffice. On the other hand, since this application is about optical stacks, it may be appropriate to choose a polymer as the pressure sensitive adhesive polymer that does not significantly affect the optical properties of the optical stack. For example, the pressure sensitive adhesive polymer can be an acrylic polymer.
在本申請案中,術語「丙烯酸聚合物」可指構成作為聚合單元的(甲基)丙烯酸或其衍生物的酯化產物的聚合物。此處,(甲基)丙烯酸指丙烯酸或甲基丙烯酸。 In the present application, the term "acrylic acid polymer" may refer to a polymer constituting an esterification product of (meth)acrylic acid or a derivative thereof as a polymerized unit. Here, (meth)acrylic acid refers to acrylic acid or methacrylic acid.
在一個實例中,丙烯酸聚合物可包括(甲基)丙烯酸烷基酯單體的聚合單元。此外,(甲基)丙烯酸烷基酯單體可由下式5表示。亦即,丙烯酸聚合物可包括下式5的單體的聚合單元。 In one example, the acrylic polymer can include polymerized units of an alkyl (meth)acrylate monomer. In addition, the alkyl (meth)acrylate monomer may be represented by Formula 5 below. That is, the acrylic polymer may include polymerized units of monomers of Formula 5 below.
在本申請案中,當任何單體已形成聚合物時,術語「聚合單元」可指由單體在聚合物中形成的骨架。 In this application, when any monomer has formed a polymer, the term "polymerized unit" may refer to the backbone formed by the monomer in the polymer.
在式5中,Q為氫或烷基,且B為直鏈或支鏈烷基。慮及內聚力、玻璃轉變溫度及黏著性等,上式5中的B可為具有1至14個碳原子的直鏈、支鏈或環狀烷基。在另一實例中,式5的B中存在的烷基可為具有2至14、3至14、4至14、4至12或4至8個碳原子的直鏈、支鏈或環狀烷基。 In Formula 5, Q is hydrogen or an alkyl group, and B is a linear or branched alkyl group. In consideration of cohesive force, glass transition temperature, adhesiveness, etc., B in the above formula 5 may be a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms. In another example, the alkyl group present in B of Formula 5 can be a straight chain, branched chain or cyclic alkanes having 2 to 14, 3 to 14, 4 to 14, 4 to 12 or 4 to 8 carbon atoms base.
在一個實例中,式5中的Q可為烷基。在此種情況下,作為上式5的Q中存在的烷基,可使用具有1至20、1至16、1至12、1至8或1至4個碳原子的烷基。烷基可為直鏈、支鏈或環狀的。此外,烷基可任選地被一或多個取代基取代。 In one example, Q in Formula 5 may be an alkyl group. In this case, as the alkyl group present in Q of the above formula 5, an alkyl group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms can be used. Alkyl groups can be linear, branched or cyclic. In addition, an alkyl group may be optionally substituted with one or more substituents.
在另一實例中,式5中的Q可為氫。 In another example, Q in Formula 5 may be hydrogen.
慮及壓敏黏合劑聚合物的內聚力及玻璃轉變溫度,丙烯酸聚合物包括單體的聚合單元可為適宜的,其中Q為氫,且B為具有1至14個碳原子的直鏈或支鏈烷基。上式5的單體的實例可包括單體單元,例如(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)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸月桂酯及/或(甲基)丙烯酸十四烷基酯。在本申請案中,術語「(甲基)丙烯酸酯」用於指丙烯酸酯或甲基丙烯酸酯。一般而言,丙烯酸正丁酯用作式5的單體。 Considering the cohesion and glass transition temperature of the pressure-sensitive adhesive polymer, an acrylic polymer may be suitable including polymerized units of monomers wherein Q is hydrogen and B is a linear or branched chain having 1 to 14 carbon atoms. alkyl. Examples of monomers of the above formula 5 may include monomer units such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, tertiary butyl (meth)acrylate, second butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate base) 2-ethylbutyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate and/or (meth) ) myristyl acrylate. In this application, the term "(meth)acrylate" is used to refer to either acrylate or methacrylate. Generally, n-butyl acrylate is used as the monomer of formula 5.
在一個實例中,丙烯酸聚合物可包括式5的單體的聚合單元作為主要組分。亦即,以相關聚合物中的總單體的聚合單元的總和計,丙烯酸聚合物可以約50重量%或大於50重量%、55重量%或大於55重量%、60重量%或大於60重量%、65重量%或大於65重量%、70重量%或大於70重量%、75重量%或大於75重量%、80重量%或大於80重量%、85重量%或大於85重量%、 90重量%或大於90重量%或者95重量%或大於95重量%的比率包括其。在另一實例中,所述比率可為約100重量%或小於100重量%或者約99重量%或小於99重量%左右。 In one example, the acrylic polymer may include polymerized units of the monomer of Formula 5 as a main component. That is, the acrylic polymer can be about 50% by weight or greater, 55% by weight or greater, 60% by weight or greater than 60% by weight, based on the sum of the polymerized units of the total monomers in the relevant polymer , 65% by weight or more, 70% by weight or more than 70% by weight, 75% by weight or more than 75% by weight, 80% by weight or more than 80% by weight, 85% by weight or more than 85% by weight, A ratio of 90% by weight or more or 95% by weight or more is included therein. In another example, the ratio may be about 100% by weight or less, or about 99% by weight or less.
丙烯酸聚合物可更包括具有極性基團的可共聚單體的聚合單元作為附加聚合單元,以提高內聚力等。 The acrylic polymer may further include a polymerized unit of a copolymerizable monomer having a polar group as an additional polymerized unit to improve cohesion and the like.
此處,具有極性官能基的可共聚單體可指可與形成丙烯酸聚合物的其他化合物(例如(甲基)丙烯酸酯化合物)共聚的單體如上式5,且在共聚後可為側鏈或末端提供極性官能基。極性官能基可為例如,能夠藉由施加熱與下述多官能交聯劑反應以實施交聯結構或者用於改善壓敏黏合層的潤濕性的官能基。極性官能基可被例舉為例如羥基、羧基或其酸酐基、例如磺酸基或磷酸基等酸基、縮水甘油基、胺基或異氰酸酯基等。 Here, the copolymerizable monomer having a polar functional group may refer to a monomer that can be copolymerized with other compounds (such as (meth)acrylate compounds) forming an acrylic polymer such as the above formula 5, and may be a side chain or The terminal provides a polar functional group. The polar functional group may be, for example, a functional group capable of reacting with a polyfunctional crosslinking agent described below by applying heat to implement a crosslinked structure or for improving wettability of the pressure-sensitive adhesive layer. The polar functional group can be exemplified by, for example, a hydroxyl group, a carboxyl group or an acid anhydride group thereof, an acid group such as a sulfonic acid group or a phosphoric acid group, a glycidyl group, an amine group, or an isocyanate group, and the like.
具有極性基團的可共聚單體可為例如具有羥基的可共聚單體,且具體而言,可為具有羥基烷基的(甲基)丙烯酸酯。具有羥基的可共聚單體同時包括與形成丙烯酸聚合物的其他單體的可共聚位點、以及羥基,因此其可為能夠在聚合後為丙烯酸聚合物提供羥基的單體。 The copolymerizable monomer having a polar group may be, for example, a copolymerizable monomer having a hydroxyl group, and specifically, a (meth)acrylate having a hydroxyalkyl group. The copolymerizable monomer having a hydroxyl group includes both a copolymerizable site with other monomers forming an acrylic polymer, and a hydroxyl group, so it may be a monomer capable of providing a hydroxyl group to an acrylic polymer after polymerization.
具有羥基的可共聚單體可被例舉為(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯或(甲基)丙烯酸6-羥己酯等,但不限於此。應用丙烯酸4-羥丁酯作為具有羥基的可共聚單體可更有利於提高內聚力等。 Copolymerizable monomers having hydroxyl groups can be exemplified by 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or (meth)acrylic acid 6-hydroxyhexyl ester, etc., but not limited thereto. The use of 4-hydroxybutyl acrylate as a copolymerizable monomer with hydroxyl groups can be more beneficial to improve cohesion and the like.
構成丙烯酸聚合物的聚合單元之間的比率沒有特別限 制,其可在確保壓敏黏合劑聚合物的適當內聚力及玻璃轉變溫度的範圍內適當調整。例如,以100重量份的上式5的單體的聚合單元計,丙烯酸聚合物可包括比率在約0.1重量份至約30重量份範圍內的具有極性基團的可共聚單體的聚合單元。 The ratio between the polymerized units constituting the acrylic polymer is not particularly limited It can be properly adjusted within the range of ensuring proper cohesion and glass transition temperature of the pressure-sensitive adhesive polymer. For example, the acrylic polymer may include polymerized units of a copolymerizable monomer having a polar group in a ratio ranging from about 0.1 parts by weight to about 30 parts by weight based on 100 parts by weight of polymerized units of the monomer of Formula 5 above.
在本申請案中,除非另有說明,否則術語重量份可指各組分之間的重量比。在另一實例中,所述比率可為約0.5重量份或大於0.5重量份、0.7重量份或大於0.7重量份或者0.9重量份或大於0.9重量份,或者可為約25重量份或小於25重量份、20重量份或小於20重量份、15重量份或小於15重量份、10重量份或小於10重量份、5重量份或小於5重量份或者3重量份或小於3重量份,但此比率可慮及所期望的內聚力或潤濕性等而適當改變。 In the present application, unless otherwise specified, the term parts by weight may refer to a weight ratio between components. In another example, the ratio may be about 0.5 parts by weight or greater, 0.7 parts by weight or greater, or 0.9 parts by weight or greater, or may be about 25 parts by weight or less parts, 20 parts by weight or less than 20 parts by weight, 15 parts by weight or less than 15 parts by weight, 10 parts by weight or less than 10 parts by weight, 5 parts by weight or less than 5 parts by weight, or 3 parts by weight or less than 3 parts by weight, but the ratio It can be appropriately changed in consideration of desired cohesive force, wettability, and the like.
除具有羥基的可共聚單體之外,自控制聚合物的玻璃轉變溫度或賦予其他官能性的觀點來看,丙烯酸聚合物可包括作為具有極性基團的可共聚單體的其他可共聚單體的聚合單元。 In addition to the copolymerizable monomer having a hydroxyl group, the acrylic polymer may include other copolymerizable monomers as copolymerizable monomers having a polar group from the viewpoint of controlling the glass transition temperature of the polymer or imparting other functionality aggregation unit.
其他可共聚單體的實例可包括例如,例如含氮單體,例如(甲基)丙烯腈、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺或N-丁氧基甲基(甲基)丙烯醯胺;苯乙烯系單體,例如苯乙烯或甲基苯乙烯;(甲基)丙烯酸縮水甘油酯;或已知共聚單體,例如羧酸乙烯酯等,例如乙酸乙烯酯。以100重量份的式5的單體的聚合單元計,此種聚合單元可例如以20重量份或小於20重量份的比率包括在丙烯酸聚合物中。 Examples of other copolymerizable monomers may include, for example, nitrogen-containing monomers such as (meth)acrylonitrile, (meth)acrylamide, N-methyl(meth)acrylamide, N-vinylpyrrole pyridone, N-vinylcaprolactam or N-butoxymethyl(meth)acrylamide; styrenic monomers such as styrene or methylstyrene; glycidyl (meth)acrylate ; or known comonomers, such as vinyl carboxylates, etc., such as vinyl acetate. Such a polymerized unit may be included in the acrylic polymer at a ratio of, for example, 20 parts by weight or less based on 100 parts by weight of polymerized units of the monomer of Formula 5.
自改善例如壓敏黏合劑聚合物的內聚力、壓敏黏合劑效 能或潤濕性等物理性質的觀點來看,丙烯酸聚合物的物理性質亦可適當調整。 Self-improvement such as pressure-sensitive adhesive polymer cohesion, pressure-sensitive adhesive The physical properties of the acrylic polymer can also be appropriately adjusted from the viewpoint of physical properties such as performance and wettability.
在一個實例中,作為丙烯酸聚合物,可使用重量平均分子量(Mw)為800,000或大於800,000的聚合物。 In one example, as the acrylic polymer, a polymer having a weight average molecular weight (Mw) of 800,000 or more may be used.
在本申請案中,術語「重量平均分子量」為藉由凝膠滲透層析儀(gel permeation chromatograph,GPC)量測的標準聚苯乙烯的換算值,其中在本說明書中,除非另有說明,否則「分子量」可指「重量平均分子量」。當聚合物的分子量為800,000或大於800,000時,壓敏黏合劑的耐久性可保持在合適的範圍內。在另一實例中,分子量可為約850,000或大於850,000、900,000或大於900,000、950,000或大於950,000或者1,000,000或大於1,000,000,且可為2,500,000或小於2,500,000、2,000,000或小於2,000,000、1,800,000或小於1,800,000、1,600,000或小於1,600,000、1,400,000或小於1,400,000、1,200,000或小於1,200,000或者1,000,000或小於1,000,000。 In the present application, the term "weight average molecular weight" is the conversion value of standard polystyrene measured by gel permeation chromatography (gel permeation chromatography, GPC), wherein in this specification, unless otherwise specified, Otherwise "molecular weight" may refer to "weight average molecular weight". When the molecular weight of the polymer is 800,000 or more, the durability of the pressure-sensitive adhesive can be maintained in an appropriate range. In another example, the molecular weight can be about 850,000 or more than 850,000, 900,000 or more than 900,000, 950,000 or more than 950,000 or 1,000,000 or more than 1,000,000,000, and it can be 2,500,000 or less than 2,500,000, 2,000,000, 1,800,000 or less than 1,800,000, or less than 1,800,000, or less than 1,800,000 or less than 1,800,000. Less than 1,600,000, 1,400,000 or less, 1,200,000 or less, or 1,000,000 or less.
自確保壓敏黏合劑聚合物的壓敏黏合劑效能及流動性以及改善台階的嵌入性質的觀點來看,當具有壓敏黏合劑聚合物的壓敏黏合構件已被應用於台階式構件時,丙烯酸聚合物的玻璃轉變溫度(Tg)亦可被適當地調整。 From the viewpoint of ensuring the pressure-sensitive adhesive performance and fluidity of the pressure-sensitive adhesive polymer and improving the embedding properties of steps, when the pressure-sensitive adhesive member having the pressure-sensitive adhesive polymer has been applied to a stepped member, The glass transition temperature (Tg) of the acrylic polymer can also be appropriately adjusted.
