TWI798354B - combination - Google Patents
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- TWI798354B TWI798354B TW108104557A TW108104557A TWI798354B TW I798354 B TWI798354 B TW I798354B TW 108104557 A TW108104557 A TW 108104557A TW 108104557 A TW108104557 A TW 108104557A TW I798354 B TWI798354 B TW I798354B
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Abstract
本發明之組合物包含：具有下述式(I)-1：
Description
本發明係關於一種組合物、垂直配向液晶硬化膜、積層體、橢圓偏光板、及有機EL(Electroluminescence，電致發光)顯示裝置。The invention relates to a composition, a vertically aligned liquid crystal cured film, a laminate, an elliptical polarizer, and an organic EL (Electroluminescence, electroluminescence) display device.
橢圓偏光板係偏光板與相位差板積層而成之光學構件，例如在以平面狀態顯示圖像之裝置(例如有機EL顯示裝置)中，用於防止構成裝置之電極上之光反射。於該橢圓偏光板中，作為相位差板，使用所謂之λ/4板。
作為該用於橢圓偏光板之相位差板，顯示逆波長分散性者就在可見光之較廣之波長範圍內發揮同等之相位差性能之方面而言較佳。作為顯示逆波長分散性之相位差板，已知有如下相位差板，其包含使顯示逆波長分散性之聚合性液晶化合物在朝水平方向配向之狀態下聚合並硬化而成之水平配向液晶硬化膜。
又，亦要求附光學補償功能之偏光板，其具有以即便在自斜向觀察之情形時，亦發揮與自正面方向觀察時相同之光學性能之方式進行補償的功能。作為此種附光學補償功能之偏光板，可列舉具備逆波長分散性之水平配向液晶硬化膜，且進而具備使聚合性液晶化合物於垂直配向之狀態下聚合硬化而成之垂直配向液晶硬化膜者。進而，於該垂直配向液晶硬化膜之中，於專利文獻1中亦提出使用顯示逆波長分散性之聚合性液晶化合物的垂直配向液晶硬化膜。
[先前技術文獻]
[專利文獻]An elliptical polarizer is an optical member formed by laminating a polarizing plate and a phase difference plate. For example, in a device that displays images in a flat state (such as an organic EL display device), it is used to prevent light reflection on the electrodes constituting the device. In this elliptically polarizing plate, a so-called λ/4 plate is used as a retardation plate.
As the retardation plate for use in such an elliptically polarizing plate, one showing reverse wavelength dispersion is preferable in terms of exhibiting the same retardation performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, there is known a retardation plate comprising a horizontally aligned liquid crystal hardened by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a state aligned in the horizontal direction. membrane.
In addition, a polarizing plate with an optical compensation function is also required, which has a compensation function to exhibit the same optical performance as when viewed from the front direction even when viewed from an oblique direction. As such a polarizing plate with an optical compensation function, a horizontally aligned liquid crystal cured film with reverse wavelength dispersion, and a vertically aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound in a vertically aligned state can be mentioned. . Furthermore, among this vertical alignment liquid crystal cured film, the vertical alignment liquid crystal cured film using the polymerizable liquid crystal compound which shows reverse wavelength dispersion property is also proposed in
[專利文獻1]日本專利特開2015-57646號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-57646
[發明所欲解決之問題][Problem to be solved by the invention]
然而，由於顯示逆波長分散性之液晶化合物之分子重心不穩定，故而僅液晶化合物則會產生大量配向缺陷而不易垂直配向。因此，於製作垂直配向液晶硬化膜時，需要垂直配向用之配向膜。然而，於該情形時，必需形成垂直配向用之配向膜之步驟，因此有生產性降低之問題。However, since the center of gravity of the molecules of liquid crystal compounds exhibiting inverse wavelength dispersion is unstable, only liquid crystal compounds generate a large number of alignment defects and are not easy to vertically align. Therefore, when making a vertically aligned liquid crystal cured film, an alignment film for vertical alignment is required. However, in this case, since the process of forming the alignment film for vertical alignment is necessary, there exists a problem that productivity falls.
本發明係鑒於上述課題而完成者，其目的在於提供一種能夠形成即便無配向膜亦抑制配向缺陷之產生之垂直配向液晶硬化膜的組合物。 [解決問題之技術手段]This invention was made in view of the said subject, and it aims at providing the composition which can form the vertical alignment liquid crystal cured film which suppresses generation|occurrence|production of an alignment defect even if there is no alignment film. [Technical means to solve the problem]
本發明者為了解決上述課題而進行了銳意研究，結果完成了本發明。即，本發明中包含以下態樣。
[1]一種組合物，其包含：具有下述式(I)-1：
[化1]
根據本發明，可提供一種能夠形成即便無配向膜亦抑制配向缺陷之產生之垂直配向液晶硬化膜的組合物。According to the present invention, it is possible to provide a composition capable of forming a vertical alignment liquid crystal cured film that suppresses generation of alignment defects even without an alignment film.
以下，對本發明之實施形態詳細地進行說明。再者，於本說明書中，有時將丙烯酸及甲基丙烯酸稱為「(甲基)丙烯酸」。又，有時於化合物名之後加上「系」，對化合物及其衍生物進行統稱。於在化合物名之後加上「系」來表示聚合物名之情形時，意指聚合物之重複單元源自化合物或其衍生物、或者對源自化合物或其衍生物之重複單元於聚合後實施化學修飾等而成之聚合物。Embodiments of the present invention will be described in detail below. In addition, in this specification, acrylic acid and methacrylic acid may be called "(meth)acrylic acid." In addition, "series" is sometimes added after the name of the compound to collectively refer to the compound and its derivatives. When adding "is" after the compound name to indicate the name of the polymer, it means that the repeating unit of the polymer is derived from the compound or its derivative, or that the repeating unit derived from the compound or its derivative is polymerized. Chemically modified polymers.
＜組合物＞
本發明之組合物(以下，有時記載為垂直配向液晶硬化膜形成用組合物)包含：具有下述式(I)-1：
[化4]
組合物除了上述式(I)-1所表示之1種以上之液晶化合物、以及非離子性矽烷化合物及/或離子性化合物以外，亦可視需要進而包含其他成分。The composition may further contain other components, if necessary, in addition to the one or more liquid crystal compounds represented by the above formula (I)-1, and the nonionic silane compound and/or the ionic compound.