在一個實例中,丙烯酸聚合物的玻璃轉變溫度可小於0℃。在另一實例中,玻璃轉變溫度可為-10℃或小於-10℃、-20℃或小於-20℃、-30℃或小於-30℃、-40℃或小於-40℃、-45℃或小 於-45℃或者-50℃或小於-50℃,且其下限沒有特別限制,但其可為-100℃或大於-100℃、-90℃或大於-90℃、-80℃或大於-80℃、-70℃或大於-70℃、-60℃或大於-60℃或者-55℃或大於-55℃。 In one example, the glass transition temperature of the acrylic polymer can be less than 0°C. In another example, the glass transition temperature may be -10°C or less, -20°C or less, -30°C or less, -40°C or less, -45°C or small At -45°C or -50°C or less than -50°C, and its lower limit is not particularly limited, but it may be -100°C or greater than -100°C, -90°C or greater than -90°C, -80°C or greater than -80°C °C, -70 °C or greater than -70 °C, -60 °C or greater than -60 °C, or -55 °C or greater than -55 °C.
此處,任何聚合物的玻璃轉變溫度可為例如,藉由將構成聚合物的單體的均聚物的玻璃轉變溫度及其配製重量比率代入已知的福克斯(Fox)方程式來計算的值。 Here, the glass transition temperature of any polymer may be, for example, a value calculated by substituting the glass transition temperature of a homopolymer of monomers constituting the polymer and its formulation weight ratio into the known Fox's equation.
丙烯酸聚合物可藉由已知的聚合方法製備。例如,藉由根據期望的重量比率合適地配製(甲基)丙烯酸酯單體及含極性基團可共聚單體及/或其他共聚單體等而獲得的單體混合物可應用於例如溶液聚合、光聚合、本體聚合、懸浮聚合或乳液聚合等慣常聚合方法,以製備丙烯酸聚合物。在聚合製程中,若需要,則亦可一起使用聚合起始劑、鏈轉移劑等。 Acrylic polymers can be prepared by known polymerization methods. For example, monomer mixtures obtained by appropriately formulating (meth)acrylate monomers and polar group-containing copolymerizable monomers and/or other comonomers etc. according to desired weight ratios can be applied, for example, to solution polymerization, Conventional polymerization methods such as photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization to prepare acrylic polymers. In the polymerization process, if necessary, a polymerization initiator, a chain transfer agent, and the like may also be used together.
在一個實例中,自吸收紫外線(例如,波長為380奈米或大於380奈米的紫外線)並對光學疊層賦予阻擋紫外線的功能的觀點來看,除了壓敏黏合劑聚合物之外,壓敏黏合劑組成物更包含紫外線吸收劑。已進行各種嘗試以在藉由將各種紫外線吸收劑應用於壓敏黏合劑組成物來確保特別是對藍色光的吸收效能的同時不損害最終產品的視覺欣賞性質,但在改善產品的視覺欣賞性質方面存在限制。 In one example, from the viewpoint of absorbing ultraviolet rays (for example, ultraviolet rays having a wavelength of 380 nm or more) and imparting a function of blocking ultraviolet rays to the optical laminate, in addition to the pressure-sensitive adhesive polymer, the pressure-sensitive adhesive polymer The sensitive adhesive composition further includes an ultraviolet absorber. Various attempts have been made to ensure the absorption performance of blue light in particular by applying various ultraviolet absorbers to pressure-sensitive adhesive compositions without impairing the visual appreciation properties of the final product, but in improving the visual appreciation properties of the product. There are limitations.
本發明人已確認到,藉由應用特定化合物作為應用於壓敏黏合劑組成物的紫外線吸收劑,或者藉由將特定化合物及另一化合物的組合應用於壓敏黏合劑組成物,可達成本申請案的目 的,並且得出了本發明。 The present inventors have confirmed that the cost can be achieved by applying a specific compound as an ultraviolet absorber applied to a pressure-sensitive adhesive composition, or by applying a combination of a specific compound and another compound to a pressure-sensitive adhesive composition. The purpose of the application , and have drawn the present invention.
在本申請案中,術語「紫外線吸收能力」可指在波長的透射率光譜中、例如在介於10奈米至450奈米範圍內的波長中的任何波長處或者在上述範圍內的波長的整個區域內顯示出最小透射率或者在波長的吸收率光譜中、例如在介於10奈米至450奈米範圍內的波長中的任何波長處或在上述範圍內的波長的整個區域內顯示出最大吸收率的物理性質。 In the present application, the term "ultraviolet absorbing power" may refer to the transmittance spectrum of wavelengths, such as at any wavelength in the wavelength range of 10 nm to 450 nm or within the above-mentioned range. Shows minimum transmittance over the entire region or in the absorbance spectrum of wavelengths, for example at any wavelength in the range of wavelengths between 10 nm to 450 nm or over the entire range of wavelengths in the above range The physical property of maximum absorption.
在本申請案中,術語「最大吸收波長」可指表示最小透射率或最大吸收率的波長。 In this application, the term "maximum absorption wavelength" may refer to the wavelength representing the minimum transmittance or maximum absorption.
藉由包含特定化合物、具體而言丙二腈系化合物作為紫外線吸收劑,壓敏黏合劑組成物可具有優異的阻擋具有380奈米或大於380奈米的藍色區域的光的效能。因此,當具有由壓敏黏合劑組成物形成的壓敏黏合層的光學疊層(例如,偏光板)被應用於在藍色區域中易受曝光影響的有機發光二極體等時,可將有機發光二極體的藍色光源的壽命縮短最小化。 By including a specific compound, specifically, a malononitrile-based compound as an ultraviolet absorber, the pressure-sensitive adhesive composition can have excellent performance in blocking light having a blue region of 380 nm or more. Therefore, when an optical laminate (for example, a polarizing plate) having a pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive composition is applied to an organic light emitting diode or the like susceptible to light exposure in a blue region, the The lifetime shortening of the blue light source of the OLED is minimized.
此外,在本申請案中,藉由包含下述特定丙二腈系化合物作為紫外線吸收劑,壓敏黏合劑組成物可使最終產品(例如由壓敏黏合劑組成物形成的偏光板)的顏色值的變化最小化。 In addition, in this application, the pressure-sensitive adhesive composition can make the color of the final product (such as a polarizing plate formed of the pressure-sensitive adhesive composition) by including the following specific malononitrile-based compound as an ultraviolet absorber. The change in value is minimized.
亦即,本申請案的光學疊層被設計成使被施加以形成構成所述光學疊層的壓敏黏合層的壓敏黏合劑組成物包含特定化合物作為紫外線吸收劑,因此即使當所述光學疊層已被暴露於紫外線等時,其亦可同時確保優異的耐久性,而不會顯著降低光學性 質(例如,視覺欣賞性質,例如透射率及色差)。 That is, the optical laminate of the present application is designed such that the pressure-sensitive adhesive composition applied to form the pressure-sensitive adhesive layer constituting the optical laminate contains a specific compound as an ultraviolet absorber, so that even when the optical It also ensures excellent durability when the laminate has been exposed to ultraviolet rays, etc., without significantly degrading optical properties properties (eg, visual appreciation properties such as transmittance and chromatic aberration).
如上所述,在本申請案中,作為應用於壓敏黏合劑組成物的紫外線吸收劑,包含特定化合物,具體而言丙二腈系化合物。此處,丙二腈系化合物指包括丙二腈(NC≡CC≡N)的衍生物的化合物。 As described above, in the present application, a specific compound, specifically, a malononitrile-based compound is included as the ultraviolet absorber used in the pressure-sensitive adhesive composition. Here, the malononitrile-based compound refers to a compound including a derivative of malononitrile (NC≡CC≡N).
在一個實例中,作為應用於壓敏黏合劑組成物的丙二腈系化合物,亦可應用最大吸收波長在特定範圍內的丙二腈系化合物。亦即,丙二腈系化合物的最大吸收波長可在特定範圍內。具體而言,丙二腈系化合物的最大吸收波長可介於紫外線範圍內,例如10奈米至450奈米。在另一實例中,丙二腈系化合物的最大吸收波長可介於340奈米或大於340奈米、350奈米或大於350奈米或者360奈米或大於360奈米的範圍內,且介於448奈米或小於448奈米或者446奈米或小於446奈米的範圍內。 In one example, as the malononitrile compound used in the pressure-sensitive adhesive composition, a malononitrile compound having a maximum absorption wavelength within a specific range may also be used. That is, the maximum absorption wavelength of the malononitrile-based compound may be within a specific range. Specifically, the maximum absorption wavelength of the malononitrile compound may be in the ultraviolet range, for example, 10 nm to 450 nm. In another example, the maximum absorption wavelength of the malononitrile compound may be within a range of 340 nm or greater, 350 nm or greater, or 360 nm or greater, and between In the range of 448 nm or less or 446 nm or less.
在本申請案中,將具有特定結構的丙二腈系化合物應用於壓敏黏合劑組成物。具體而言,在本申請案中,應用於壓敏黏合劑組成物的紫外線吸收劑為丙二腈系化合物,具體而言,為下式1的化合物:[式1]
在式1中,R1至R5各自獨立地為氫、烷基、-OX1或-NX1 2,其中X1為氫或烷基,但R1至R5中的至少一者為-OX1或-NX1 2。
In
在一個實例中,式1中的R1至R5可各自獨立地為氫或-OX1,但R1至R5中的兩者或更多者為-OX1。具體而言,R1至R5中的兩者為-OX1可為適宜的。
In one example, R 1 to R 5 in
在另一實例中,上式1中的R1至R5中的兩者可為-OX1或-NX1 2。在此種情況下,當式1中的R1至R5中的任一者為-OX1或-NX1 2時,在具有其的間位處的取代基亦可為-OX1或-NX1 2。
In another example, two of R 1 to R 5 in
在另一實例中,上式1中的R1、R3及R5中的兩者可為-OX1或-NX1 2。具體而言,當上式1中的R3為-OH時,R1或R5(其為具有R3的間位處的官能基)可為-OX1(其中X1為烷基),且更具體而言,當上式1中的R3為-OH時,R5為-OX1(其中X1為烷基)可為適宜的。
In another example, two of R 1 , R 3 and R 5 in
在一個實例中,壓敏黏合劑組成物亦可單獨包含丙二腈系化合物,具體而言,僅上式1的化合物作為紫外線吸收劑。
In one example, the pressure-sensitive adhesive composition may also include a malononitrile compound alone, specifically, only the compound of the
在本申請案中,作為應用於壓敏黏合劑組成物的紫外線吸收劑,不同種類的化合物亦可進一步與上述式1的丙二腈系化
合物一起包括在內。
In the present application, as the ultraviolet absorber applied to the pressure-sensitive adhesive composition, different types of compounds can also be further combined with the malononitrile of the
在一個實例中,壓敏黏合劑組成物可更包含吡唑啉系化合物。當壓敏黏合劑組成物更包含吡唑啉系化合物時,用壓敏黏合劑組成物設計的最終產品能夠以更佳的效能阻擋波長在380奈米或大於380奈米的藍色區域中的光,由此將易受藍色光照射影響的有機發光二極體的藍色光源的壽命降低最小化。此外,當紫外線吸收劑如上所述混合時,用壓敏黏合劑組成物設計的最終產品的顏色值的變化可最小化,且其耐久性可被改善。 In one example, the pressure-sensitive adhesive composition may further include a pyrazoline-based compound. When the pressure-sensitive adhesive composition further includes a pyrazoline-based compound, the final product designed with the pressure-sensitive adhesive composition can block light in the blue region with a wavelength of 380 nm or greater than 380 nm with better efficiency. light, thereby minimizing the lifetime reduction of the blue light source of the organic light-emitting diode, which is susceptible to blue light irradiation. In addition, when the ultraviolet absorber is mixed as described above, the change in the color value of the final product designed with the pressure-sensitive adhesive composition can be minimized, and its durability can be improved.
在本申請案中,吡唑啉系化合物可指包括衍生自吡唑啉的結構的化合物,即吡唑啉衍生物。吡唑啉為具有C3H6N2的分子式的不飽和雜環化合物。 In the present application, the pyrazoline-based compound may refer to a compound including a structure derived from pyrazoline, that is, a pyrazoline derivative. Pyrazoline is an unsaturated heterocyclic compound having a molecular formula of C 3 H 6 N 2 .
在本申請案中,在將與上述丙二腈系化合物一起應用的吡唑啉系化合物中,特別地,可應用最大吸收波長在特定範圍內的化合物。具體而言,吡唑啉系化合物的最大吸收波長可介於10奈米至410奈米範圍內。在另一實例中,其可為100奈米或大於100奈米、200奈米或大於200奈米、300奈米或大於300奈米、350奈米或大於350奈米、360奈米或大於360奈米、370奈米或大於370奈米、380奈米或大於380奈米或者385奈米或大於385奈米,且可為405奈米或小於405奈米或者400奈米或小於400奈米。 In the present application, among the pyrazoline-based compounds to be used together with the above-mentioned malononitrile-based compounds, in particular, compounds having a maximum absorption wavelength within a specific range can be used. Specifically, the maximum absorption wavelength of the pyrazoline compound may be in the range of 10 nm to 410 nm. In another example, it may be 100 nm or greater, 200 nm or greater, 300 nm or greater, 350 nm or greater, 360 nm or greater 360 nm, 370 nm or greater, 380 nm or greater, or 385 nm or greater, and may be 405 nm or less or 400 nm or less Meter.
在本申請案中,吡唑啉系化合物(其可與作為紫外線吸收劑的丙二腈系化合物一起被配製至壓敏黏合劑組成物)可由下
式2表示:
式2中的R6至R9各自獨立地為氫、烷基或下式3的取代基,但R6至R9中的至少一者為式3的取代基:
在上式3中,A可為單鍵、伸烷基、伸烯基、伸炔基、-C(=O)O-或-OC(=O)-。在上式3中,R10至R14可各自獨立地為氫、烷基、烯基、炔基、芳基、烷氧基、硝基、胺基或羥基。上式3中的A可鍵結至式2的雜不飽和環。 In Formula 3 above, A may be a single bond, an alkylene group, an alkenylene group, an alkynylene group, -C(=O)O- or -OC(=O)-. In Formula 3 above, R 10 to R 14 may each independently be hydrogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, nitro, amino, or hydroxyl. A in Formula 3 above may be bonded to the heterounsaturated ring of Formula 2.
此處,除非另有說明,否則術語「烷基」、「烷氧基」或「伸烷基」可各自獨立地指具有1至20、1至16、1至12、1至8個碳原子或1至4個碳原子的直鏈、支鏈或環狀烷基、烷氧基或伸烷基。烷基、烷氧基或伸烷基可任選地被一或多個取代基取代。 Here, unless otherwise stated, the terms "alkyl", "alkoxy" or "alkylene" may each independently refer to a group having 1 to 20, 1 to 16, 1 to 12, 1 to 8 carbon atoms Or a linear, branched or cyclic alkyl, alkoxy or alkylene group of 1 to 4 carbon atoms. An alkyl, alkoxy or alkylene group may be optionally substituted with one or more substituents.
此處,除非另有說明,否則術語「烯基」、「伸烯基」、「炔基」或「伸炔基」可各自獨立地指具有2至20、2至16、2至12、2至8或2至4個碳原子的直鏈、支鏈或環狀烯基、伸烯基、炔基或伸炔基。烯基、伸烯基、炔基或伸炔基可任選地被一或多個取代基取代。 Here, unless otherwise stated, the terms "alkenyl", "alkenylene", "alkynyl" or "alkynyl" may each independently refer to Straight-chain, branched or cyclic alkenyl, alkenylene, alkynyl or alkynylene of 8 or 2 to 4 carbon atoms. An alkenyl, alkenylene, alkynyl or alkynyl group may be optionally substituted with one or more substituents.
此處,術語「單鍵」是其中在對應位點不存在單獨原子的狀態,且例如,當A為單鍵時,芳環直接連接至式2的雜不飽和環。 Here, the term "single bond" is a state in which there is no single atom at the corresponding position, and for example, when A is a single bond, an aromatic ring is directly connected to the heterounsaturated ring of Formula 2.
在上式3中,A可為單鍵、伸烷基、伸烯基、-C(=O)O-或-OC(=O)-,且具體而言,可為單鍵、具有2至6個碳原子的伸烯基或具有2至6個碳原子的伸烷基。 In the above formula 3, A may be a single bond, an alkylene group, an alkenylene group, -C(=O)O- or -OC(=O)-, and specifically, may be a single bond, having 2 to Alkenylene of 6 carbon atoms or alkylene of 2 to 6 carbon atoms.
在上式3中,R10至R14可各自獨立地為氫、烷基、烯基、炔基、胺基或羥基。適宜地,上式3中的R10至R14可各自獨立地為氫、烷基、烯基、炔基或羥基。適宜地,上式3中的R10至R14可各自獨立地為氫或烷基,其中烷基可更適宜地為具有1至12個碳原子的直鏈或支鏈烷基。 In the above formula 3, R 10 to R 14 may each independently be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an amino group, or a hydroxyl group. Suitably, R 10 to R 14 in Formula 3 above may each independently be hydrogen, alkyl, alkenyl, alkynyl or hydroxyl. Suitably, R 10 to R 14 in the above formula 3 may each independently be hydrogen or an alkyl group, wherein the alkyl group may more suitably be a linear or branched chain alkyl group having 1 to 12 carbon atoms.
在一個實例中,上式2中的R6、R7及R9中的至少一者可為上式3的取代基。此時,上式2中的R8可為氫。 In one example, at least one of R 6 , R 7 and R 9 in the above formula 2 may be a substituent of the above formula 3. At this time, R 8 in the above formula 2 may be hydrogen.
在一個實例中,上式2中的R6、R7及R9亦可為式3的取代基。其中,當上式2中的R9為式3的取代基時,式3中的A可為伸烯基。於是,此時,在構成R6及R7的式3的取代基中,A為單鍵可為適宜的。 In one example, R 6 , R 7 and R 9 in Formula 2 above may also be substituents in Formula 3. Wherein, when R9 in the above formula 2 is a substituent of formula 3, A in formula 3 can be an alkenylene group. Therefore, at this time, in the substituents of formula 3 constituting R 6 and R 7 , it may be appropriate that A is a single bond.
此處,當式2中的R9為式3的取代基(其中式3中的A為伸烯基)時,慮及化合物中存在的碳-碳或碳-氮之間的雙鍵或共軛位點改善紫外線吸收能力,上式3中的A亦可為具有2至6個碳原子或2至4個碳原子的共軛伸烯基。 Here, when R in Formula 2 is a substituent of Formula 3 (A in Formula 3 is an alkenyl group), the carbon-carbon or carbon-nitrogen existing in the compound is taken into account. The conjugated site improves the ultraviolet absorbing ability, and A in the above formula 3 may also be a conjugated alkenyl group having 2 to 6 carbon atoms or 2 to 4 carbon atoms.
在另一實例中,作為應用於壓敏黏合劑組成物的紫外線吸收劑,除了吡唑啉系化合物之外的其他化合物亦可與上述式1的丙二腈系化合物一起被進一步包括在內。具體而言,壓敏黏合劑組成物可更包含丙二酸系化合物以及如上所述的式1的丙二腈系化合物作為紫外線吸收劑。因此,用壓敏黏合劑組成物設計的最終產品的視覺欣賞性質的劣化可被最小化,且當此種最終產品應用於有機發光二極體,特別是塑膠有機發光二極體時,其藍色光源的壽命縮短可被最小化。
In another example, as the ultraviolet absorber applied to the pressure-sensitive adhesive composition, other compounds other than the pyrazoline-based compound may be further included together with the malononitrile-based compound of
在本申請案中,除了丙二腈系化合物之外,當丙二酸系化合物進一步應用於壓敏黏合劑組成物作為紫外線吸收劑時,在丙二酸系化合物中可應用最大吸收波長在特定範圍內的丙二酸系化合物。此時,丙二酸系化合物的最大吸收波長可介於350奈米至410奈米的範圍內。在另一實例中,最大吸收波長可為360奈米或大於360奈米、370奈米或大於370奈米或者380奈米或大於380奈米,且可為405奈米或小於405奈米、400奈米或小於400奈米、390奈米或小於390奈米或者385奈米或小於385奈米。 In the present application, in addition to the malononitrile compound, when the malonate compound is further applied to the pressure-sensitive adhesive composition as an ultraviolet absorber, the maximum absorption wavelength can be used in the malonate compound at a specific Malonic acid compounds in the range. At this time, the maximum absorption wavelength of the malonate-based compound may be in the range of 350 nm to 410 nm. In another example, the wavelength of maximum absorption can be at or above 360 nm, at or above 370 nm, or at or above 380 nm, and can be at or below 405 nm, 400 nm or less, 390 nm or less, or 385 nm or less.
在本申請案中,丙二酸系化合物可指包括衍生自丙二酸(丙二酸酯)的結構的化合物,即丙二酸的衍生物。丙二酸為具 有C3H4O4的分子式的不飽和雜鏈化合物。 In the present application, the malonate-based compound may refer to a compound including a structure derived from malonate (malonate), that is, a derivative of malonate. Malonic acid is an unsaturated heterochain compound having the molecular formula C3H4O4 .
在一個實例中,丙二酸系化合物可由下式4表示:
在式4中,R15至R19各自獨立地為氫、烷基、-OX2或-NX2 2,其中X2為氫或烷基,但R15至R19中的至少一者為-OX2或-NX2 2,且R20或R21為氫或烷基。 In Formula 4, R 15 to R 19 are each independently hydrogen, alkyl, -OX 2 or -NX 2 2 , wherein X 2 is hydrogen or alkyl, but at least one of R 15 to R 19 is - OX 2 or —NX 2 2 , and R 20 or R 21 is hydrogen or alkyl.
在式4中,R15至R19可各自獨立地為氫或-NX2 2。此外,此處,R15至R19中的至少一者亦可為-NX2 2。具體而言,式4中的R17為-NX2 2為適宜的。 In Formula 4, R 15 to R 19 may each independently be hydrogen or —NX 2 2 . In addition, here, at least one of R 15 to R 19 may also be -NX 2 2 . Specifically, R 17 in Formula 4 is preferably -NX 2 2 .
在一個實例中,式4中的R17可為-NX2 2,其中式4中的R15至R16及R18至R19可各自獨立地為氫、烷基或-OX2。此時,在上式4中,R20及R21二者可為烷基,且具體而言,可為具有1至4個碳原子的直鏈烷基。 In one example, R 17 in Formula 4 may be -NX 2 2 , wherein R 15 to R 16 and R 18 to R 19 in Formula 4 may each independently be hydrogen, alkyl or -OX 2 . At this time, in Formula 4 above, both R 20 and R 21 may be an alkyl group, and specifically, may be a linear alkyl group having 1 to 4 carbon atoms.
作為存在於上式4中的R15至R19中的任一者、或R20至R21中的任一者中的烷基,可使用具有1至20、1至16、1至12、 1至8或1至4個碳原子的烷基。 As the alkyl group present in any one of R 15 to R 19 in the above formula 4, or any one of R 20 to R 21 , there can be used those having 1 to 20, 1 to 16, 1 to 12, An alkyl group of 1 to 8 or 1 to 4 carbon atoms.
在本申請案中,慮及本申請案的目的,可調整應用於壓敏黏合劑組成物的紫外線吸收劑的含量。以100重量份的壓敏黏合劑聚合物計,所述壓敏黏合劑組成物可包含比率為0.01重量份至10重量份的紫外線吸收劑。在另一實例中,所述比率可為0.1重量份或大於0.1重量份、0.5重量份或大於0.5重量份、1重量份或大於1重量份或者1.5重量份或大於1.5重量份,且可為9重量份或小於9重量份、7重量份或小於7重量份或者5重量份或小於5重量份。此處,當丙二腈化合物單獨應用於壓敏黏合劑組成物作為紫外線吸收劑時,紫外線吸收劑的比率可指單一化合物的比率,且當丙二腈系化合物及丙二酸系或吡唑啉系化合物一起應用時,其亦可指所應用的紫外線吸收劑的總含量。 In the present application, the content of the ultraviolet absorber applied to the pressure-sensitive adhesive composition may be adjusted in consideration of the purpose of the present application. The pressure sensitive adhesive composition may include the ultraviolet absorber in a ratio of 0.01 to 10 parts by weight based on 100 parts by weight of the pressure sensitive adhesive polymer. In another example, the ratio may be 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, or 1.5 parts by weight or more, and may be 9 parts by weight or less, 7 parts by weight or less than 7 parts by weight, or 5 parts by weight or less than 5 parts by weight. Here, when the malononitrile compound is used alone in the pressure-sensitive adhesive composition as an ultraviolet absorber, the ratio of the ultraviolet absorber may refer to the ratio of a single compound, and when the malononitrile compound and the malonate or pyrazole When the morphine compound is used together, it may also refer to the total content of the applied ultraviolet absorber.
在另一實例中,壓敏黏合劑組成物中的丙二腈系化合物的比率可獨立地調整。具體而言,以100重量份的壓敏黏合劑聚合物計,壓敏黏合劑組成物可包含比率在0.01重量份至10重量份範圍內的上式1的丙二腈系化合物。在另一實例中,所述比率可為0.1重量份或大於0.1重量份、0.5重量份或大於0.5重量份、1重量份或大於1重量份或者2重量份或大於2重量份,且可為9重量份或小於9重量份、8重量份或小於8重量份、7重量份或小於7重量份、6重量份或小於6重量份、5重量份或小於5重量份或者4.5重量份或小於4.5重量份。
In another example, the ratio of the malononitrile compound in the pressure sensitive adhesive composition can be adjusted independently. Specifically, based on 100 parts by weight of the pressure-sensitive adhesive polymer, the pressure-sensitive adhesive composition may include the malononitrile compound of the
此時,當壓敏黏合劑組成物更包含吡唑啉系化合物及丙 二腈系化合物時,吡唑啉系化合物的比率對丙二腈系化合物的比率亦可獨立地調整。具體而言,以100重量份的丙二腈系化合物計,吡唑啉系化合物的比率可介於1重量份至30重量份範圍內。在另一實例中,所述比率可為2重量份或大於2重量份、3重量份或大於3重量份、4重量份或大於4重量份、5重量份或大於5重量份或者6重量份或大於6重量份,且可為29重量份或小於29重量份、28重量份或小於28重量份、27重量份或小於27重量份、26重量份或小於26重量份、25重量份或小於25重量份、24重量份或小於24重量份、23重量份或小於23重量份、22重量份或小於22重量份、21重量份或小於21重量份或者20重量份或小於20重量份。 At this time, when the pressure-sensitive adhesive composition further includes a pyrazoline compound and acrylic In the case of a dinitrile-based compound, the ratio of the pyrazoline-based compound to the ratio of the malononitrile-based compound can also be adjusted independently. Specifically, based on 100 parts by weight of the malononitrile compound, the ratio of the pyrazoline compound may range from 1 part by weight to 30 parts by weight. In another example, the ratio may be 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, or 6 parts by weight Or greater than 6 parts by weight, and can be 29 parts by weight or less than 29 parts by weight, 28 parts by weight or less than 28 parts by weight, 27 parts by weight or less than 27 parts by weight, 26 parts by weight or less than 26 parts by weight, 25 parts by weight or less 25 parts by weight, 24 parts by weight or less than 24 parts by weight, 23 parts by weight or less than 23 parts by weight, 22 parts by weight or less than 22 parts by weight, 21 parts by weight or less than 21 parts by weight or 20 parts by weight or less than 20 parts by weight.
在另一實例中,當壓敏黏合劑組成物更包含丙二酸系化合物以及丙二腈系化合物時,丙二酸系化合物的比率對丙二腈系化合物的比率亦可獨立地調整。具體而言,以100重量份的丙二腈系化合物計,丙二酸系化合物的比率可介於10重量份至90重量份範圍內。在另一實例中,所述比率可為15重量份或大於15重量份、20重量份或大於20重量份、30重量份或大於30重量份、31重量份或大於31重量份、32重量份或大於32重量份或者33重量份或大於33重量份,且可為85重量份或小於85重量份、80重量份或小於80重量份、75重量份或小於75重量份、70重量份或小於70重量份、69重量份或小於69重量份、68重量份或小於68重量份或者67重量份或小於67重量份。 In another example, when the pressure-sensitive adhesive composition further includes a malonate-based compound and a malononitrile-based compound, the ratio of the malonate-based compound to the ratio of the malononitrile-based compound can also be adjusted independently. Specifically, based on 100 parts by weight of the malononitrile compound, the ratio of the malonate compound may range from 10 parts by weight to 90 parts by weight. In another example, the ratio may be 15 parts by weight or greater, 20 parts by weight or greater, 30 parts by weight or greater, 31 parts by weight or greater, 32 parts by weight Or more than 32 parts by weight or 33 parts by weight or more than 33 parts by weight, and can be 85 parts by weight or less than 85 parts by weight, 80 parts by weight or less than 80 parts by weight, 75 parts by weight or less than 75 parts by weight, 70 parts by weight or less 70 parts by weight, 69 parts by weight or less than 69 parts by weight, 68 parts by weight or less than 68 parts by weight, or 67 parts by weight or less than 67 parts by weight.