本發明之組合物能夠形成即便無配向膜亦抑制配向缺陷之產生之垂直配向液晶硬化膜。其理由推測如下。具有式(I)-1所表示之結構之1種以上之液晶化合物(以下，有時記載為液晶化合物(I)-1)於式(I)-1中，Ar表示具有2個以上之環結構之2價基，該2個以上之環結構中之1個為6員環，於該6員環之1、4位與L1 及L2 鍵結，故而有形成T字型之結構之傾向。具有此種結構之化合物一般有顯示逆波長分散性之傾向，液晶化合物(I)-1通常表現逆波長分散性。另一方面，液晶化合物(I)-1由於具有T字型結構，故而通常單獨時不易進行垂直配向。本發明之組合物包含液晶化合物(I)-1、以及選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者。於液晶硬化膜之製造中，若將組合物塗佈於基材而形成塗佈膜，且將塗佈膜加熱使之乾燥而形成乾燥覆膜，則於乾燥覆膜中，由於非離子性矽烷化合物與液晶化合物(I)-1之親和性及/或離子性化合物與液晶化合物(I)-1之親和性，產生離子性化合物存在於基材表面側，且/或非離子性矽烷化合物存在於乾燥覆膜之與基材為相反側之表面側的分佈。此種分佈由於提高垂直配向限制力，故而有液晶化合物(I)-1於乾燥覆膜內相對於基材表面朝垂直方向配向之傾向。因此，能夠保持液晶化合物(I)-1垂直配向之狀態而形成硬化膜。因此，認為本實施形態之組合物即便不於基材上形成配向膜，亦能夠形成垂直配向液晶硬化膜。作為選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者，可列舉僅包含非離子性矽烷化合物、僅包含離子性化合物、以及包含非離子性矽烷化合物及離子性化合物兩者之3種態樣。雖然僅非離子性矽烷化合物及離子性化合物任一者亦具有提高垂直配向限制力之效果，但就進一步提高垂直配向限制力之觀點而言，較佳為同時包含非離子性矽烷化合物及離子性化合物。The composition of the present invention can form a vertical alignment liquid crystal cured film that suppresses the generation of alignment defects even without an alignment film. The reason for this is presumed as follows. One or more liquid crystal compounds having a structure represented by formula (I)-1 (hereinafter sometimes referred to as liquid crystal compound (I)-1) In formula (I)-1, Ar represents a ring having two or more The divalent group of the structure, one of the two or more ring structures is a 6-membered ring, and the 1 and 4 positions of the 6-membered ring are bonded to L1 and L2 , so there is a possibility of forming a T-shaped structure tendency. Compounds having such a structure generally tend to exhibit reverse wavelength dispersion, and liquid crystal compound (I)-1 generally exhibits reverse wavelength dispersion. On the other hand, since the liquid crystal compound (I)-1 has a T-shaped structure, it is generally difficult to perform vertical alignment alone. The composition of the present invention contains liquid crystal compound (I)-1, and at least one member selected from the group consisting of nonionic silane compounds and ionic compounds. In the production of liquid crystal cured film, if the composition is applied to the substrate to form a coating film, and the coating film is heated to dry to form a dry film, in the dry film, due to the non-ionic silane The affinity between the compound and the liquid crystal compound (I)-1 and/or the affinity between the ionic compound and the liquid crystal compound (I)-1 results in the presence of the ionic compound on the surface side of the substrate and/or the presence of the nonionic silane compound Distribution on the surface side of the dry film opposite to the substrate. Such a distribution tends to align vertically with respect to the surface of the substrate in the dry film because the vertical alignment confinement force is increased. Therefore, it is possible to form a cured film while maintaining the state of the vertical alignment of the liquid crystal compound (I)-1. Therefore, even if the composition of this embodiment does not form an alignment film on a base material, it is considered that a cured film of a vertical alignment liquid crystal can be formed. As at least one selected from the group consisting of nonionic silane compounds and ionic compounds, only nonionic silane compounds, only ionic compounds, and both nonionic silane compounds and ionic compounds are listed. There are three kinds of states. Although only any one of the nonionic silane compound and the ionic compound has the effect of improving the vertical alignment confinement force, it is preferable to include both the nonionic silane compound and the ionic compound from the viewpoint of further improving the vertical alignment confinement force. compound.
[1.液晶化合物]
液晶化合物(I)-1係具有下述式(I)-1：
[化5]
式(I)-1中，Ar表示具有2個以上之環結構之2價基，該2個以上之環結構中之1個為6員環，於該6員環之1位及4位與L1 及L2 鍵結， L1 及L2 分別獨立表示單鍵或二價連結基， G1 及G2 分別獨立表示二價芳香族基或二價脂環式烴基，該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基、或硝基，該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子， *表示鍵結鍵。In the formula (I)-1, Ar represents a divalent group having two or more ring structures, and one of the two or more ring structures is a 6-membered ring, and the 1st and 4th positions of the 6-membered ring and L 1 and L 2 are bonded, L 1 and L 2 independently represent a single bond or a divalent linking group, G 1 and G 2 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and the divalent aromatic The hydrogen atom contained in the group and the divalent alicyclic hydrocarbon group can be independently substituted by a halogen atom, an alkyl group with 1 to 4 carbons, a fluoroalkyl group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons. A group, a cyano group, or a nitro group, the carbon atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * indicates a bond.
Ar表示具有2個以上之環結構之2價基。於本說明書中，Ar所具有之環結構之單位為單環。例如，於下述液晶化合物A、(A)-2、及(A)-3中，Ar分別具有4個、2個、及3個環結構。2個以上之環結構可2個以上之單環縮合而相互相鄰，亦可2個以上之單環經由化學鍵而相互鍵結，亦可2個以上之單環不縮合且不經由化學鍵地相鄰。又，可單環經由化學鍵而與單環縮合而成之縮合環(多環)相互鍵結，亦可多環與多環經由化學鍵而相互鍵結。將2個以上之環鍵結之化學鍵例如可包含如共軛雙鍵(更具體而言為-C=C-及-C=N-等)及羰基般擴展共軛系之空間上之擴散的鍵或基。Ar represents a divalent group having two or more ring structures. In this specification, the unit of the ring structure which Ar has is a monocyclic ring. For example, in the following liquid crystal compounds A, (A)-2, and (A)-3, Ar has 4, 2, and 3 ring structures, respectively. In the ring structure of two or more, two or more single rings may be condensed and adjacent to each other, or two or more single rings may be bonded to each other through chemical bonds, or two or more single rings may not be condensed and not bonded to each other. adjacent. Moreover, condensed rings (polycyclic rings) obtained by condensing a monocyclic ring and a monocyclic ring may be bonded to each other via a chemical bond, or polycyclic rings may be bonded to each other via a chemical bond. The chemical bond that binds two or more rings may include, for example, a conjugated double bond (more specifically, -C=C- and -C=N-, etc.) and a carbonyl group that expands the spatial diffusion of the conjugated system. key or base.
作為單環，例如可列舉單環式之烴環(更具體而言為環烷烴環及苯環等)、及單環式之雜環。作為單環式之雜環，例如可列舉5員環之雜環(更具體而言為吡咯環、呋喃環、噻吩環、㗁唑環、咪唑環、吡唑環、噻唑環、***環、吡咯啶環、四氫呋喃環、及四氫噻吩環等)、及6員環之雜環(更具體而言為吡啶環、吡𠯤環、嘧啶環、噻𠯤環、及哌啶環等)。多環為具有2環以上之環結構之結構，該環結構可為芳香環，亦可為烴環。作為多環，例如可列舉包含縮合環及單環式之雜環者。縮合環例如為該等單環中同一種類之單環縮合2個以上而成之環、及不同種類之單環縮合2個以上而成之環。作為縮合環，例如可列舉多環式之烴環(更具體而言為萘環、蒽環、及菲環等)、及多環式之雜環(更具體而言為喹啉環、喹㗁啉環、苯并呋喃環、苯并噻吩環、茀環、吲哚環、咔唑環、苯并咪唑環、苯并噻唑環、噻吩并噻唑環、苯并㗁唑環、1,3-苯二硫酚環、及啡啉環等)。該等縮合環中，就表現逆波長分散特性之觀點而言，較佳為多環結構，更佳為多環式之雜環結構。As a monocyclic ring, a monocyclic hydrocarbon ring (more specifically, a cycloalkane ring, a benzene ring, etc.), and a monocyclic heterocyclic ring are mentioned, for example. Examples of monocyclic heterocyclic rings include 5-membered heterocyclic rings (more specifically, pyrrole rings, furan rings, thiophene rings, azole rings, imidazole rings, pyrazole rings, thiazole rings, triazole rings, pyrrolidine ring, tetrahydrofuran ring, and tetrahydrothiophene ring, etc.), and 6-membered heterocycles (more specifically, pyridine ring, pyridine ring, pyrimidine ring, thiol ring, and piperidine ring, etc.). A polycyclic ring is a structure having a ring structure of two or more rings, and the ring structure may be an aromatic ring or a hydrocarbon ring. Examples of polycyclic rings include condensed rings and monocyclic heterocyclic rings. The condensed ring is, for example, a ring formed by condensing two or more monocyclic rings of the same type among these monocyclic rings, and a ring formed by condensing two or more monocyclic rings of different types. As the condensed ring, for example, polycyclic hydrocarbon rings (more specifically, naphthalene rings, anthracene rings, and phenanthrene rings), and polycyclic heterocycles (more specifically, quinoline rings, quinolyl rings, etc.) Oline ring, benzofuran ring, benzothiophene ring, oxene ring, indole ring, carbazole ring, benzimidazole ring, benzothiazole ring, thienothiazole ring, benzoxazole ring, 1,3-benzene dithiol ring, and phenanthroline ring, etc.). Among these condensed rings, a polycyclic structure is preferable, and a polycyclic heterocyclic structure is more preferable from the viewpoint of expressing inverse wavelength dispersion characteristics.