壓敏黏合劑組成物可更包含交聯劑。交聯劑可為多官能交聯劑。例如,交聯劑可藉由施加熱與壓敏黏合劑聚合物反應,以形成交聯結構。在一個實例中,在包含壓敏黏合劑組成物的固化產物的壓敏黏合層中,壓敏黏合劑聚合物可以藉由交聯劑進行交聯的狀態存在。 The pressure-sensitive adhesive composition may further include a crosslinking agent. The crosslinking agent can be a multifunctional crosslinking agent. For example, the cross-linking agent can react with the pressure-sensitive adhesive polymer by applying heat to form a cross-linking structure. In one example, in the pressure-sensitive adhesive layer including the cured product of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive polymer may exist in a state of being cross-linked by a cross-linking agent.
作為交聯劑,例如,可使用交聯劑,例如異氰酸酯交聯劑、環氧交聯劑、氮丙啶交聯劑及金屬螯合物交聯劑,但不限於此。作為異氰酸酯交聯劑,可例舉多官能異氰酸酯化合物,例如甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異硼二異氰酸酯、四甲基二甲苯二異氰酸酯或者藉由多官能異氰酸酯化合物與例如三羥甲基丙烷等多元醇化合物反應而獲得的化合物;作為環氧交聯劑,可例舉選自由乙二醇二縮水甘油醚、三縮水甘油醚、三羥甲基丙烷三縮水甘油基三縮水甘油醚、N,N,N’,N’-四縮水甘油基乙二胺及甘油二縮水甘油醚組成的群組中的一或多種;且作為氮丙啶交聯劑,可例舉選自由N,N’-甲苯-2,4-雙(1-氮丙啶甲醯胺)、N,N’-二苯基甲烷-4,4’-雙(1-氮丙啶甲醯胺)、三乙烯三聚氰胺、二間苯二醯-1-(2-甲基氮丙啶)(bisisoprothaloyl-1-(2-methyl aziridine))及三-1-氮丙啶基氧化膦組成的群組中的一或多種,但不限於此。此外,金屬螯合物交聯劑可例舉為其中例如鋁、鐵、鋅、錫、鈦、銻、鎂及/或釩等多價金屬與乙醯丙酮或乙醯乙酸乙酯等配位的化合物,但不限於此。 As the crosslinking agent, for example, a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent may be used, but is not limited thereto. As the isocyanate crosslinking agent, polyfunctional isocyanate compounds such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate Or a compound obtained by reacting a polyfunctional isocyanate compound with a polyol compound such as trimethylolpropane; as an epoxy crosslinking agent, it may be selected from ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane, etc. One or more of the group consisting of hydroxymethylpropane triglycidyl triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine and glycerol diglycidyl ether; and as aziridine Pyridine cross-linking agent, can for example be selected from N,N'-toluene-2,4-bis(1-aziridine carboxamide), N,N'-diphenylmethane-4,4'-bis( 1-Aziridine Formamide), Triethylenemelamine, Bisisoprothaloyl-1-(2-methylaziridine) (bisisoprothaloyl-1-(2-methyl aziridine)) and Tris-1-Aziridine One or more of the group consisting of pyridyl phosphine oxides, but not limited thereto. In addition, the metal chelate crosslinking agent can be exemplified as one in which polyvalent metals such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and/or vanadium are coordinated with acetylacetone or ethyl acetylacetate, etc. compounds, but not limited to them.
以100重量份的壓敏黏合劑聚合物計,壓敏黏合劑組成 物可包含例如比率為0.01重量份至10重量份的交聯劑,但不限於此。慮及壓敏黏合劑的內聚力或耐久性等,所述比率可適當地改變。例如,在另一實例中,所述比率可為約9重量份或小於9重量份、8重量份或小於8重量份、7重量份或小於7重量份、6重量份或小於6重量份、5重量份或小於5重量份、4重量份或小於4重量份、3重量份或小於3重量份、2重量份或小於2重量份、1重量份或小於1重量份、0.5重量份或小於0.5重量份或者0.1重量份或小於0.1重量份,或者亦可為0.05重量份或大於0.05重量份左右。 Based on 100 parts by weight of the pressure-sensitive adhesive polymer, the composition of the pressure-sensitive adhesive The compound may include, for example, a crosslinking agent in a ratio of 0.01 to 10 parts by weight, but is not limited thereto. The ratio may be appropriately changed in consideration of cohesion or durability of the pressure-sensitive adhesive, or the like. For example, in another example, the ratio may be about 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less than 5 parts by weight, 4 parts by weight or less than 4 parts by weight, 3 parts by weight or less than 3 parts by weight, 2 parts by weight or less than 2 parts by weight, 1 part by weight or less than 1 part by weight, 0.5 parts by weight or less 0.5 parts by weight or 0.1 parts by weight or less than 0.1 parts by weight, or 0.05 parts by weight or more than 0.05 parts by weight.
為防止變黃等,除了所述組分之外,可向壓敏黏合層中進一步添加選自由抗氧化劑、紫外線穩定劑、熱穩定劑、塑化劑、抗靜電劑、填料、消泡劑、界面活性劑、成核劑、阻燃劑、耐候穩定劑、潤滑劑及離型劑組成的群組中的一或多種添加劑,以使得可達成本發明的目的。 In order to prevent yellowing and the like, in addition to the components, a group selected from antioxidants, ultraviolet stabilizers, heat stabilizers, plasticizers, antistatic agents, fillers, defoamers, One or more additives in the group consisting of surfactant, nucleating agent, flame retardant, weather-resistant stabilizer, lubricant and release agent, so that the purpose of the present invention can be achieved.
壓敏黏合劑組成物可更包含溶劑。溶劑可包括芳族烴,例如甲苯、苯及二甲苯;脂族烴,例如環己烷及十氫化萘;酯,例如乙酸乙酯及乙酸丁酯;酮,例如丙酮、甲乙酮及甲基異丁基酮;醇,例如甲醇、乙醇、異丙醇、丁醇、異丁醇、甲基溶纖劑、乙基溶纖劑及丁基溶纖劑;醚,例如四氫呋喃及二噁烷;鹵代烴,例如二氯甲烷、氯仿及四氯化碳;二甲基甲醯胺;二甲基亞碸等。該些溶劑可單獨使用或以兩種或更多種的組合形式使用。 The pressure-sensitive adhesive composition may further include a solvent. Solvents may include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as cyclohexane and decahydronaphthalene; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl Alcohols, such as methanol, ethanol, isopropanol, butanol, isobutanol, methyl cellosolve, ethyl cellosolve and butyl cellosolve; ethers, such as tetrahydrofuran and dioxane; halogenated hydrocarbons, For example, dichloromethane, chloroform, and carbon tetrachloride; dimethylformamide; dimethylsulfoxide, etc. These solvents may be used alone or in combination of two or more.
在本申請案中,壓敏黏合劑組成物可具有更顯著的效 果,尤其是當光學疊層為偏光板時。具體而言,當光學膜為偏光器時,光學疊層可為偏光板,且特別地,施加由壓敏黏合劑組成物構成的壓敏黏合層可為重要的。在下文中,光學疊層及偏光板亦可在相同的意義上使用。 In this application, the pressure-sensitive adhesive composition can have more significant effect effect, especially when the optical stack is a polarizer. Specifically, when the optical film is a polarizer, the optical laminate may be a polarizing plate, and in particular, it may be important to apply a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition. Hereinafter, optical laminates and polarizing plates can also be used in the same sense.
在本申請案中,術語「偏光器」意指具有偏光功能的膜、片材或元件。偏光器是能夠自在各種方向上振動的入射光提取在一個方向上振動的光的功能元件。 In this application, the term "polarizer" means a film, sheet or element having a polarizing function. A polarizer is a functional element capable of extracting light vibrating in one direction from incident light vibrating in various directions.
偏光器可為吸收偏光器。在本申請案中,術語「吸收偏光器」意指對入射光表現出選擇性透射及吸收特性的光學元件。吸收偏光器可透射在各種方向上振動的入射光中在一個方向上振動的光,且吸收在其他方向上振動的光。 The polarizer can be an absorbing polarizer. In this application, the term "absorbing polarizer" means an optical element that exhibits selective transmission and absorption properties for incident light. The absorbing polarizer can transmit light vibrating in one direction and absorb light vibrating in other directions among incident light vibrating in various directions.
偏光器可為線性偏光器。在本申請案中,術語「線性偏光器」意指其中選擇性透射的光為在任何一個方向上振動的經線性偏光光,而選擇性吸收的光為在與經線性偏光光的振動方向正交的方向上振動的經線性偏光光的偏光器。 The polarizer may be a linear polarizer. In this application, the term "linear polarizer" means a linearly polarized light in which the selectively transmitted light vibrates in either direction, and the selectively absorbed light is linearly polarized in the normal direction of vibration of the linearly polarized light. A polarizer that oscillates linearly polarized light in the cross direction.
作為偏光器,例如,可使用其中碘被染色在例如聚乙烯醇(polyvinyl alcohol,PVA)拉伸膜等聚合物拉伸膜上的偏光器,或者其中以定向狀態聚合的液晶被用作主體,且根據液晶的定向排列的各向異性染料被用作客體的客體-主體偏光器(guest-host polarizer),但不限於此。亦即,偏光器可包含聚乙烯醇系化合物。 As the polarizer, for example, a polarizer in which iodine is dyed on a polymer stretched film such as a polyvinyl alcohol (polyvinyl alcohol, PVA) stretched film or the like is used as a host, or in which a liquid crystal polymerized in an aligned state is used, And an anisotropic dye aligned according to the alignment of liquid crystals is used as a guest-host polarizer of the guest, but is not limited thereto. That is, the polarizer may contain a polyvinyl alcohol-based compound.
慮及本申請案的目的,可適當地調整偏光器的透射率及偏光度。例如,偏光器的透射率可為42.5%至55%,且偏光度可 為65%至99.9997%。 Considering the purpose of this application, the transmittance and polarization degree of the polarizer can be adjusted appropriately. For example, the transmittance of the polarizer can be 42.5% to 55%, and the degree of polarization can be 65% to 99.9997%.
慮及本申請案的目的,可適當地調整壓敏黏合層的厚度。壓敏黏合層可具有例如1微米至30微米左右的厚度。壓敏黏合層的厚度可具體而言為1微米或大於1微米、3微米或大於3微米或者5微米或大於5微米,且可為25微米或小於25微米、20微米或小於20微米或者15微米或小於15微米。在此厚度範圍內,提供一種具有優異的阻擋包括藍色區域的紫外線的效能、偏光板的顏色特性及可靠性評價時的耐久性的光學疊層可為有利的。 In consideration of the purpose of the present application, the thickness of the pressure-sensitive adhesive layer can be appropriately adjusted. The pressure-sensitive adhesive layer may have a thickness of, for example, about 1 micron to 30 microns. The thickness of the pressure-sensitive adhesive layer may specifically be 1 micron or more, 3 microns or more, or 5 microns or more, and may be 25 microns or less, 20 microns or less, or 15 microns. microns or less than 15 microns. Within this thickness range, it may be advantageous to provide an optical laminate excellent in blocking efficacy of ultraviolet rays including a blue region, color characteristics of a polarizing plate, and durability in reliability evaluation.
壓敏黏合層可具有優異的阻擋包括380奈米或大於380奈米的藍色區域的紫外線的性質。壓敏黏合層對於波長範圍為例如380奈米或大於380奈米至400奈米或小於400奈米的光可具有小於3%的透射率。例如,壓敏黏合層對於波長範圍為例如大於400奈米至410奈米或小於410奈米的光可具有小於20%的透射率。在本申請案中,術語「特定波長範圍內的透射率」可為對所述波長範圍內的任何一個特定波長的透射率,可為對所述範圍內的某些波長範圍的透射率,或者可意指對所述範圍內的所有波長的透射率。 The pressure-sensitive adhesive layer may have an excellent property of blocking ultraviolet rays including a blue region of 380 nm or more. The pressure sensitive adhesive layer may have a transmittance of less than 3% for light in a wavelength range of, for example, 380 nm or greater to 400 nm or less. For example, the pressure sensitive adhesive layer may have a transmittance of less than 20% for light in a wavelength range of, for example, greater than 400 nm to 410 nm or less than 410 nm. In this application, the term "transmittance within a specific wavelength range" may be the transmittance to any specific wavelength within the wavelength range, may be the transmittance to certain wavelength ranges within the range, or Transmittance for all wavelengths within the range may be meant.
本申請案的光學疊層可具有優異的阻擋包括380奈米或大於380奈米的藍色區域的紫外線的性質。具體而言,光學疊層在例如380奈米或大於380奈米至400奈米或小於400奈米的波長範圍內可具有1%或小於1%的透射率。 The optical stack of the present application may have an excellent property of blocking ultraviolet rays including a blue region of 380 nm or more. Specifically, the optical stack can have a transmission of 1% or less over a wavelength range of, for example, 380 nm or greater to 400 nm or less.
例如,光學疊層在大於400奈米至410奈米或小於410奈米的波長範圍內可具有10%或小於10%的透射率。例如,光學疊層對於波長為380奈米的光可具有1%或小於1%、0.5%或小於0.5%、0.1%或小於0.1%或者0.05%或小於0.05%的透射率。例如,光學疊層對於波長為390奈米的光可具有1%或小於1%、0.5%或小於0.5%、0.2%或小於0.2%、0.15%或小於0.15%、0.10%或小於0.10%或者0.06%或小於0.06%的透射率。例如,光學疊層對於波長為400奈米的光可具有1%或小於1%或者0.95%或小於0.95%的透射率。例如,光學疊層對於波長為410奈米的光可具有10%或小於10%、8%或小於8%或者7%或小於7%的透射率。 For example, the optical stack can have a transmission of 10% or less in the wavelength range of greater than 400 nm to 410 nm or less than 410 nm. For example, the optical stack can have a transmission of 1% or less, 0.5% or less, 0.1% or less, or 0.05% or less for light having a wavelength of 380 nm. For example, the optical stack may have 1% or less, 0.5% or less, 0.2% or less, 0.15% or less, 0.15% or less, 0.10% or less, or 0.06% or less than 0.06% transmittance. For example, the optical stack may have a transmission of 1% or less, or 0.95% or less, for light having a wavelength of 400 nanometers. For example, the optical stack can have a transmission of 10% or less, 8% or less, or 7% or less for light having a wavelength of 410 nanometers.
光學疊層可具有優異的顏色特性。例如,光學疊層在CIE實驗室顏色座標系(CIE Lab color coordinate system)中的b*值可為7.5或小於7.5、7或小於7、6.5或小於6.5、6.0或小於6.0、5.9或小於5.9、5.8或小於5.8或者5.7或小於5.7。此外,光學疊層可例如在CIE實驗室顏色座標系中的a*值可為-3.9或大於-3.9、-3.5或大於-3.5、-3.0或大於-3.0或者-2.8或大於-2.8。 Optical stacks can have excellent color properties. For example, the b* value of the optical stack in the CIE Lab color coordinate system can be 7.5 or less, 7 or less, 6.5 or less 6.5, 6.0 or less 6.0, 5.9 or less , 5.8 or less than 5.8 or 5.7 or less than 5.7. Additionally, the optical stack can have an a* value of -3.9 or greater, -3.5 or greater, -3.0 or greater, or -2.8 or greater, eg, in the CIE laboratory color coordinate system.
a*b*顏色座標系可意指稱為L*a*b*的顏色座標系的a*顏色座標及b*顏色座標。實驗室座標系為基於國際照明委員會(Commission Internaltion de L’ Eclairage,C.I.E.)色度圖的顏色座標系,其為基於亮度要素(L*)及兩個顏色軸(a*軸及b*軸)來顯示顏色的座標系。在L*a*b*座標系中,a*軸為綠色及紅色的兩色軸,且b*軸為藍色及黃色的兩色軸。b*值越高,偏光板的顏 色越接近黃色。此時,若b*值太高,則偏光板的變黃程度變得嚴重,且因此甚至在整個產品的視覺欣賞中亦可能出現問題。b*值的下限可為例如1.0或大於1.0、1.5或大於1.5、2.0或大於2.0、2.5或大於2.5、3.0或大於3.0或者3.3或大於3.3。a*值的上限可例如為小於0、-0.5或小於-0.5、-1.0或小於-1.0或者-1.4或小於-1.4。慮及偏光板所應用的產品的種類、客戶的需求等,可適當地調整偏光板所需的顏色值,但鑑於不會在產品的視覺欣賞中造成問題,例如,3.0至7.0左右或3.0至5.3左右的b*值可為適宜的。 The a*b* color coordinate system may mean a* color coordinates and b* color coordinates of a color coordinate system called L*a*b*. The laboratory coordinate system is a color coordinate system based on the chromaticity diagram of the International Commission on Illumination (Commission Internaltion de L'Eclairage, C.I.E.), which is based on the luminance element (L*) and two color axes (a* axis and b* axis) to display the coordinate system of the color. In the L*a*b* coordinate system, the a* axis is a two-color axis of green and red, and the b* axis is a two-color axis of blue and yellow. The higher the b* value, the color of the polarizer The color is closer to yellow. At this time, if the b* value is too high, the degree of yellowing of the polarizing plate becomes severe, and thus there may be a problem even in visual appreciation of the entire product. The lower limit of the b* value may be, for example, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, or 3.3 or more. The upper limit of the value of a* can be, for example, less than 0, -0.5 or less than -0.5, -1.0 or less than -1.0 or -1.4 or less than -1.4. Considering the type of products to which the polarizing plate is applied, the needs of customers, etc., the color value required by the polarizing plate can be adjusted appropriately, but in view of not causing problems in the visual appreciation of the product, for example, around 3.0 to 7.0 or 3.0 to A b* value around 5.3 may be suitable.
在本申請案中,藉由將如上所述單獨作為紫外線吸收劑的式1的丙二腈系化合物配製至壓敏黏合劑組成物,或者將如上所述的丙二腈系化合物及式2的吡唑啉系化合物或者上式4的丙二酸系化合物混合並將混合物配製至壓敏黏合劑組成物,由此形成的偏光板可有效地阻擋藍色區域中的光,且同時表現出優異的光學特性,乃因偏光板的b*值不會顯著偏離上述範圍。
In the present application, by formulating the above-mentioned malononitrile compound of
CIE L*a*b*顏色座標系中的每個數值可藉由應用量測顏色座標系的每個座標的一般方法來量測,例如,其可在量測位置放置具有積分球形式的偵測器的儀器(例如,紫外線-可見光分光計)之後,根據製造商的手冊來量測。在一個實例中,亦可相對於光學疊層本身量測CIE L*a*b*顏色空間的每個座標。 Each value in the CIE L*a*b* color coordinate system can be measured by applying the general method of measuring each coordinate of the color coordinate system, for example, it is possible to place a detector in the form of an integrating sphere at the measurement position After measuring the instrument (for example, ultraviolet-visible spectrometer), measure according to the manufacturer's manual. In one example, each coordinate of the CIE L*a*b* color space can also be measured relative to the optical stack itself.
光學疊層可具有優異的耐久性。在一個實例中,在80℃的溫度下的高溫可靠性評價或在60℃的溫度及90%的相對濕度下將其儲存1000小時的可靠性評價中,光學疊層可不會導致壓敏黏 合層界面處的隆起(lifting)。 Optical stacks can have excellent durability. In one example, the optical laminate may not cause pressure-sensitive adhesive in a high-temperature reliability evaluation at a temperature of 80°C or when it is stored for 1000 hours at a temperature of 60°C and a relative humidity of 90%. Lifting at the layer interface.
在光學疊層中,壓敏黏合層可直接接觸光學膜,或者在壓敏黏合層與光學膜之間可存在另一層。 In an optical stack, the pressure sensitive adhesive layer may directly contact the optical film, or there may be another layer between the pressure sensitive adhesive layer and the optical film.
在一個實例中,當光學膜為偏光器時,光學疊層可更包括延遲層。延遲層可具有將經圓偏光光轉換成經線性偏光光或者將經線性偏光光轉換成經圓偏光光的功能。 In one example, when the optical film is a polarizer, the optical stack may further include a retardation layer. The retardation layer may have a function of converting circularly polarized light into linearly polarized light or converting linearly polarized light into circularly polarized light.
延遲層對於波長在100奈米至180奈米範圍內的550奈米的光可具有面內延遲(in-plane retardation)。此處,當延遲層的面內延遲在上述範圍內時,亦可稱延遲膜具有1/4波長相位延遲特性。 The retardation layer may have in-plane retardation for light of 550 nm having a wavelength in the range of 100 nm to 180 nm. Here, when the in-plane retardation of the retardation layer is within the above range, it can also be said that the retardation film has 1/4 wavelength phase retardation characteristics.
在本申請案中,術語「n波長相位延遲特性」指能夠在所述波長範圍的至少一部分內將入射光相位延遲所述入射光的波長的n倍的特性。亦即,1/4波長相位延遲特性可為將入射經線性偏光光轉換成經橢圓偏光光或經圓偏光光,並將反向入射經橢圓偏光光或經圓偏光光轉換成經線性偏光光的特性。亦即,延遲層對波長為550奈米的光的面內延遲可在上述範圍內,此可根據下面將要闡述的方程式1來計算。在另一實例中,延遲膜的面內延遲可為105奈米或大於105奈米、110奈米或大於110奈米、115奈米或大於115奈米、120奈米或大於120奈米、125奈米或大於125奈米或者130奈米或大於130奈米,且可為290奈米或小於290奈米、280奈米或小於280奈米、270奈米或小於270奈米、260奈米或小於260奈米、250奈米或小於250奈米、240奈米或小於
240奈米、230奈米或小於230奈米、220奈米或小於220奈米、210奈米或小於210奈米、200奈米或小於200奈米、190奈米或小於190奈米、180奈米或小於180奈米、170奈米或小於170奈米、160奈米或小於160奈米、150奈米或小於150奈米或者145奈米或小於145奈米。
In the present application, the term "n-wavelength phase retardation characteristic" refers to a characteristic capable of retarding the phase of incident light by n times the wavelength of the incident light within at least a part of the wavelength range. That is, the 1/4 wavelength phase retardation characteristic can convert incident linearly polarized light into elliptically polarized light or circularly polarized light, and convert reversely incident elliptically polarized light or circularly polarized light into linearly polarized light characteristics. That is, the in-plane retardation of the retardation layer for light having a wavelength of 550 nm may be within the above range, which may be calculated according to
在本申請案中,術語「平面延遲(Rin)」為根據下面的方程式1確定的值。另一方面,延遲層的慢軸可與偏光器的吸收軸成約40度至50度、約43度至47度且較佳為約45度。例如,延遲層可為聚合物拉伸膜或液晶化合物的固化層。
In this application, the term "plane retardation (R in )" is a value determined according to
[方程式1]Rin=d×(nx-ny)。 [Equation 1] Rin=d×(nx-ny).
在方程式1中,d為延遲層的厚度,且nx、ny及nz分別表示延遲層在x軸、y軸及z軸方向上的折射率。x軸意指平行於延遲層的平面慢軸的方向,y軸意指平行於延遲層的平面快軸的方向,且z軸意指延遲層的厚度方向。慢軸方向指在平面上具有最大折射率的方向,快軸方向指在延遲層的平面上與慢軸正交的方向,且厚度方向指由慢軸及快軸形成的平面的法線方向。在本申請案中,除非另有說明,否則術語「折射率」指波長為約550奈米的光的折射率。
In
延遲層可為具有所謂的反向波長色散特性的功能層。在本申請案中,術語「反向波長色散特性」可指滿足下面方程式2的特性: [方程式2]R(450)/R(550)<R(650)/R(550)。 The retardation layer may be a functional layer having so-called reverse wavelength dispersion characteristics. In the present application, the term "reverse wavelength dispersion characteristic" may refer to a characteristic satisfying Equation 2 below: [Equation 2] R(450)/R(550)<R(650)/R(550).
在方程式2中,R(450)為延遲層對波長為450奈米的光的面內延遲,R(550)為延遲層對波長為550奈米的光的面內延遲,且R(650)為延遲層對波長為650奈米的光的面內延遲。 In Equation 2, R(450) is the in-plane retardation of the retardation layer for light with a wavelength of 450 nm, R(550) is the in-plane retardation of the retardation layer for light with a wavelength of 550 nm, and R(650) is the in-plane retardation of the retardation layer to light with a wavelength of 650 nm.
延遲層的面內延遲可各自根據上面的方程式1來計算。然而,在波長為450奈米的光的面內延遲中,波長為450奈米的光的折射率在方程式1中被應用為nx及ny;在波長為550奈米的光的面內延遲中,波長為550奈米的光的折射率在方程式1中應用為nx及ny;且在波長為650奈米的光的面內延遲中,波長為650奈米的光的折射率在方程式1中被應用為nx及ny。
The in-plane retardations of the retardation layers can each be calculated according to
滿足上述方程式2的延遲層可表現出在寬波長範圍內設計的相位延遲特性。藉由在延遲層中調整上式2的R(450)/R(550)及/或R(650)/R(550),可提供更佳的效果。 The retardation layer satisfying Equation 2 above can exhibit phase retardation characteristics engineered over a wide wavelength range. Better effects can be provided by adjusting R(450)/R(550) and/or R(650)/R(550) in the above formula 2 in the retardation layer.
在一個實例中,以上方程式4中的R(450)/R(550)可介於0.6至0.99的範圍內。在另一實例中,R(450)/R(550)可為0.61或大於0.61、0.62或大於0.62、0.63或大於0.63、0.64或大於0.64、0.65或大於0.65、0.66或大於0.66、0.67或大於0.67、0.69或大於0.69、0.70或大於0.70、0.71或大於0.71、0.72或大於0.72、0.73或大於0.73、0.74或大於0.74、0.75或大於0.75、0.76或大於0.76、0.77或大於0.77、0.78或大於0.78、0.79或大於0.79、0.80或大於0.80、0.81或大於0.81、0.82或大於0.82、0.83或大 於0.83、0.84或大於0.84、0.85或大於0.85、0.86或大於0.86、0.87或大於0.87、0.88或大於0.88、0.89或大於0.89或者0.90或大於0.90。在另一實例中,R(450)/R(550)可為0.98或小於0.98、0.97或小於0.97、0.96或小於0.96、0.95或小於0.95、0.94或小於0.94、0.93或小於0.93、0.92或小於0.92、0.91或小於0.91、0.90或小於0.90、0.89或小於0.89、0.88或小於0.88或者0.87或小於0.87、0.86或小於0.86或者0.85或小於0.85。方程式4中的R(650)/R(550)可介於1.00至1.19的範圍內。R(650)/R(550)可為1.18或小於1.18、1.17或小於1.17、1.16或小於1.16、1.15或小於1.15、1.14或小於1.14、1.13或小於1.13、1.12或小於1.12、1.11或小於1.11、1.1或小於1.1或者1.08或小於1.08左右。在另一實例中,R(650)/R(550)可為1.01或大於1.01、1.02或大於1.02、1.03或大於1.03、1.04或大於1.04、1.05或大於1.05、1.06或大於1.06、1.07或大於1.07、1.08或大於1.08或者1.09或大於1.09。 In one example, R(450)/R(550) in Equation 4 above may be in the range of 0.6 to 0.99. In another example, R(450)/R(550) can be 0.61 or greater than 0.61, 0.62 or greater than 0.62, 0.63 or greater than 0.63, 0.64 or greater than 0.64, 0.65 or greater than 0.65, 0.66 or greater than 0.66, 0.67 or greater 0.67, 0.69 or more, 0.69, 0.70 or more, 0.71 or more 0.78, 0.79 or greater than 0.79, 0.80 or greater than 0.80, 0.81 or greater than 0.81, 0.82 or greater than 0.82, 0.83 or greater 0.83, 0.84 or greater than 0.84, 0.85 or greater than 0.85, 0.86 or greater than 0.86, 0.87 or greater than 0.87, 0.88 or greater than 0.88, 0.89 or greater than 0.89, or 0.90 or greater than 0.90. In another example, R(450)/R(550) may be 0.98 or less than 0.98, 0.97 or less than 0.97, 0.96 or less than 0.96, 0.95 or less than 0.95, 0.94 or less than 0.94, 0.93 or less than 0.93, 0.92 or less 0.92, 0.91 or less than 0.91, 0.90 or less than 0.90, 0.89 or less than 0.89, 0.88 or less than 0.88 or 0.87 or less than 0.87, 0.86 or less than 0.86 or 0.85 or less. R(650)/R(550) in Equation 4 may range from 1.00 to 1.19. R(650)/R(550) can be 1.18 or less than 1.18, 1.17 or less than 1.17, 1.16 or less than 1.16, 1.15 or less than 1.15, 1.14 or less than 1.14, 1.13 or less than 1.13, 1.12 or less than 1.12, 1.11 or less , 1.1 or less than 1.1 or 1.08 or less than 1.08. In another example, R(650)/R(550) may be 1.01 or greater than 1.01, 1.02 or greater than 1.02, 1.03 or greater than 1.03, 1.04 or greater than 1.04, 1.05 or greater than 1.05, 1.06 or greater than 1.06, 1.07 or greater 1.07, 1.08 or greater than 1.08 or 1.09 or greater than 1.09.