單環及多環可具有取代基。作為單環及多環可具有之取代基，例如可列舉氫原子、碳數1～20之烷基、及碳數1～20之烷氧基，該等取代基可進而具有氰基、亞胺基、烷多烯基、氰基、或胺基，該取代基中之碳原子可進而被取代為氧原子、氮原子、或硫原子(於該情形時，鍵結於碳原子上之氫原子可根據取代之原子之價數而增減)。該等取代基之中，可如亞胺基、烷多烯基、氰基、羥基、及胺基般擴展共軛系之空間上之擴散。該等取代基可進而經取代。Monocyclic and polycyclic may have substituents. Examples of substituents that monocyclic and polycyclic rings may have include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and these substituents may further have a cyano group or an imine group. group, alkanolenyl group, cyano group, or amino group, the carbon atom in the substituent group can be further replaced by an oxygen atom, a nitrogen atom, or a sulfur atom (in this case, a hydrogen atom bonded to a carbon atom can be increased or decreased according to the valence of the substituted atom). Among these substituents, such as imino group, alkanolenyl group, cyano group, hydroxyl group, and amine group, the steric diffusion of the conjugated system can be extended. These substituents may in turn be substituted.
作為Ar所具有之6員環，例如可列舉苯環及環己烷環。6員環可包含雜原子作為環員原子。作為包含6員環之縮合環，例如可列舉喹啉環、喹㗁啉環、苯并呋喃環、苯并噻吩環、茀環、吲哚環、咔唑環、苯并咪唑環、苯并噻唑環、噻吩并噻唑環、苯并㗁唑環、1,3-苯二硫酚環、及啡啉環。As a 6-membered ring which Ar has, a benzene ring and a cyclohexane ring are mentioned, for example. The 6-membered ring may contain heteroatoms as ring member atoms. Examples of condensed rings including 6-membered rings include quinoline rings, quinoline rings, benzofuran rings, benzothiophene rings, oxene rings, indole rings, carbazole rings, benzimidazole rings, and benzothiazole rings. ring, thienothiazole ring, benzoxazole ring, 1,3-benzenedithiol ring, and phenanthroline ring.
就進一步提高偏光板之逆波長分散性之觀點而言，Ar較佳為表示包含具有1個以上之硫原子作為環員原子之環結構的2價基。就進一步提高逆波長分散性之觀點而言，Ar較佳為表示下述式所表示之2價基。*表示鍵結鍵。
[化6]
作為L1 及L2 所表示之二價連結基，例如可列舉碳數1～4之伸烷基、-O-、-S-、-Ra1 ORa2 -、-Ra3 COORa4 -、-Ra5 OCORa6 -、Ra7 OC=OORa8 -、-N=N-、-CRc =CRd -、及-C≡C-。此處，Ra1 ～Ra8 分別獨立表示單鍵或碳數1～4之伸烷基(更具體而言為亞甲基、伸乙基、伸丙基、及伸丁基等)，Rc 及Rd 分別獨立表示碳數1～4之烷基(更具體而言為甲基、乙基、丙基、及丁基等)或氫原子。Examples of divalent linking groups represented by L 1 and L 2 include alkylene groups having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -, -R a3 COOR a4 -, - R a5 OCOR a6 -, R a7 OC=OOR a8 -, -N=N-, -CR c =CR d -, and -C≡C-. Here, R a1 to R a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms (more specifically, a methylene group, an ethylene group, a propylidene group, a butylene group, etc.), and R c and R d each independently represent an alkyl group having 1 to 4 carbon atoms (more specifically, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) or a hydrogen atom.
L1 及L2 較佳為分別獨立表示單鍵、碳數1～4之伸烷基、-O-、-S-、-Ra1 ORa2 -、-Ra3 COORa4 -、-Ra5 OCORa6 -、Ra7 OC=OORa8 -、-N=N-、-CRc =CRd -、或-C≡C-。L1 及L2 更佳為分別獨立表示單鍵、-ORa2-1 -、-CH2 -、-CH2 CH2 -、-COORa4-1 -、或OCORa6-1 -。此處，Ra2-1 、Ra4-1 、及Ra6-1 分別獨立表示單鍵、-CH2 -、或-CH2 CH2 -。L1 及L2 進而較佳為分別獨立表示單鍵、-O-、-CH2 CH2 -、-COO-、-COOCH2 CH2 -、或-OCO-。L 1 and L 2 are preferably each independently representing a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -, -R a3 COOR a4 -, -R a5 OCOR a6 -, R a7 OC=OOR a8 -, -N=N-, -CR c =CR d -, or -C≡C-. More preferably, L 1 and L 2 each independently represent a single bond, -OR a2-1 -, -CH 2 -, -CH 2 CH 2 -, -COOR a4-1 -, or OCOR a6-1 -. Here, R a2-1 , R a4-1 , and R a6-1 each independently represent a single bond, -CH 2 -, or -CH 2 CH 2 -. More preferably, L 1 and L 2 each independently represent a single bond, -O-, -CH 2 CH 2 -, -COO-, -COOCH 2 CH 2 -, or -OCO-.
作為G1 及G2 所表示之二價芳香族基，例如可列舉伸苯二基及伸萘二基(naphthylylenediyl)。二價芳香族基可經鹵素原子(更具體而言為氟原子、氯原子、及溴原子等)或碳數1～4之烷基之類之取代基取代。二價芳香族基可具有雜原子(更具體而言為氧原子、硫原子、及氮原子等)作為環員原子。作為G1 及G2 所表示之二價脂環式烴基，例如可列舉環戊二基、環己二基、及環庚二基。二價脂環式烴基可經鹵素原子及碳數1～4之烷基之類之取代基取代。Examples of the divalent aromatic group represented by G 1 and G 2 include phenylenediyl and naphthylylenediyl. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms. A divalent aromatic group may have a hetero atom (more specifically, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a ring member atom. Examples of the divalent alicyclic hydrocarbon group represented by G 1 and G 2 include cyclopentanediyl, cyclohexanediyl, and cycloheptanediyl. The divalent alicyclic hydrocarbon group may be substituted by a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.
本說明書中，芳香族基係指具有平面性之環狀結構之基，該環狀結構所具有之π電子數依據休克爾定律為[4n＋2]個(n表示1以上之正整數)。於包含-N=及S-之類之雜原子作為環員原子而形成環狀結構之情形時，亦包括包含該等雜原子上之非共價鍵電子對在內滿足休克爾定律，具有芳香族性之情形。In this specification, an aromatic group refers to a group having a planar ring structure, and the number of π electrons in the ring structure is [4n+2] according to Huckel's law (n represents a positive integer of 1 or more). In the case of forming a ring structure including heteroatoms such as -N= and S- as ring member atoms, it also includes the non-covalent bond electron pairs on these heteroatoms to satisfy Huckel's law, with aromatic The case of ethnicity.
G1 及G2 較佳為分別獨立為可經選自由鹵素原子及碳數1～4之烷基所組成之群中之至少1個取代基取代的1,4-伸苯二基、可經選自由鹵素原子及碳數1～4之烷基所組成之群中之至少1個取代基取代的1,4-環己二基，更佳為經甲基取代之1,4-伸苯二基、未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基，尤佳為未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基。又，較佳為存在複數個之G1 及G2 中之至少1個為二價脂環式烴基，又，更佳為鍵結於L1 或L2 之G1 及G2 中之至少1個為二價脂環式烴基。G 1 and G 2 are preferably each independently 1,4-phenylenediyl that may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbons, and may be substituted by 1,4-cyclohexanediyl substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted by methyl base, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, especially unsubstituted 1,4-phenylenediyl, or unsubstituted Substituted 1,4-trans cyclohexanediyl. Also, it is preferable that at least one of the plurality of G 1 and G 2 is a divalent alicyclic hydrocarbon group, and more preferably at least one of G 1 and G 2 that is bonded to L 1 or L 2 One is a divalent alicyclic hydrocarbon group.
液晶化合物(I)-1較佳為於波長260～400 nm之區域具有極大吸收。於液晶化合物(I)-1具備具有雜原子之芳香族基或使共軛系擴張之結構之情形時，與苯環相比，近紫外區域之吸收向長波長側偏移，因此多數情況下於260 nm以上之波長區域具有極大吸收，若如此於260 nm以上之波長區域具有極大吸收，則就提高逆波長分散性之觀點而言較佳。又，於在大於波長400 nm之波長區域具有極大吸收之情形時，有產生著色之情況，故而液晶化合物(I)-1較佳為於波長400 nm以下之區域具有極大吸收。進而，就進一步提高波長分散性之觀點而言，更佳為於波長280 nm以上400 nm以下之區域具有極大吸收，進而較佳為於波長300 nm以上400 nm以下之區域具有極大吸收。The liquid crystal compound (I)-1 preferably has a maximum absorption in the region of wavelength 260-400 nm. When the liquid crystal compound (I)-1 has an aromatic group having a heteroatom or a structure in which a conjugated system is extended, the absorption in the near-ultraviolet region is shifted to the long-wavelength side compared with the benzene ring, so in many cases It has a maximum absorption in the wavelength region of 260 nm or more, and it is preferable from the viewpoint of improving the inverse wavelength dispersion if it has the maximum absorption in the wavelength region of 260 nm or more. Also, when there is maximum absorption in a wavelength region longer than 400 nm, coloring may occur, so liquid crystal compound (I)-1 preferably has maximum absorption in a wavelength region below 400 nm. Furthermore, from the viewpoint of further improving the wavelength dispersibility, it is more preferable to have maximum absorption in the wavelength range of 280 nm to 400 nm, and further preferably to have maximum absorption in the wavelength range of 300 nm to 400 nm.
液晶化合物(I)-1較佳為具有下述式(I)-2：
[化7]
式(I)-2中，Ar表示具有2個以上之環結構之2價基，該2個以上之環結構中之1個為6員環，於該6員環之1位及4位與L1 及L2 鍵結， L1 、L2 、及B1 分別獨立表示單鍵或二價連結基， G1 、G2 、及G3 分別獨立表示二價芳香族基或二價脂環式烴基，該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基、或硝基，該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子， *表示鍵結鍵。In the formula (I)-2, Ar represents a divalent group having two or more ring structures, and one of the two or more ring structures is a 6-membered ring, and the 1st and 4th positions of the 6-membered ring and L 1 and L 2 are bonded, L 1 , L 2 , and B 1 independently represent a single bond or a divalent linking group, G 1 , G 2 , and G 3 independently represent a divalent aromatic group or a divalent alicyclic ring The hydrogen atom contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently replaced by a halogen atom, an alkyl group with 1 to 4 carbons, a fluoroalkyl group with 1 to 4 carbons, An alkoxy group, cyano group, or nitro group with 1 to 4 carbons, the carbon atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by oxygen atom, sulfur atom, or nitrogen Atom, * indicates bonded bond.
式(I)-2中之Ar、L1 、L2 、G1 、及G2 分別與式(I)-1中之Ar、L1 、L2 、G1 、及G2 含義相同。Ar, L 1 , L 2 , G 1 , and G 2 in formula (I)-2 have the same meanings as Ar, L 1 , L 2 , G 1 , and G 2 in formula (I)-1, respectively.
B1 較佳為表示單鍵、碳數1～4之伸烷基、-O-、-S-、-Ra1 ORa2 -、-Ra3 COORa4 -、-Ra5 OCORa6 -、Ra7 OC=OORa8 -、-N=N-、-CRc =CRd -、或-C≡C-。L1 及L2 更佳為分別獨立表示單鍵、-ORa2-1 -、-CH2 -、-CH2 CH2 -、-COORa4-1 -、或-OCORa6-1 -。此處，Ra2-1 、Ra4-1 、Ra6-1 分別獨立表示單鍵、-CH2 -、或-CH2 CH2 -。L1 及L2 進而較佳為分別獨立表示單鍵、-O-、-CH2 CH2 -、-COO-、-COOCH2 CH2 -、或-OCO-。B 1 preferably represents a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -, -R a3 COOR a4 -, -R a5 OCOR a6 -, R a7 OC=OOR a8 -, -N=N-, -CR c =CR d -, or -C≡C-. More preferably, L 1 and L 2 each independently represent a single bond, -OR a2-1 -, -CH 2 -, -CH 2 CH 2 -, -COOR a4-1 -, or -OCOR a6-1 -. Here, R a2-1 , R a4-1 , and R a6-1 each independently represent a single bond, -CH 2 -, or -CH 2 CH 2 -. More preferably, L 1 and L 2 each independently represent a single bond, -O-, -CH 2 CH 2 -, -COO-, -COOCH 2 CH 2 -, or -OCO-.
作為G3 所表示之二價芳香族基，例如可列舉伸苯二基及伸萘二基。二價芳香族基可經鹵素原子(更具體而言為氟原子、氯原子、及溴原子等)或碳數1～4之烷基之類之取代基取代。作為G3 所表示之二價脂環式烴基，例如可列舉環戊二基、環己二基、及環庚二基。二價脂環式烴基可經鹵素原子或碳數1～4之烷基之類之取代基取代。Examples of the divalent aromatic group represented by G3 include phenylenediyl and naphthalenediyl. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent alicyclic hydrocarbon group represented by G3 include cyclopentanediyl, cyclohexanediyl, and cycloheptanediyl. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.
G3
較佳為分別獨立為可經選自由鹵素原子及碳數1～4之烷基所組成之群中之至少1個取代基取代的1,4-伸苯二基、可經選自由鹵素原子及碳數1～4之烷基所組成之群中之至少1個取代基取代的1,4-環己二基，更佳為經甲基取代之1,4-伸苯二基、未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基，尤佳為未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基。 G3 is preferably each independently 1,4-phenylenediyl which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbons, and which may be substituted by at least one substituent selected from a
液晶化合物(I)-1更佳為具有下述式(I)-3：
[化8]
式(I)-3中，Ar表示具有2個以上之環結構之2價基，該2個以上之環結構中之1個為6員環，於該6員環之1位及4位與L1 及L2 鍵結， L1 、L2 、B1 、及B2 分別獨立表示單鍵或二價連結基， G1 、G2 、G3 、及G4 分別獨立表示二價芳香族基或二價脂環式烴基，該二價芳香族基或該二價脂環式烴基所包含之氫原子可被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基、或硝基，該二價芳香族基或該二價脂環式烴基所包含之碳原子可被取代為氧原子、硫原子、或氮原子， *表示鍵結鍵。In the formula (I)-3, Ar represents a divalent group having two or more ring structures, and one of the two or more ring structures is a 6-membered ring, and the 1st and 4th positions of the 6-membered ring and L 1 and L 2 are bonded, L 1 , L 2 , B 1 , and B 2 independently represent a single bond or a divalent linking group, G 1 , G 2 , G 3 , and G 4 independently represent a divalent aromatic A group or a divalent alicyclic hydrocarbon group, the hydrogen atoms contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 4 carbons, or an alkyl group with 1 to 4 carbons Fluoroalkyl group, alkoxy group with 1 to 4 carbons, cyano group, or nitro group, the carbon atoms contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group can be replaced by oxygen atom, sulfur atom, or a nitrogen atom, and * indicates a bonding bond.
式(I)-3中之Ar、L1 、L2 、G1 、及G2 分別與式(I)-1中之Ar、L1 、L2 、G1 、及G2 含義相同。式(I)-3中之B1 及G3 分別與式(I)-2中之B1 及G3 含義相同。Ar, L 1 , L 2 , G 1 , and G 2 in formula (I)-3 have the same meanings as Ar, L 1 , L 2 , G 1 , and G 2 in formula (I)-1, respectively. B 1 and G 3 in formula (I)-3 have the same meanings as B 1 and G 3 in formula (I)-2, respectively.
B2 較佳為表示單鍵、碳數1～4之伸烷基、-O-、-S-、-Ra1 ORa2 -、-Ra3 COORa4 -、-Ra5 OCORa6 -、Ra7 OC=OORa8 -、-N=N-、-CRc =CRd -、或-C≡C-。L1 及L2 更佳為分別獨立表示單鍵、-ORa2-1 -、-CH2 -、-CH2 CH2 -、-COORa4-1 -、或-OCORa6-1 -。此處，Ra2-1 、Ra4-1 、Ra6-1 分別獨立表示單鍵、-CH2 -、或-CH2 CH2 -。L1 及L2 進而較佳為分別獨立表示單鍵、-O-、-CH2 CH2 -、-COO-、-COOCH2 CH2 -、或-OCO-。B 2 preferably represents a single bond, an alkylene group with 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -, -R a3 COOR a4 -, -R a5 OCOR a6 -, R a7 OC=OOR a8 -, -N=N-, -CR c =CR d -, or -C≡C-. More preferably, L 1 and L 2 each independently represent a single bond, -OR a2-1 -, -CH 2 -, -CH 2 CH 2 -, -COOR a4-1 -, or -OCOR a6-1 -. Here, R a2-1 , R a4-1 , and R a6-1 each independently represent a single bond, -CH 2 -, or -CH 2 CH 2 -. More preferably, L 1 and L 2 each independently represent a single bond, -O-, -CH 2 CH 2 -, -COO-, -COOCH 2 CH 2 -, or -OCO-.