在上述範圍內調整延遲層的物理性質的方式沒有特別限制。例如,當使用可聚合液晶組成物生產延遲膜時,其亦可藉由調整包含在可聚合液晶組成物中的可聚合液晶化合物的種類及比率的方法來控制,或者亦可藉由調整延遲膜的厚度來控制。 The way of adjusting the physical properties of the retardation layer within the above range is not particularly limited. For example, when a retardation film is produced using a polymerizable liquid crystal composition, it can also be controlled by adjusting the type and ratio of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, or by adjusting the retardation film to control the thickness.
為確保上述延遲特性,應用液晶聚合物層或可聚合液晶組成物的固化層作為延遲層可為有利的,且特別地,應用包含具有特定反向波長特性的可聚合液晶化合物的可聚合液晶組成物的 固化層可為有利的。此外,當應用此種可聚合液晶組成物時,即使不根據需要包含紫外線吸收劑及光穩定劑,亦可製成本申請案的光學疊層以確保期望的紫外線阻擋特性。 In order to ensure the above-mentioned retardation characteristics, it may be advantageous to apply a liquid crystal polymer layer or a cured layer of a polymerizable liquid crystal composition as a retardation layer, and in particular, to apply a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having a specific reverse wavelength characteristic material A cured layer may be advantageous. In addition, when such a polymerizable liquid crystal composition is used, the optical laminate of the present application can be made to ensure the desired ultraviolet blocking properties even if the ultraviolet absorber and light stabilizer are not included as required.
當光學疊層更包括延遲層時,壓敏黏合層可存在於偏光器與延遲層之間或者延遲層的外側上。然而,慮及下面將要闡述的有機發光裝置的製造製程中的缺陷問題,下面將要闡述的黏合層存在於偏光器與延遲層之間,且壓敏黏合層存在於延遲層的外側上是合適的。 When the optical stack further includes a retardation layer, a pressure-sensitive adhesive layer may exist between the polarizer and the retardation layer or on the outside of the retardation layer. However, in consideration of defects in the manufacturing process of organic light-emitting devices to be described below, it is appropriate that an adhesive layer to be described below exists between the polarizer and the retardation layer, and a pressure-sensitive adhesive layer exist on the outer side of the retardation layer. .
在本申請案中,術語「延遲層的外側」可指基於延遲層的偏光器側的相對側上的位置,其可包括直接接觸延遲層的位置或者不直接接觸延遲層的位置。在本申請案中,術語「偏光器的外側」可指基於偏光器的延遲層側的相對側上的位置,其可包括直接接觸偏光器的位置或者不直接接觸偏光器的位置。亦即,在化學疊層中,延遲層存在於基於光學膜(例如,偏光器)的壓敏黏合層的相對側上可為適宜的。 In the present application, the term "outside of the retardation layer" may refer to a position on the opposite side based on the polarizer side of the retardation layer, which may include a position directly contacting the retardation layer or a position not directly contacting the retardation layer. In the present application, the term "outer side of the polarizer" may refer to a position on the opposite side based on the retardation layer side of the polarizer, which may include a position directly contacting the polarizer or a position not directly contacting the polarizer. That is, in chemical lamination, it may be desirable for the retardation layer to be present on the opposite side of the pressure-sensitive adhesive layer based on an optical film (eg, polarizer).
在本申請案中,術語「黏合層」可指在附著至被黏物而移除一次時便無法再附著的層,乃因其在完全固化後保持固體狀態。此處,黏合層可藉由例如將黏合劑組成物施加至偏光器的一側,並藉由乾燥、加熱或用電磁波照射等將其固化來形成。此處,術語「黏合劑組成物的固化」可指藉由物理作用或化學反應使黏合劑組成物表達黏合性質的製程。 In the present application, the term "adhesive layer" may refer to a layer that cannot be reattached once it is attached to an adherend and removed once because it maintains a solid state after being fully cured. Here, the adhesive layer can be formed by, for example, applying the adhesive composition to one side of the polarizer, and curing it by drying, heating, or irradiating with electromagnetic waves, or the like. Here, the term "curing of the adhesive composition" may refer to a process of making the adhesive composition express adhesive properties through physical action or chemical reaction.
黏合層可指由黏合劑組成物形成的層。此外,黏合劑組 成物可包含黏合劑作為主要組分,且用於主要組分的組分如上所述。可用作黏合劑的材料的具體種類沒有特別限制,只要其被固化以表達所期望的黏合性質即可。作為黏合劑,例如,可使用以下中的一種或者兩種或更多種:聚乙烯醇系黏合劑;丙烯酸黏合劑;乙酸乙烯酯系黏合劑;胺基甲酸酯系黏合劑;聚酯系黏合劑;聚烯烴系黏合劑;聚乙烯基烷基醚系黏合劑;橡膠系黏合劑;氯乙烯-乙酸乙烯酯系黏合劑;苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene,SBS)黏合劑;氫化苯乙烯-丁二烯-苯乙烯產物(hydrogenated styrene-butadiene-styrene product,SEBS)系黏合劑;乙烯系黏合劑;及丙烯酸酯系黏合劑等。此種黏合層可藉由固化例如水系、溶劑系或無溶劑黏合劑組成物來製備。此外,黏合層可包含處於固化狀態的熱固性型、室溫固化型、水分固化型或光可固化黏合劑組成物。此外,黏合層的較佳實例可包括包含水性聚乙烯醇系黏合劑組成物;無溶劑丙烯酸黏合劑組成物;或固化狀態的無溶劑乙酸乙烯酯系黏合劑組成物等的黏合層。 The adhesive layer may refer to a layer formed of an adhesive composition. In addition, the binder group The finished product may contain a binder as a main component, and components for the main component are as described above. The specific kind of material that can be used as the adhesive is not particularly limited as long as it is cured to express the desired adhesive properties. As the adhesive, for example, one or two or more of the following can be used: polyvinyl alcohol-based adhesives; acrylic adhesives; vinyl acetate-based adhesives; urethane-based adhesives; Adhesives; polyolefin adhesives; polyvinyl alkyl ether adhesives; rubber adhesives; vinyl chloride-vinyl acetate adhesives; styrene-butadiene-styrene (styrene-butadiene-styrene, SBS) adhesives; hydrogenated styrene-butadiene-styrene products (hydrogenated styrene-butadiene-styrene product, SEBS) adhesives; vinyl adhesives; and acrylate adhesives, etc. Such adhesive layers can be prepared by curing, for example, water-based, solvent-based or solvent-free adhesive compositions. In addition, the adhesive layer may comprise a thermosetting, room temperature curing, moisture curing or light curable adhesive composition in a cured state. In addition, preferable examples of the adhesive layer may include an adhesive layer comprising a water-based polyvinyl alcohol-based adhesive composition; a solvent-free acrylic adhesive composition; or a solvent-free vinyl acetate-based adhesive composition in a cured state, or the like.
當光學膜為偏光器時,本申請案的光學疊層可為偏光板。在偏光板中,如圖1所示,黏合層(30)可存在於偏光器(10)與延遲層(20)之間,且壓敏黏合層(40)可存在於延遲層(20)的外側上。在根據圖1的結構的偏光板中,在黏合層與偏光器之間可包括或可不包括下面將闡述的中間層,例如偏光器保護膜、除了延遲層之外的延遲膜或延遲膜的基底膜等。根據此種結構, 其可保護包括在偏光板中的液晶配向膜免受額外的紫外線照射,因此是有利的。當液晶膜(液晶化合物的固化層)用作延遲層時,可使用液晶配向膜。 When the optical film is a polarizer, the optical stack of the present application can be a polarizer. In the polarizing plate, as shown in FIG. 1, an adhesive layer (30) may exist between the polarizer (10) and the retardation layer (20), and a pressure-sensitive adhesive layer (40) may exist between the retardation layer (20). on the outside. In the polarizing plate according to the structure of FIG. 1 , an intermediate layer to be described below, such as a polarizer protective film, a retardation film other than the retardation layer, or a base of the retardation film may or may not be included between the adhesive layer and the polarizer. film etc. According to this structure, It can protect the liquid crystal alignment film included in the polarizing plate from additional ultraviolet rays, and thus is advantageous. When a liquid crystal film (cured layer of a liquid crystal compound) is used as a retardation layer, a liquid crystal alignment film can be used.
除了延遲層之外,偏光板可更包括附加層。 In addition to the retardation layer, the polarizing plate may further include additional layers.
在一個實例中,偏光板可更包括存在於偏光器外側的一或多層上層、存在於延遲層外側的下層以及存在於偏光器與延遲層之間的中間層。壓敏黏合層可存在於偏光器與上層之間、偏光器與中間層之間、延遲層與中間層之間、延遲層與下層之間以及延遲層外側的位置中的一或多個位置處。然而,慮及下面將要闡述的有機發光裝置的製造製程中的缺陷問題,黏合層存在於偏光器與上層之間、偏光器與中間層之間、延遲層與中間層之間以及延遲層與下層之間為合適的,且壓敏黏合層存在於延遲層外側。 In one example, the polarizing plate may further include one or more upper layers outside the polarizer, a lower layer outside the retardation layer, and an intermediate layer between the polarizer and the retardation layer. The pressure-sensitive adhesive layer may be present at one or more of positions between the polarizer and the upper layer, between the polarizer and the middle layer, between the retardation layer and the middle layer, between the retardation layer and the lower layer, and at positions outside the retardation layer . However, considering the defects in the manufacturing process of the organic light-emitting device described below, the adhesive layer exists between the polarizer and the upper layer, between the polarizer and the intermediate layer, between the retardation layer and the intermediate layer, and between the retardation layer and the lower layer. Between is suitable, and the pressure-sensitive adhesive layer is present on the outside of the retardation layer.
如圖2所示,上層(103)可疊層在偏光器(101)的面向延遲層(102)的相對側上。在此種情況下,壓敏黏合層可存在於上層與偏光器之間、偏光器與延遲層之間以及延遲層外側的位置中的一或多個位置處。然而,慮及下面將要闡述的有機發光裝置的製造製程中的缺陷問題,黏合層存在於上層與偏光器之間以及偏光器與延遲層之間的位置中的一或多個位置處是合適的,且壓敏黏合層存在於延遲層外側。 As shown in FIG. 2, the upper layer (103) may be laminated on the opposite side of the polarizer (101) facing the retardation layer (102). In this case, the pressure-sensitive adhesive layer may exist at one or more of positions between the upper layer and the polarizer, between the polarizer and the retardation layer, and positions outside the retardation layer. However, in consideration of defects in the manufacturing process of organic light-emitting devices to be described below, it is appropriate for the adhesive layer to exist at one or more of the positions between the upper layer and the polarizer and between the polarizer and the retardation layer. , and the pressure-sensitive adhesive layer exists outside the retardation layer.
作為上層的類型,可例舉偏光器的保護膜、硬塗層、除了延遲層之外的延遲膜、抗反射層或液晶塗層等,但不限於此。用作上層的每種構造的具體類型沒有特別限制,例如,可不加限 制地使用工業中用於構成例如偏光板等光學膜的各種膜。上層可為所示層的單層,或者可具有包括所示層中的兩層或更多層的疊層結構的多層式結構。 As the type of the upper layer, a protective film of a polarizer, a hard coat layer, a retardation film other than a retardation layer, an antireflection layer, or a liquid crystal coating, etc. are exemplified, but not limited thereto. The specific type of each structure used as the upper layer is not particularly limited, for example, unlimited Various films used in industry to constitute optical films such as polarizing plates are systematically used. The upper layer may be a single layer of the illustrated layers, or may have a multi-layered structure including a laminated structure of two or more of the illustrated layers.
如圖3所示,下層(203)可疊層在延遲層(202)的面向偏光器(201)的表面的相對側上。在此種情況下,壓敏黏合層可存在於下層與延遲層之間、偏光器與延遲層之間以及延遲層外側的位置中的一或多個位置處。然而,慮及下面將要闡述的有機發光裝置的製造製程中的缺陷問題,黏合層存在於下層與延遲層之間以及偏光器與延遲層之間的位置中的一或多個位置處是合適的,且壓敏黏合層存在於延遲層外側。在圖3的情況下,可如圖2所示添加上層。例如,如圖3所示,在下層存在的狀態下,例如硬塗層或低反射層等上層可存在於偏光器的外側上,且保護膜亦可存在於偏光器的一側或兩側上。 As shown in FIG. 3, the lower layer (203) may be laminated on the opposite side of the surface of the retardation layer (202) facing the polarizer (201). In this case, the pressure-sensitive adhesive layer may exist at one or more of positions between the lower layer and the retardation layer, between the polarizer and the retardation layer, and positions outside the retardation layer. However, in consideration of defects in the manufacturing process of organic light-emitting devices to be described below, it is appropriate for the adhesive layer to exist at one or more of the positions between the lower layer and the retardation layer and between the polarizer and the retardation layer. , and the pressure-sensitive adhesive layer exists outside the retardation layer. In the case of Figure 3, an upper layer can be added as shown in Figure 2. For example, as shown in FIG. 3, in the state where the lower layer exists, an upper layer such as a hard coat layer or a low reflection layer may exist on the outer side of the polarizer, and a protective film may also exist on one or both sides of the polarizer. .
作為下層的類型,可例舉用於將除延遲膜之外的延遲膜或偏光板附著至另一元件的壓敏黏合層或黏合層、黏合層、或者用於保護壓敏黏合層或黏合層的保護膜或離型膜。在此種情況下,作為下層的壓敏黏合層亦可為本申請案的上述壓敏黏合層。下層可為所示層的單層,或者可具有包括所示層中的兩層或更多層的疊層結構的多層式結構。 As the type of the lower layer, a pressure-sensitive adhesive layer or an adhesive layer for attaching a retardation film or a polarizing plate other than a retardation film to another element, an adhesive layer, or a pressure-sensitive adhesive layer or an adhesive layer for protecting protective film or release film. In this case, the pressure-sensitive adhesive layer as the lower layer may also be the above-mentioned pressure-sensitive adhesive layer of the present application. The lower layer may be a single layer of the illustrated layers, or may have a multi-layered structure including a laminated structure of two or more of the illustrated layers.
如圖4所示,中間層(303)可存在於偏光器(301)與延遲層(302)之間。在此種情況下,壓敏黏合層可存在於中間層與偏光器之間、中間層與延遲層之間以及延遲層外側的位置中的 一或多個位置處。然而,慮及下面將要闡述的有機發光裝置的製造製程中的缺陷問題,黏合層存在於中間層與偏光器之間以及中間層與延遲層之間的位置中的一或多個位置處是合適的,且壓敏黏合層存在於延遲層外側。儘管在圖4的結構中沒有示出,但圖2的結構中的上層及/或圖3的結構中的下層亦可存在。 As shown in FIG. 4, an intermediate layer (303) may exist between the polarizer (301) and the retardation layer (302). In this case, the pressure-sensitive adhesive layer may exist in positions between the intermediate layer and the polarizer, between the intermediate layer and the retardation layer, and outside the retardation layer. at one or more locations. However, in consideration of defects in the manufacturing process of organic light-emitting devices to be described below, it is appropriate for the adhesive layer to exist at one or more of the positions between the intermediate layer and the polarizer and between the intermediate layer and the retardation layer. , and the pressure-sensitive adhesive layer exists outside the retardation layer. Although not shown in the structure of FIG. 4, the upper layer in the structure of FIG. 2 and/or the lower layer in the structure of FIG. 3 may also be present.
作為中間層,可例舉上述偏光器保護膜、除了延遲層之外的延遲膜或延遲層的基底膜。中間層可為所示層的單層,或者可具有包括所示層中的兩層或更多層的疊層結構的多層式結構。 As the intermediate layer, the above-mentioned polarizer protective film, a retardation film other than the retardation layer, or a base film of the retardation layer may be exemplified. The intermediate layer may be a single layer of the illustrated layers, or may have a multilayer structure including a stacked structure of two or more of the illustrated layers.
作為偏光器的保護膜或延遲層的基底膜,例如,可使用纖維素膜,例如三乙醯基纖維素(triacetyl cellulose,TAC)膜;聚酯膜,例如聚(對苯二甲酸乙二醇酯)(poly(ethylene terephthalate),PET)膜;聚碳酸酯膜;聚醚碸膜;丙烯酸膜及/或聚烯烴系膜,例如聚乙烯膜、聚丙烯膜、含有環或降冰片烯結構的聚烯烴膜或乙烯-丙烯共聚物膜等,但不限於此。 As a protective film of a polarizer or a base film of a retardation layer, for example, a cellulose film such as a triacetyl cellulose (TAC) film; a polyester film such as poly(ethylene terephthalate); Poly(ethylene terephthalate), PET) film; polycarbonate film; polyether film; acrylic film and/or polyolefin film, such as polyethylene film, polypropylene film, containing ring or norbornene structure Polyolefin film or ethylene-propylene copolymer film, etc., but not limited thereto.
作為除了延遲層之外的延遲膜,可例舉具有正厚度方向延遲值的延遲膜。在本申請案中,術語「厚度方向延遲(Rth)」可為根據以下方程式3確定的值。當偏光板更包括具有正厚度方向延遲值的延遲膜時,其在視角下可具有優異的抗反射特性及顏色特性。作為延遲膜,可使用滿足以下方程式4或方程式5的延遲膜。滿足以下方程式4的延遲膜可稱為+C板,且滿足以下方程式5的延遲膜可稱為+B板。此種延遲膜可例舉為聚合物拉伸膜、垂直定向液晶層、斜定向液晶層或傾斜定向液晶層等,但不限於 此。在一個實例中,延遲膜的光軸(慢軸)在平面上的投影可平行於或正交於偏光器的吸收軸。 As the retardation film other than the retardation layer, a retardation film having a positive thickness direction retardation value can be exemplified. In the present application, the term "thickness direction retardation (Rth)" may be a value determined according to Equation 3 below. When the polarizing plate further includes a retardation film having a positive retardation value in the thickness direction, it may have excellent anti-reflection characteristics and color characteristics at viewing angles. As the retardation film, a retardation film satisfying Equation 4 or Equation 5 below may be used. A retardation film satisfying Equation 4 below may be referred to as a +C plate, and a retardation film satisfying Equation 5 below may be referred to as a +B plate. Such a retardation film can be, for example, a polymer stretched film, a vertically aligned liquid crystal layer, an obliquely aligned liquid crystal layer, or an obliquely aligned liquid crystal layer, etc., but is not limited to this. In one example, the projection of the optical axis (slow axis) of the retardation film on a plane may be parallel or orthogonal to the absorption axis of the polarizer.
[方程式3]Rth=d×(nz-ny) [Equation 3] Rth=d×(nz-ny)
[方程式4]nx=ny<nz [Equation 4] nx=ny<nz
[方程式5]nx>ny且nz>ny [Equation 5] nx>ny and nz>ny
在方程式3中,d為延遲層的厚度,且在方程式3至方程式5中,nx、ny及nz各自如上所定義。 In Equation 3, d is the thickness of the retardation layer, and in Equations 3 to 5, nx, ny, and nz are each as defined above.
圖5及圖6各自說明性地示出根據本申請案的一個實例的偏光板的結構。根據圖5的偏光板可依序包括硬塗層(403)、偏光器(401)、偏光器保護膜(404)、黏合層(405)、延遲層基底膜(406)、延遲層(402)、+C板(407)及壓敏黏合層(408)。根據圖6的偏光板可依序包括硬塗層(403)、偏光器(401)、黏合層(405)、延遲層基底膜(406)、延遲層(402)、+C板(407)及壓敏黏合層(408)。 5 and 6 each illustratively show the structure of a polarizing plate according to one example of the present application. The polarizing plate according to FIG. 5 may sequentially include a hard coat layer (403), a polarizer (401), a polarizer protective film (404), an adhesive layer (405), a retardation layer base film (406), and a retardation layer (402). , +C plate (407) and pressure sensitive adhesive layer (408). The polarizing plate according to FIG. 6 may sequentially include a hard coat layer (403), a polarizer (401), an adhesive layer (405), a retardation layer base film (406), a retardation layer (402), a +C plate (407) and A pressure sensitive adhesive layer (408).
本申請案亦是有關於有機發光裝置。有機發光裝置可包括光學疊層及有機發光面板。當光學疊層為偏光板且偏光板包括延遲層時,延遲層可被設置成與有機發光面板相鄰。 The present application is also related to organic light emitting devices. An organic light emitting device may include an optical stack and an organic light emitting panel. When the optical stack is a polarizing plate and the polarizing plate includes a retardation layer, the retardation layer may be disposed adjacent to the organic light emitting panel.
在有機發光裝置中,光學疊層可經由壓敏黏合層附著至有機發光面板。亦即,在有機發光裝置中,光學膜可經由壓敏黏 合層附著至有機發光面板。 In organic light emitting devices, the optical stack can be attached to the organic light emitting panel via a pressure sensitive adhesive layer. That is, in organic light-emitting devices, the optical film can be The composite layer is attached to the organic light emitting panel.
此外,由於光學疊層經由壓敏黏合層附著至有機發光面板,因此當在有機發光裝置的製造製程中出現缺陷時,相對低成本的光學疊層被移除,且另一光學疊層被重新附著,由此亦可解決當在製造製程中出現缺陷時丟棄昂貴的有機發光面板的問題。 In addition, since the optical stack is attached to the organic light-emitting panel through the pressure-sensitive adhesive layer, when a defect occurs during the manufacturing process of the organic light-emitting device, a relatively low-cost optical stack is removed and another optical stack is re- It can also solve the problem of discarding expensive organic light-emitting panels when defects occur during the manufacturing process.
在一個實例中,有機發光面板可包括基板;以及依序設置在基板的第一表面上的第一電極層;有機發光層;及第二電極層,其中所述光學疊層可位於自所述有機發光面板發射光的一側上。 In one example, the organic light-emitting panel may include a substrate; and a first electrode layer sequentially disposed on a first surface of the substrate; an organic light-emitting layer; and a second electrode layer, wherein the optical stack can be located from the The organic light-emitting panel emits light on one side.
例如,如下所述,當有機發光裝置具有其中光朝向基板發射的底部發射結構時,光學疊層(例如,偏光板)可設置在基板外側。此外,當有機發光裝置具有其中光朝向將在下面闡述的封裝基板發射的頂部發射結構時,光學疊層可設置在封裝基板的外側。藉由防止外部光被由金屬製成的反射層(例如有機發光裝置的電極及配線)反射並自有機發光裝置中射出,偏光板可提高有機發光裝置的可見性。 For example, as described below, when an organic light emitting device has a bottom emission structure in which light is emitted toward a substrate, an optical stack (eg, a polarizing plate) may be disposed outside the substrate. Also, when the organic light emitting device has a top emission structure in which light is emitted toward an encapsulation substrate to be explained below, the optical stack may be disposed outside the encapsulation substrate. The polarizing plate can improve visibility of the organic light emitting device by preventing external light from being reflected by a reflective layer made of metal, such as electrodes and wiring of the organic light emitting device, and emitted from the organic light emitting device.
圖7說明性地示出本申請案的有機發光裝置的結構。當光學疊層為偏光板時,如圖7所示,有機發光裝置可包括基板(701),以及依序設置在基板的第一表面上的第一電極層(702)、有機發光層(703)及第二電極層(704),且偏光板(100)可包括在基板的第二表面上。 FIG. 7 illustratively shows the structure of the organic light emitting device of the present application. When the optical stack is a polarizing plate, as shown in FIG. 7, the organic light-emitting device may include a substrate (701), a first electrode layer (702), an organic light-emitting layer (703) sequentially arranged on the first surface of the substrate ) and the second electrode layer (704), and the polarizer (100) may be included on the second surface of the substrate.
本申請案的光學疊層特別適用於塑膠有機發光裝置。因 此,有機發光裝置的基板可為塑膠基板。包括塑膠基板的有機發光裝置在可捲曲、可撓性或可彎曲的有機發光裝置的實施中可為有利的。 The optical stack of the present application is particularly suitable for plastic organic light-emitting devices. because Therefore, the substrate of the organic light emitting device may be a plastic substrate. Organic light emitting devices comprising plastic substrates may be advantageous in the implementation of rollable, flexible or bendable organic light emitting devices.
塑膠基板可包含聚合物。所述聚合物可例舉為聚醯亞胺、聚醯胺酸、聚萘二甲酸乙二醇酯、聚醚醚酮、聚碳酸酯、聚對苯二甲酸乙二醇酯、聚醚硫醚、聚碸或丙烯酸聚合物等。在一個實例中,就製程溫度而言,塑膠基板可包含具有優異高溫耐久性的聚醯亞胺。 The plastic substrate may contain polymers. The polymer may be exemplified by polyimide, polyamic acid, polyethylene naphthalate, polyether ether ketone, polycarbonate, polyethylene terephthalate, polyether sulfide , Polymer or acrylic polymer etc. In one example, the plastic substrate may include polyimide which has excellent high temperature durability in terms of process temperature.
作為基板,可使用半透明基板。半透明基板對於可見光區域中的光可具有例如50%或大於50%、60%或大於60%、70%或大於70%或80%的透射率。 As the substrate, a translucent substrate can be used. The translucent substrate may have a transmittance of, for example, 50% or more, 60% or more, 70% or more, or 80% for light in the visible region.
第一電極層及第二電極層中的一者可為陽極,且另一者可為陰極。陽極是注入電洞的電極,其可由具有高功函數的導電材料製成,且陰極是注入電子的電極,其可由具有低功函數的導電材料製成。在一個實例中,第一電極層可為陽極,且第二電極層可為陰極。 One of the first electrode layer and the second electrode layer may be an anode, and the other may be a cathode. The anode is a hole-injecting electrode, which may be made of a conductive material with a high work function, and the cathode is an electron-injecting electrode, which may be made of a conductive material with a low work function. In one example, the first electrode layer can be an anode, and the second electrode layer can be a cathode.
陽極可為透明電極,且陰極可為反射電極。陽極可包含透明金屬氧化物,例如,ITO、IZO、AZO、GZO、ATO或SnO2等。陰極可包含金屬,例如Ag、Au、Al等。 The anode can be a transparent electrode, and the cathode can be a reflective electrode. The anode may comprise a transparent metal oxide, for example, ITO, IZO, AZO, GZO, ATO, or SnO2 , among others. The cathode may comprise metals such as Ag, Au, Al, and the like.
有機發光層可包含能夠當電力已施加至第一電極層及第二電極層時發射光的有機材料。在被稱為所謂的底部發射裝置的結構中,第一電極層可由透明電極層形成,且第二電極層可由反 射電極層形成。此外,在被稱為所謂的頂部發射裝置的結構中,第一電極層是由反射電極層形成,且第二電極層是由透明電極層形成。由電極層注入的電子及電洞可在有機發光層中重組以產生光。光可朝向底部發射裝置中的基板發射,且朝向頂部發射裝置中的第二電極層發射。 The organic light emitting layer may include an organic material capable of emitting light when power has been applied to the first electrode layer and the second electrode layer. In a structure called a so-called bottom emission device, the first electrode layer may be formed of a transparent electrode layer, and the second electrode layer may be formed of a reverse electrode layer. The emitter layer is formed. Furthermore, in a structure called a so-called top emission device, the first electrode layer is formed of a reflective electrode layer, and the second electrode layer is formed of a transparent electrode layer. Electrons and holes injected from the electrode layer can be recombined in the organic light-emitting layer to generate light. Light may be emitted toward the substrate in bottom emission devices, and toward the second electrode layer in top emission devices.
有機發射層可包括紅色發射層、綠色發射層及藍色發射層。發射層可包含分別發射紅色、綠色及藍色的已知有機材料。在一個實例中,有機發光裝置可藉由三個原色發光層在分別發射不同顏色的同時形成一個畫素(點、圖像元素)的方法(RGB方法)來驅動,或者可藉由以下方法(WOLED方法)來驅動:藉由疊層所述三個原色發光層以發射白色來形成一個畫素,然後藉由在白色發光層的頂部上設置彩色濾光片層來實施各種顏色。 The organic emission layer may include a red emission layer, a green emission layer, and a blue emission layer. The emissive layer may include known organic materials that emit red, green, and blue colors, respectively. In one example, the organic light emitting device may be driven by a method (RGB method) in which three primary color light emitting layers respectively emit different colors while forming one pixel (a dot, a picture element), or may be driven by the following method ( WOLED method) to drive: one pixel is formed by laminating the three primary color light-emitting layers to emit white, and then various colors are implemented by providing a color filter layer on top of the white light-emitting layer.