作為G4 所表示之二價芳香族基，例如可列舉伸苯二基或伸萘二基。二價芳香族基可經鹵素原子(更具體而言為氟原子、氯原子、及溴原子等)或碳數1～4之烷基之類之取代基取代。作為G3 所表示之二價脂環式烴基，例如可列舉環戊二基、環己二基、及環庚二基。二價脂環式烴基可經鹵素原子或碳數1～4之烷基之類之取代基取代。Examples of the divalent aromatic group represented by G 4 include phenylenediyl or naphthalenediyl. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent alicyclic hydrocarbon group represented by G3 include cyclopentanediyl, cyclohexanediyl, and cycloheptanediyl. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.
G4
較佳為可經選自由鹵素原子及碳數1～4之烷基所組成之群中之至少1個取代基取代的1,4-伸苯二基、可經選自由鹵素原子及碳數1～4之烷基所組成之群中之至少1個取代基取代的1,4-環己二基，更佳為經甲基取代之1,4-伸苯二基、未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基，尤佳為未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基。 G4 is preferably 1,4-phenylenediyl that may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and may be substituted by at least one substituent selected from a halogen atom and a
液晶化合物(I)-1可具有1個以上之聚合性基。於本說明書中，聚合性基係指能夠藉由自光聚合起始劑產生之活性自由基或酸之類之活性種而參與聚合之基。作為聚合性基，例如可列舉環氧基、乙烯基、乙烯氧基、1-氯乙烯基、異丙烯基、4-乙烯基苯基、丙烯醯氧基、甲基丙烯醯氧基、環氧乙烷基、及氧雜環丁基。該等聚合性基之中，較佳為丙烯醯氧基及甲基丙烯醯氧基。於本說明書中，具有聚合性基之液晶化合物(I)-1可藉由聚合反應形成聚合物。Liquid crystal compound (I)-1 may have one or more polymerizable groups. In this specification, a polymerizable group refers to a group capable of participating in polymerization by active species such as active radicals or acids generated from a photopolymerization initiator. Examples of polymerizable groups include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, epoxy Ethyl, and oxetanyl. Among these polymerizable groups, an acryloxy group and a methacryloxy group are preferable. In this specification, the liquid crystal compound (I)-1 having a polymerizable group can form a polymer through a polymerization reaction.
作為液晶化合物(I)-1，例如可列舉具有式(A)-1～式(A)-5所表示之結構之液晶化合物。As liquid crystal compound (I)-1, the liquid crystal compound which has the structure represented by formula (A)-1 - a formula (A)-5 is mentioned, for example.
(液晶化合物A)
[化9]
液晶化合物(I)-1之含量(於包含複數種液晶化合物之情形時為其含量之合計)較佳為相對於組合物之固形物成分100質量份為50～99.5質量份，更佳為60～99質量份，進而較佳為70～99質量份。於本說明書中，組合物之固形物成分之質量係指自該組合物去除溶劑後之成分之合計質量。The content of the liquid crystal compound (I)-1 (the sum of the contents when a plurality of liquid crystal compounds are included) is preferably 50 to 99.5 parts by mass relative to 100 parts by mass of the solid content of the composition, more preferably 60 parts by mass. -99 parts by mass, more preferably 70-99 parts by mass. In this specification, the mass of the solid content of a composition means the total mass of the components after removing a solvent from this composition.
[2.非離子性矽烷化合物] 於本說明書中，非離子性矽烷化合物係非離子性且包含Si元素之化合物。非離子性矽烷化合物於垂直配向液晶硬化膜之製作中，能夠充分地提高液晶化合物(I)-1之垂直配向性，且藉由與離子性化合物之組合而進一步提高液晶化合物(I)-1之垂直配向性。又，非離子性矽烷化合物容易降低組合物之表面張力，能夠提昇組合物對基材之潤濕性。作為非離子性矽烷化合物，例如可列舉聚矽烷之類之矽聚合物、聚矽氧油及聚矽氧樹脂之類之聚矽氧樹脂、以及聚矽氧低聚物、倍半矽氧烷、及烷氧基矽烷之類之有機無機矽烷化合物(更具體而言為矽烷偶合劑等)。[2. Nonionic silane compound] In this specification, a nonionic silane compound is a nonionic compound containing Si element. Nonionic silane compounds can fully improve the vertical alignment of liquid crystal compound (I)-1 in the production of vertical alignment liquid crystal cured film, and further improve the vertical alignment of liquid crystal compound (I)-1 by combining with ionic compounds. the vertical alignment. In addition, the nonionic silane compound is easy to reduce the surface tension of the composition, and can improve the wettability of the composition to the substrate. Examples of nonionic silane compounds include silicone polymers such as polysilanes, silicone oils and silicone resins such as silicone resins, silicone oligomers, silsesquioxanes, and organoinorganic silane compounds such as alkoxysilanes (more specifically, silane coupling agents, etc.).
非離子性矽烷化合物可為聚矽氧單體型，亦可為聚矽氧低聚物(聚合物)型。若以(單體)-(單體)共聚物之形式表示聚矽氧低聚物，則可列舉：3-巰基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-巰基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-巰基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、及3-巰基丙基三乙氧基矽烷-四乙氧基矽烷共聚物之類之含巰基丙基之共聚物；巰基甲基三甲氧基矽烷-四甲氧基矽烷共聚物、巰基甲基三甲氧基矽烷-四乙氧基矽烷共聚物、巰基甲基三乙氧基矽烷-四甲氧基矽烷共聚物、及巰基甲基三乙氧基矽烷-四乙氧基矽烷共聚物之類之含巰基甲基之共聚物；3-甲基丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-甲基丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含甲基丙烯醯氧基丙基之共聚物；3-丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及3-丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含丙烯醯氧基丙基之共聚物；乙烯基三甲氧基矽烷-四甲氧基矽烷共聚物、乙烯基三甲氧基矽烷-四乙氧基矽烷共聚物、乙烯基三乙氧基矽烷-四甲氧基矽烷共聚物、乙烯基三乙氧基矽烷-四乙氧基矽烷共聚物、乙烯基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、乙烯基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、乙烯基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及乙烯基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含乙烯基之共聚物；3-胺基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及3-胺基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含胺基之共聚物等。該等非離子性矽烷化合物可單獨使用1種，或者亦可組合2種以上使用。又，亦可使用調平劑之項所例示之含矽烷之化合物。該等非離子性矽烷化合物之中，就進一步提高密接性之觀點而言，較佳為矽烷偶合劑。The nonionic silane compound can be polysiloxane monomer type or polysiloxane oligomer (polymer) type. If polysiloxane oligomers are expressed in the form of (monomer)-(monomer) copolymers, examples include: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl Trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer Copolymers containing mercaptopropyl group; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane 3-Methacryloxypropyltrimethylsilane Oxysilane-Tetramethoxysilane Copolymer, 3-Methacryloxypropyltrimethoxysilane-Tetraethoxysilane Copolymer, 3-Methacryloxypropyltriethoxysilane -Tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane -Tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxy methacryloxypropyl group-containing silane-tetramethoxysilane copolymer, and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymer; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxysilane propyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyl di Methoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxy Copolymers containing acryloxypropyl groups such as silane-tetramethoxysilane copolymer and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; ethylene Trimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane Silane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethoxysilane Diethoxysilane-tetramethoxysilane copolymer, and vinyl-containing copolymers such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyl trimethyl Oxysilane-Tetramethoxysilane Copolymer, 3-Aminopropyltrimethoxysilane-Tetraethoxysilane Copolymer, 3-Aminopropyltriethoxysilane-Tetramethoxysilane Copolymer , 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyl methyl Dimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-aminopropylmethyldiethoxysilane Amine-containing copolymers such as silane-tetraethoxysilane copolymers, etc. These nonionic silane compounds may be used alone or in combination of two or more. Moreover, the silane-containing compound exemplified in the section of the leveling agent can also be used. Among these nonionic silane compounds, a silane coupling agent is preferable from the viewpoint of further improving adhesion.
矽烷偶合劑係於末端具有選自由乙烯基、環氧基、苯乙烯基、甲基丙烯醯基、丙烯醯基、胺基、異氰尿酸酯基、脲基、巰基、異氰酸酯基、羧基、及羥基所組成之群中之至少1種之類之官能基、及至少一個烷氧基矽烷基或矽烷醇基的包含Si元素之化合物。藉由適當選定該等官能基，能夠賦予垂直配向液晶硬化膜之機械強度之提高、垂直配向液晶硬化膜之表面改質、與鄰接於垂直配向液晶硬化膜之層(例如基材)之密接性提高等特殊之效果。就進一步提高密接性之觀點而言，矽烷偶合劑較佳為具有烷氧基矽烷基及另一不同之反應基(例如上述官能基)的矽烷偶合劑。矽烷偶合劑進而較佳為具有烷氧基矽烷基與極性基之矽烷偶合劑。若矽烷偶合劑於其分子內具有至少一個烷氧基矽烷基及至少一個極性基，則液晶化合物之垂直配向性進一步提昇，可明顯獲得垂直配向促進效果。作為極性基，例如可列舉環氧基、胺基、異氰尿酸酯基、巰基、羧基、及羥基。再者，極性基為了控制矽烷偶合劑之反應性，亦可適當具有取代基或保護基。The silane coupling agent has a terminal group selected from vinyl, epoxy, styrene, methacryl, acryl, amine, isocyanurate, ureido, mercapto, isocyanate, carboxyl, A compound containing Si element, such as at least one functional group of the group consisting of hydroxyl group and at least one alkoxysilyl group or silanol group. By properly selecting these functional groups, it is possible to provide improved mechanical strength of the vertically aligned liquid crystal cured film, surface modification of the vertically aligned liquid crystal cured film, and adhesion to a layer (such as a substrate) adjacent to the vertically aligned liquid crystal cured film. Enhance and other special effects. From the viewpoint of further improving the adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (such as the above-mentioned functional group). The silane coupling agent is further preferably a silane coupling agent having an alkoxysilyl group and a polar group. If the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment of the liquid crystal compound will be further improved, and the effect of promoting vertical alignment can be obviously obtained. As a polar group, an epoxy group, an amine group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxyl group are mentioned, for example. In addition, the polar group may have a substituent or a protecting group as appropriate in order to control the reactivity of the silane coupling agent.
作為矽烷偶合劑，例如可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基二甲氧基甲基矽烷、及3-縮水甘油氧基丙基乙氧基二甲基矽烷。Examples of silane coupling agents include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethyl Oxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.
又，作為市售之矽烷偶合劑，例如可列舉KP321、KP323、KP324、KP326、KP340、KP341、X22-161A、KF6001、KBM-1003、KBE-1003、KBM-303、KBM-402、KBM-403、KBE-402、KBE-403、KBM-1403、KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-602、KBM-603、KBM-903、KBE-903、KBE-9103、KBM-573、KBM-575、KBM-9659、KBE-585、KBM-802、KBM-803、KBE-846、及KBE-9007之類之信越化學工業(股)製造之矽烷偶合劑。Moreover, examples of commercially available silane coupling agents include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403 , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE - Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as 9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.
非離子性矽烷化合物之含有率通常相對於組合物之固形物成分，較佳為0.01～5質量%，更佳為0.05～4質量%，進而較佳為0.1～3質量%。若非離子性矽烷化合物之含有率相對於組合物之固形物成分為0.01質量%以上，則液晶化合物之垂直配向性進一步提高，若非離子性矽烷化合物之含有率相對於組合物之固形物成分，以5質量%以下含有，則組合物之塗佈性不易降低。The content of the nonionic silane compound is usually preferably from 0.01 to 5% by mass, more preferably from 0.05 to 4% by mass, and still more preferably from 0.1 to 3% by mass, based on the solid content of the composition. When the content of the nonionic silane compound is 0.01% by mass or more relative to the solid content of the composition, the vertical alignment of the liquid crystal compound is further improved, and if the content of the nonionic silane compound is greater than or equal to the solid content of the composition. If it is contained at 5% by mass or less, the coatability of the composition is less likely to decrease.
[3.離子性化合物] 離子性化合物於垂直配向液晶硬化膜之製作中，能夠充分地提高液晶化合物(I)-1之垂直配向性，且藉由與非離子性矽烷化合物之組合而進一步提高液晶化合物(I)-1之垂直配向性。[3. Ionic compounds] The ionic compound can fully improve the vertical alignment of the liquid crystal compound (I)-1 in the production of the vertically aligned liquid crystal cured film, and further improve the liquid crystal compound (I)-1 by combining it with a nonionic silane compound. the vertical alignment.
作為離子性化合物，例如可列舉鎓鹽(更具體而言為氮原子具有正電荷之四級銨鹽、三級鋶鹽、及磷原子具有正電荷之四級鏻鹽等)。該等鎓鹽之中，就進一步提高液晶化合物(I)-1之垂直配向性之觀點而言，較佳為四級鎓鹽，就提高獲取性及量產性之觀點而言，進而較佳為四級鏻鹽或四級銨鹽。鎓鹽亦可於分子內具有2個以上四級鎓鹽部位，亦可為低聚物或聚合物。Examples of ionic compounds include onium salts (more specifically, quaternary ammonium salts having a positive charge on a nitrogen atom, tertiary permeium salts, and quaternary phosphonium salts having a positive charge on a phosphorus atom). Among these onium salts, quaternary onium salts are preferred from the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1, and further preferred from the viewpoint of improving availability and mass production. It is a quaternary phosphonium salt or a quaternary ammonium salt. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.
就進一步提高液晶化合物(I)-1之垂直配向性之觀點而言，離子性化合物之分子量較佳為100以上。又，就進一步提高組合物之塗佈性之觀點而言，離子性化合物之分子量較佳為10000以下，更佳為5000以下，進而較佳為3000以下。就進一步提高液晶化合物(I)-1之垂直配向性且進一步提高組合物之塗佈性之觀點而言，離子性化合物之分子量更佳為100以上10000以下。From the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1, the molecular weight of the ionic compound is preferably 100 or more. Moreover, from the viewpoint of further improving the coatability of the composition, the molecular weight of the ionic compound is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less. The molecular weight of the ionic compound is more preferably from 100 to 10,000 from the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1 and further improving the coatability of the composition.
作為離子性化合物之陽離子成分，例如可列舉無機之陽離子及有機之陽離子。該等離子性化合物之陽離子成分之中，就抑制液晶化合物之配向缺陷產生之觀點而言，較佳為有機之陽離子。作為有機之陽離子，例如可列舉咪唑鎓陽離子、吡啶鎓陽離子、銨陽離子、鋶陽離子、及鏻陽離子。Examples of the cationic component of the ionic compound include inorganic cations and organic cations. Among the cation components of the plasmonic compound, organic cations are preferred from the viewpoint of suppressing the occurrence of alignment defects in liquid crystal compounds. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, percite cations, and phosphonium cations.