有機發光面板可更包括位於第一電極層與有機發光層之間以及第二電極層與有機發光層之間的子層。子層可包括用於平衡電子及電洞的電洞傳輸層、電洞注入層、電子注入層及電子傳輸層,但不限於此。 The organic light emitting panel may further include sublayers located between the first electrode layer and the organic light emitting layer and between the second electrode layer and the organic light emitting layer. The sublayer may include a hole transport layer, a hole injection layer, an electron injection layer, and an electron transport layer for balancing electrons and holes, but is not limited thereto.
有機發光顯示面板可更包括封裝基板。封裝基板可存在於第二電極層上。封裝基板可由玻璃、金屬及/或聚合物製成,且可封裝第一電極層、有機發光層及第二電極層,以防止水分及/或氧氣自外部引入。 The organic light emitting display panel may further include an encapsulation substrate. An encapsulation substrate may exist on the second electrode layer. The encapsulation substrate can be made of glass, metal and/or polymer, and can encapsulate the first electrode layer, the organic light emitting layer and the second electrode layer to prevent moisture and/or oxygen from being introduced from the outside.
本申請案的光學疊層具有優異的阻擋紫外線、特別是包 括380奈米或大於380奈米的藍色區域的紫外線的效能。 The optical stack of the present application has excellent UV blocking properties, especially the package The efficacy of UV rays in the blue region including 380 nm or greater.
特別地,當本申請案的光學疊層已應用於有機發光裝置時,其可將有機發光裝置中的藍色光源的壽命縮短最小化。 In particular, when the optical stack of the present application has been applied to an organic light emitting device, it can minimize the lifetime shortening of a blue light source in the organic light emitting device.
本申請案的光學疊層可同時表現出優異的耐久性,而不會大幅改變顏色值及損害光學特性。 The optical stacks of the present application can simultaneously exhibit excellent durability without substantially changing color values and compromising optical properties.
10、101、201、301、401:偏光器 10, 101, 201, 301, 401: Polarizer
20、102、202、302、402:延遲層 20, 102, 202, 302, 402: delay layer
30、405:黏合層 30, 405: adhesive layer
40、408:壓敏黏合層 40, 408: pressure sensitive adhesive layer
100:偏光板 100: polarizer
103:上層 103: upper layer
203:下層 203: lower layer
303:中間層 303: middle layer
403:硬塗層 403: hard coating
404:偏光器保護膜 404: Polarizer protective film
406:延遲層基底膜 406: Retardation layer base film
407:+C板 407:+C board
701:基板 701: Substrate
702:第一電極層 702: the first electrode layer
703:有機發光層 703: Organic light-emitting layer
704:第二電極層 704: second electrode layer
圖1至圖6為說明性地示出本申請案的光學疊層的結構的圖。 1 to 6 are diagrams illustratively showing the structure of the optical stack of the present application.
圖7為說明性地示出本申請案的有機發光裝置的結構的圖。 FIG. 7 is a diagram illustratively showing the structure of the organic light-emitting device of the present application.
圖8為製備例的氫譜核磁共振(H-nuclear magnetic resonance,H-NMR)結果。 Fig. 8 is the H-nuclear magnetic resonance (H-NMR) results of the preparation example.
在下文中,參考實例闡述本申請案。然而,本申請案的權利範圍不受以下實例的限制。 In the following, the present application is explained with reference to examples. However, the scope of rights of the present application is not limited by the following examples.
1.偏光板的光學性質評價1. Evaluation of optical properties of polarizing plates
將在實例及比較例中製備的偏光板切割成25毫米×25毫米(寬度×長度)的大小,以生產樣品。 The polarizing plates prepared in Examples and Comparative Examples were cut into a size of 25 mm×25 mm (width×length) to produce samples.
藉由使用紫外線-可見光分光計(V-7100,日本分光公司(JASCO))量測偏光板的透射率,評價對包括藍色區域的紫外線的阻擋效能。此處,當總光入射量被設定為100時,透射率表示以比率%計的透射過偏光板的光量。 By measuring the transmittance of the polarizing plate using an ultraviolet-visible spectrometer (V-7100, JASCO), the blocking performance against ultraviolet rays including a blue region was evaluated. Here, when the total light incident amount is set to 100, the transmittance means the amount of light transmitted through the polarizing plate in ratio %.
2.在可靠性條件下的耐久性評價2. Durability evaluation under reliability conditions
藉由將在實例及比較例中製備的偏光板切割成90毫米×170毫米(寬度×長度)的大小而製備的樣品是由實例及比較例中的每一者的兩片製備。 Samples prepared by cutting the polarizing plates prepared in Examples and Comparative Examples into a size of 90 mm×170 mm (width×length) were prepared from two sheets of each of Examples and Comparative Examples.
隨後,將兩片製備的樣品附著至玻璃基板(110毫米×190毫米×0.7毫米=寬度×長度×厚度)的兩側,使得各個偏光板的光學吸收軸交叉,以製備用於評價的樣品。 Subsequently, two sheets of the prepared samples were attached to both sides of a glass substrate (110 mm×190 mm×0.7 mm=width×length×thickness) such that the optical absorption axes of the respective polarizing plates cross to prepare samples for evaluation.
在附著時施加的壓力為約5千克/平方公分,且工作是在潔淨室中進行,以使在界面處不會出現氣泡或異物。 The pressure applied at the time of attachment was about 5 kg/cm 2 , and the work was performed in a clean room so that no air bubbles or foreign matter would occur at the interface.
將製備的樣品放置在可靠性室中,然後觀察在溫度為80℃的溫度條件下置留500小時後,在壓敏黏合層界面處是否出現氣泡或出現隆起(耐熱性評價)。耐熱性評價準則如下。 The prepared samples were placed in a reliability chamber, and then it was observed whether bubbles or bumps appeared at the interface of the pressure-sensitive adhesive layer after being left at a temperature of 80° C. for 500 hours (evaluation of heat resistance). The heat resistance evaluation criteria are as follows.
<耐熱性評價準則> <Heat Resistance Evaluation Criteria>
O:沒有出現隆起或氣泡 O: No bumps or air bubbles occurred
△:每1公分×1公分(寬度×長度)的單位面積出現5個或少於5個氣泡,或者出現隆起 △: There are 5 or less bubbles per unit area of 1 cm × 1 cm (width × length), or bulges appear
×:每1公分×1公分(寬度×長度)的單位面積出現多於5個氣泡,或者出現大量隆起 ×: There are more than 5 bubbles per unit area of 1 cm × 1 cm (width × length), or a large number of bulges appear
此外,將製備的樣品放置在可靠性室中,並在60℃的溫度及90%的相對濕度條件下置留1,000小時,然後觀察在壓敏黏合層界面處是否出現隆起(耐濕熱性評價)。耐濕熱性評價準則如下。 In addition, the prepared sample was placed in a reliability chamber and left for 1,000 hours at a temperature of 60°C and a relative humidity of 90%, and then it was observed whether swelling appeared at the interface of the pressure-sensitive adhesive layer (moisture and heat resistance evaluation) . The criteria for evaluating the heat and humidity resistance are as follows.
<耐濕熱性評價準則> <Evaluation Criteria for Moisture and Heat Resistance>
◎:沒有出現隆起 ◎: No swelling occurs
O:出現較少的隆起 O: Less swelling occurs
△:出現隆起 △: Swelling occurs
×:出現大量隆起 ×: A large amount of swelling occurs
3.偏光板的顏色特性評價3. Evaluation of color characteristics of polarizing plates
將實例及比較例的偏光板切割成25毫米×25毫米(寬度×長度)的大小,以製備樣品。藉由使用紫外線-可見光分光計(V-7100,由日本分光公司製造)量測偏光板的顏色座標來評價偏光板的視覺欣賞特性。 The polarizing plates of Examples and Comparative Examples were cut into a size of 25 mm×25 mm (width×length) to prepare samples. The visual appreciation characteristics of the polarizing plate were evaluated by measuring the color coordinates of the polarizing plate using an ultraviolet-visible spectrometer (V-7100, manufactured by JASCO Corporation).
製備例-製備紫外線吸收劑(A)Preparation example-preparation of ultraviolet absorber (A)
根據以下順序製備下式A的丙二腈化合物(2-(4-羥基-2-甲氧基苯亞甲基)丙二腈)。 A malononitrile compound (2-(4-hydroxy-2-methoxybenzylidene)malononitrile) of the following formula A was prepared according to the following procedure.
1)將下式A1的化合物及下式A2的化合物以1:1的莫耳比率置於含有乙醇的反應器中並攪拌。 1) Put the compound of the following formula A1 and the compound of the following formula A2 in a molar ratio of 1:1 in a reactor containing ethanol and stir.
2)將1,8-二氮雜雙環(5.4.0)十一碳-7-烯(1,8-diazabicyclo(5.4.0)undec-7-ene,DBU)以式A1的化合物的輸入量的0.1倍的當量緩慢引入反應器中。 2) 1,8-diazabicyclo (5.4.0) undec-7-ene (1,8-diazabicyclo (5.4.0) undec-7-ene, DBU) with the input amount of the compound of formula A1 The equivalent of 0.1 times of the is slowly introduced into the reactor.
3)將其在約25℃的溫度下攪拌約12小時。 3) Stir it at a temperature of about 25°C for about 12 hours.
4)以與步驟2)中引入的乙醇相同的莫耳添加鹽酸(Hydrochloric acid,HCl)。 4) Add hydrochloric acid (Hydrochloric acid, HCl) at the same molarity as the ethanol introduced in step 2).
5)反應完成後,過濾步驟4)的所得物,以獲得固體狀態的最終產物。 5) After the reaction is completed, the resultant of step 4) is filtered to obtain the final product in a solid state.
所獲得的式A的化合物的NMR分析結果如圖8所示。 The NMR analysis results of the obtained compound of formula A are shown in FIG. 8 .
使用安捷倫公司(Agilent)的NMR分光計(A500a,500百萬赫茲)來執行H-NMR分析。具體而言,在作為溶劑的二甲基亞碸(dimethyl sulfoxide,DMSO)中將分析物稀釋至約10毫克/毫升的濃度左右以進行核磁共振量測,其中化學位移是以ppm來表達。 H-NMR analysis was performed using an Agilent NMR spectrometer (A500a, 500 megahertz). Specifically, the analyte is diluted to a concentration of about 10 mg/ml in dimethyl sulfoxide (DMSO) as a solvent for NMR measurement, wherein the chemical shift is expressed in ppm.
使用凝膠滲透層析法(GPC),在以下條件下量測了壓敏 黏合劑聚合物的重量平均分子量。為製作校準曲線,使用安捷倫系統的標準聚苯乙烯對量測結果進行轉換。 Pressure sensitivity was measured using gel permeation chromatography (GPC) under the following conditions The weight average molecular weight of the binder polymer. To create a calibration curve, the measurements were converted using polystyrene standards from the Agilent system.
量測儀器:安捷倫GPC(安捷倫1200系列,美國) Measuring instrument: Agilent GPC (Agilent 1200 series, USA)
管柱:連接的兩個PL混合B Column: two PL mixed B connected
管柱溫度:40℃ Column temperature: 40°C
洗脫劑:四氫呋喃(tetrahydrofuran,THF) Eluent: tetrahydrofuran (tetrahydrofuran, THF)
流速:1.0毫升/分鐘 Flow rate: 1.0ml/min
濃度:~2毫克/毫升(100微升注射液) Concentration: ~2 mg/ml (100 μl injection)
生產壓敏黏合層Production of pressure sensitive adhesive layers
將壓敏黏合劑組成物塗佈在經離型處理的聚(對苯二甲酸乙二醇酯)(PET)膜(厚度:38微米,MRF-38,三菱化學公司(Mitsubishi chemical))的經離型處理的表面上,以在乾燥後具有約10微米的厚度,並在烘箱(瑪瑞斯(Mathis)烘箱)中在80℃下熱固化3分鐘,以生產壓敏黏合層。 The pressure-sensitive adhesive composition was coated on a release-treated poly(ethylene terephthalate) (PET) film (thickness: 38 μm, MRF-38, Mitsubishi chemical). on the release-treated surface to have a thickness of about 10 micrometers after drying, and thermally cured in an oven (Mathis oven) at 80° C. for 3 minutes to produce a pressure-sensitive adhesive layer.
生產偏光板(光學疊層)Production of polarizing plates (optical laminates)
藉由將製備的壓敏黏合層疊層(堆疊)在已知偏光板的一側上來製備偏光板,在已知偏光板上,用厚度為約60微米的三乙醯基纖維素(TAC)保護膜保護聚(乙烯醇)(PVA)系列偏光器的兩側。 A polarizing plate was prepared by laminating (stacking) the prepared pressure-sensitive adhesive layer on one side of a known polarizing plate protected with triacetyl cellulose (TAC) having a thickness of about 60 μm. A film protects both sides of the poly(vinyl alcohol) (PVA) series polarizer.
在上面的實例及比較例中製備的壓敏黏合劑組成物的組成及光學疊層的物理性質評價結果在下面的表1中闡述。 The compositions of the pressure-sensitive adhesive compositions prepared in the above Examples and Comparative Examples and the evaluation results of physical properties of the optical laminates are set forth in Table 1 below.
[表1]
根據表1,由於本申請案的光學疊層對於波長為380奈米或大於380奈米的光,特別是波長介於380奈米至400奈米範圍內的光具有小於1%的透射率,以使其對於波長在上述範圍內的光具有高阻擋性質,因此可看出其適合於保護有機發光裝置的藍色光源。此外可看出,衍生自未應用在本申請案中定義的化合物的壓敏黏合劑組成物的比較例的光學疊層具有極高的a*值及相對高的b*值,由此導致較差的視覺欣賞性質,且特別是由於高的b*值而變黃。然而可看出,滿足本申請案中定義的條件的光學疊層具有適當的a*值及b*值,由此不僅具有優異的視覺欣賞性質,且亦 具有優異的耐久性。 According to Table 1, since the optical stack of the present application has a transmittance of less than 1% for light with a wavelength of 380 nm or greater than 380 nm, especially light with a wavelength in the range of 380 nm to 400 nm, So that it has a high blocking property for light having a wavelength within the above-mentioned range, it can thus be seen that it is suitable for protecting blue light sources of organic light-emitting devices. Furthermore, it can be seen that the optical laminates of the comparative examples derived from pressure-sensitive adhesive compositions not using the compounds defined in this application have extremely high a* values and relatively high b* values, resulting in poor Visually appreciative properties, and especially yellow due to high b* values. However, it can be seen that optical stacks satisfying the conditions defined in this application have appropriate a* and b* values, thereby not only having excellent visual appreciation properties, but also Has excellent durability.
10:偏光器 10: Polarizer
20:延遲層 20: Delay layer
30:黏合層 30: Adhesive layer
40:壓敏黏合層 40: Pressure sensitive adhesive layer
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