另一方面，離子性化合物一般具有抗衡陰離子。作為成為上述陽離子成分之抗衡離子的陰離子成分，例如可列舉無機之陰離子或有機之陰離子。該等陰離子成分之中，就抑制液晶化合物之配向缺陷產生之觀點而言，較佳為有機之陰離子。又，陽離子與陰離子並非必須一對一地對應。作為陰離子成分，例如可列舉如下者。 氯化物陰離子[Cl- ]、 溴化物陰離子[Br- ]、 碘化物陰離子[I- ]、 四氯鋁酸根陰離子[AlCl4 - ]、 七氯二鋁酸根陰離子[Al2 Cl7 - ]、 四氟硼酸根陰離子[BF4 - ]、 六氟磷酸根陰離子[PF6 - ]、 過氯酸根陰離子[ClO4 - ]、 硝酸根陰離子[NO3 - ]、 乙酸根陰離子[CH3 COO- ]、 三氟乙酸根陰離子[CF3 COO- ]、 氟磺酸根陰離子[FSO3 - ]、 甲磺酸根陰離子[CH3 SO3 - ]、 三氟甲磺酸根陰離子[CF3 SO3 - ]、 對甲苯磺酸根陰離子[p-CH3 C6 H4 SO3 - ]、 雙(氟磺醯)亞胺陰離子[(FSO2 )2 N- ]、 雙(三氟甲磺醯)亞胺陰離子[(CF3 SO2 )2 N- ]、 三(三氟甲磺醯)甲烷陰離子[(CF3 SO2 )3 C- ]、 六氟砷酸根陰離子[AsF6 - ]、 六氟銻酸根陰離子[SbF6 - ]、 六氟鈮酸根陰離子[NbF6 - ]、 六氟鉭酸根陰離子[TaF6 - ]、 二甲基次膦酸根陰離子[(CH3 )2 POO- ]、 (聚)氫氟氟化物陰離子[F(HF)n - ](例如，n表示1～3之整數)、 二氰亞胺陰離子[(CN)2 N- ]、 硫氰化物陰離子[SCN- ]、 全氟丁磺酸根陰離子[C4 F9 SO3 - ]、 雙(五氟乙磺醯)亞胺陰離子[(C2 F5 SO2 )2 N- ]、 全氟丁酸根陰離子[C3 F7 COO- ]、及 (三氟甲磺醯基)(三氟甲烷羰基)醯亞胺陰離子[(CF3 SO2 )(CF3 CO)N- ]。On the other hand, ionic compounds generally have a counter anion. As an anion component used as a counter ion of the said cation component, an inorganic anion or an organic anion is mentioned, for example. Among these anion components, organic anions are preferred from the viewpoint of suppressing the occurrence of alignment defects in liquid crystal compounds. In addition, cations and anions do not necessarily correspond to one-to-one. As an anion component, the following are mentioned, for example. Chloride anion [Cl - ], bromide anion [Br - ], iodide anion [I - ], tetrachloroaluminate anion [AlCl 4 - ], heptachlorodialuminate anion [Al 2 Cl 7 - ], tetrachloroaluminate anion [Al 2 Cl 7 - ], Fluoborate anion [BF 4 - ], hexafluorophosphate anion [PF 6 - ], perchlorate anion [ClO 4 - ], nitrate anion [NO 3 - ], acetate anion [CH 3 COO - ], Trifluoroacetate anion [CF 3 COO - ], fluorosulfonate anion [FSO 3 - ], mesylate anion [CH 3 SO 3 - ], trifluoromethanesulfonate anion [CF 3 SO 3 - ], p-toluene Sulfonate anion [p-CH 3 C 6 H 4 SO 3 - ], bis(fluorosulfonyl)imide anion [(FSO 2 ) 2 N - ], bis(trifluoromethanesulfonyl)imide anion [(CF 3 SO 2 ) 2 N - ], tris(trifluoromethanesulfonyl)methane anion [(CF 3 SO 2 ) 3 C - ], hexafluoroarsenate anion [AsF 6 - ], hexafluoroantimonate anion [SbF 6 - ], hexafluoroniobate anion [NbF 6 - ], hexafluorotantalate anion [TaF 6 - ], dimethylphosphinate anion [(CH 3 ) 2 POO - ], (poly)hydrofluorofluoride anion [F(HF) n - ] (for example, n represents an integer of 1 to 3), dicyanoimide anion [(CN) 2 N - ], thiocyanide anion [SCN - ], perfluorobutanesulfonate anion [ C 4 F 9 SO 3 - ], bis(pentafluoroethanesulfonyl)imide anion [(C 2 F 5 SO 2 ) 2 N - ], perfluorobutyrate anion [C 3 F 7 COO - ], and (Trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF 3 SO 2 )(CF 3 CO)N − ].
作為離子性化合物之具體例，可自上述陽離子成分與陰離子成分之組合適當選擇。作為具體之陽離子成分與陰離子成分組合之化合物，可列舉如下者。As a specific example of an ionic compound, it can select suitably from the combination of the said cationic component and anionic component. Specific compounds in which a cationic component and an anionic component are combined include the following.
(吡啶鎓鹽) 六氟磷酸N-己基吡啶鎓、 六氟磷酸N-辛基吡啶鎓、 六氟磷酸N-甲基-4-己基吡啶鎓、 六氟磷酸N-丁基-4-甲基吡啶鎓、 六氟磷酸N-辛基-4-甲基吡啶鎓、 雙(氟磺醯)亞胺N-己基吡啶鎓、 雙(氟磺醯)亞胺N-辛基吡啶鎓、 雙(氟磺醯)亞胺N-甲基-4-己基吡啶鎓、 雙(氟磺醯)亞胺N-丁基-4-甲基吡啶鎓、 雙(氟磺醯)亞胺N-辛基-4-甲基吡啶鎓、 雙(三氟甲磺醯)亞胺N-己基吡啶鎓、 雙(三氟甲磺醯)亞胺N-辛基吡啶鎓、 雙(三氟甲磺醯)亞胺N-甲基-4-己基吡啶鎓、 雙(三氟甲磺醯)亞胺N-丁基-4-甲基吡啶鎓、 雙(三氟甲磺醯)亞胺N-辛基-4-甲基吡啶鎓、 對甲苯磺酸N-己基吡啶鎓、 對甲苯磺酸N-辛基吡啶鎓、 對甲苯磺酸N-甲基-4-己基吡啶鎓、 對甲苯磺酸N-丁基-4-甲基吡啶鎓、及 對甲苯磺酸N-辛基-4-甲基吡啶鎓。(pyridinium salt) N-hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, Bis(fluorosulfonyl)imide N-hexylpyridinium, Bis(fluorosulfonyl)imide N-octylpyridinium, Bis(fluorosulfonyl)imide N-methyl-4-hexylpyridinium, Bis(fluorosulfonyl)imide N-butyl-4-methylpyridinium, Bis(fluorosulfonyl)imide N-octyl-4-methylpyridinium, Bis(trifluoromethanesulfonyl)imide N-hexylpyridinium, Bis(trifluoromethanesulfonyl)imide N-octylpyridinium, Bis(trifluoromethanesulfonyl)imide N-methyl-4-hexylpyridinium, Bis(trifluoromethanesulfonyl)imide N-butyl-4-methylpyridinium, Bis(trifluoromethanesulfonyl)imide N-octyl-4-methylpyridinium, N-hexylpyridinium p-toluenesulfonate, N-octylpyridinium p-toluenesulfonate, N-methyl-4-hexylpyridinium p-toluenesulfonate, N-butyl-4-methylpyridinium p-toluenesulfonate, and N-octyl-4-methylpyridinium p-toluenesulfonate.
(咪唑鎓鹽) 六氟磷酸1-乙基-3-甲基咪唑鎓、 雙(氟磺醯)亞胺1-乙基-3-甲基咪唑鎓、 雙(三氟甲磺醯)亞胺1-乙基-3-甲基咪唑鎓、 對甲苯磺酸1-乙基-3-甲基咪唑鎓、 甲磺酸1-丁基-3-甲基咪唑鎓等。(imidazolium salt) 1-ethyl-3-methylimidazolium hexafluorophosphate, Bis(fluorosulfonyl)imide 1-ethyl-3-methylimidazolium, Bis(trifluoromethanesulfonyl)imide 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, etc.
(吡咯啶鎓鹽) 六氟磷酸N-丁基-N-甲基吡咯啶鎓、 雙(氟磺醯)亞胺N-丁基-N-甲基吡咯啶鎓、 雙(三氟甲磺醯)亞胺N-丁基-N-甲基吡咯啶鎓、 對甲苯磺酸N-丁基-N-甲基吡咯啶鎓等。(pyrrolidinium salt) N-butyl-N-methylpyrrolidinium hexafluorophosphate, Bis(fluorosulfonyl)imide N-butyl-N-methylpyrrolidinium, Bis(trifluoromethanesulfonyl)imide N-butyl-N-methylpyrrolidinium, N-butyl-N-methylpyrrolidinium p-toluenesulfonate, etc.
(銨鹽) 六氟磷酸四丁基銨、 雙(氟磺醯)亞胺四丁基銨、 雙(氟磺醯)亞胺四己基銨、 雙(氟磺醯)亞胺三辛基甲基銨、 雙(氟磺醯)亞胺(2-羥基乙基)三甲基銨、 雙(三氟甲磺醯)亞胺四丁基銨、 雙(三氟甲磺醯)亞胺四己基銨、 雙(三氟甲磺醯)亞胺三辛基甲基銨、 雙(三氟甲磺醯)亞胺(2-羥基乙基)三甲基銨、 對甲苯磺酸四丁基銨、 對甲苯磺酸四己基銨、 對甲苯磺酸三辛基甲基銨、 對甲苯磺酸(2-羥基乙基)三甲基銨、 二甲基亞膦酸(2-羥基乙基)三甲基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丙基)-1,1,1-三丁基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丙基)-1,1,1-三甲基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丁基)-1,1,1-三丁基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丁基)-1,1,1-三甲基銨、 雙(三氟甲磺醯)亞胺N-{(3-三乙氧基矽烷基丙基)胺甲醯氧基乙基)}-N,N,N-三甲基銨、及 雙(三氟甲磺醯)亞胺N-[2-{3-(3-三甲氧基矽烷基丙基胺基)-1-側氧基丙氧基}乙基]-N,N,N-三甲基銨。(ammonium salt) Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium bis(fluorosulfonyl)imide, Bis(fluorosulfonyl)imide tetrahexylammonium, bis(fluorosulfonyl)imide trioctylmethylammonium, Bis(fluorosulfonyl)imide (2-hydroxyethyl)trimethylammonium, Tetrabutylammonium bis(trifluoromethanesulfonyl)imide, Tetrahexylammonium bis(trifluoromethanesulfonyl)imide, bis(trifluoromethanesulfonyl)imide trioctylmethylammonium, bis(trifluoromethanesulfonyl)imide(2-hydroxyethyl)trimethylammonium, Tetrabutylammonium p-toluenesulfonate, Tetrahexylammonium p-toluenesulfonate, Trioctylmethylammonium p-toluenesulfonate, (2-Hydroxyethyl)trimethylammonium p-toluenesulfonate, (2-Hydroxyethyl)trimethylammonium dimethylphosphonous acid, Bis(trifluoromethanesulfonyl)imide 1-(3-trimethoxysilylpropyl)-1,1,1-tributylammonium, Bis(trifluoromethanesulfonyl)imide 1-(3-trimethoxysilylpropyl)-1,1,1-trimethylammonium, Bis(trifluoromethanesulfonyl)imide 1-(3-trimethoxysilylbutyl)-1,1,1-tributylammonium, Bis(trifluoromethanesulfonyl)imide 1-(3-trimethoxysilylbutyl)-1,1,1-trimethylammonium, Bis(trifluoromethanesulfonyl)imide N-{(3-triethoxysilylpropyl)aminoformyloxyethyl)}-N,N,N-trimethylammonium, and Bis(trifluoromethanesulfonyl)imide N-[2-{3-(3-trimethoxysilylpropylamino)-1-oxopropoxy}ethyl]-N,N,N - Trimethylammonium.
(鏻鹽)
雙(三氟甲磺醯)亞胺三丁基(2-甲氧基乙基)鏻、
雙(三氟甲磺醯)亞胺三丁基甲基鏻、
雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[(三甲氧基矽烷基)甲基]鏻、
雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[2-(三甲氧基矽烷基)乙基]鏻、
雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[3-(三甲氧基矽烷基)丙基]鏻、
雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[4-(三甲氧基矽烷基)丁基]鏻、
雙(三氟甲磺醯)亞胺1,1,1-三丁基-1-[(三甲氧基矽烷基)甲基]鏻、
雙(三氟甲磺醯)亞胺1,1,1-三丁基-1-[2-(三甲氧基矽烷基)乙基]鏻、及
雙(三氟甲磺醯)亞胺1,1,1-三丁基-1-[3-(三甲氧基矽烷基)丙基]鏻。(phosphonium salt)
Bis(trifluoromethanesulfonyl)imide tributyl(2-methoxyethyl)phosphonium,
Bis(trifluoromethanesulfonyl)imide tributylmethylphosphonium,
Bis(trifluoromethanesulfonyl)
該等離子性化合物可分別單獨使用，或者亦可組合2種以上使用。又，就進一步提高液晶化合物之垂直配向性之觀點而言，離子性化合物較佳為於陽離子部位之分子結構中具有Si元素及/或F元素。其原因在於，若離子性化合物於陽離子部位之分子結構中具有Si元素及/或F元素，則能夠使離子性化合物偏析至垂直配向液晶硬化膜之表面。該等離子性化合物之中，較佳為整體由非金屬元素構成之離子性化合物(更具體而言為下述離子性化合物(1)～(3)等)。These ionic compounds may be used alone, respectively, or may be used in combination of two or more. Also, from the viewpoint of further improving the vertical alignment of the liquid crystal compound, the ionic compound preferably has Si element and/or F element in the molecular structure of the cation site. The reason is that if the ionic compound has Si element and/or F element in the molecular structure of the cation site, the ionic compound can be segregated to the surface of the vertically aligned liquid crystal cured film. Among these ionic compounds, ionic compounds (more specifically, the following ionic compounds (1) to (3) and the like) which are entirely composed of nonmetallic elements are preferred.
(離子性化合物(1))
[化14]
作為提高液晶化合物之垂直配向性之方法，例如可列舉使用具有鏈長一定程度較長之烷基之界面活性劑對基材表面進行處理之方法。該方法例如記載於「液晶便覽」之第2章 液晶之配向與物性(丸善股份有限公司發行)等。如此藉由界面活性劑而提高液晶化合物之垂直配向性之方法可應用於離子性化合物。即，作為提高液晶化合物之垂直配向性之方法，例如可列舉使用具有鏈長一定程度較長之烷基之離子性化合物對基材表面進行處理之方法。更具體而言，就提高液晶化合物之垂直配向性之觀點而言，離子性化合物較佳為滿足下述式(10)。 5＜M＜16 (10) 式(10)中，M由下述式(11)表示。 M＝(直接鍵結於具有正電荷之原子上之取代基中，至分子鏈末端之共價鍵數最多之取代基的自具有正電荷之原子起至分子鏈末端之共價鍵數)÷(具有正電荷之原子之數) (11)As a method of improving the vertical alignment property of a liquid crystal compound, the method of treating the surface of a base material with the surfactant which has an alkyl group with a certain length of chain length is mentioned, for example. This method is described, for example, in Chapter 2: Alignment and Physical Properties of Liquid Crystals in "Liquid Crystal Handbook" (published by Maruzen Co., Ltd.). Such a method of improving the vertical alignment of liquid crystal compounds by using surfactants can be applied to ionic compounds. That is, as a method of improving the vertical alignment property of a liquid crystal compound, the method of treating the surface of a base material with the ionic compound which has an alkyl group with a certain length of chain length is mentioned, for example. More specifically, the ionic compound preferably satisfies the following formula (10) from the viewpoint of improving the vertical alignment of the liquid crystal compound. 5<M<16 (10) In formula (10), M is represented by the following formula (11). M=(among the substituents directly bonded to atoms with positive charge, the number of covalent bonds from the atom with positive charge to the end of the molecular chain of the substituent with the largest number of covalent bonds to the end of the molecular chain)÷ (Number of atoms with a positive charge) (11)
再者，於在離子性化合物之分子中存在2個以上具有正電荷之原子之情形時，關於具有2個以上具有正電荷之原子之取代基，將自視作基點之具有正電荷之原子開始算起，至最近之另一具有正電荷之原子的共價鍵數作為上述M之定義中所記載之「自具有正電荷之原子起至分子鏈末端之共價鍵數」。又，於離子性化合物為具有2個以上重複單元之低聚物或聚合物之情形時，將結構單元視作一分子，算出上述M。於具有正電荷之原子組入至環結構之情形時，將經由環結構至該具有正電荷之原子之共價鍵數、或至環結構上鍵結之取代基之末端之共價鍵數中共價鍵數較多者作為上述M之定義中所記載之「自具有正電荷之原子起至分子鏈末端之共價鍵數」。Furthermore, when there are two or more positively charged atoms in the molecule of the ionic compound, regarding the substituent having two or more positively charged atoms, start from the positively charged atom as the base point Count the number of covalent bonds to the nearest atom with a positive charge as the "number of covalent bonds from the atom with a positive charge to the end of the molecular chain" described in the definition of M above. Moreover, when an ionic compound is an oligomer or a polymer which has 2 or more repeating units, the said M is calculated considering a structural unit as one molecule. When an atom with a positive charge is incorporated into a ring structure, the number of covalent bonds to the atom with a positive charge via the ring structure, or the number of covalent bonds to the end of the substituent bonded to the ring structure is totaled The one with the larger number of valence bonds is the "number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above.
離子性化合物之含有率通常相對於組合物之固形物成分，較佳為0.01～5質量%，更佳為0.05～4質量%，進而較佳為0.1～3質量%。若離子性化合物之含有率於組合物之固形物成分中為0.01質量%以上，則液晶化合物之垂直配向性進一步提高，若離子性化合物之含有率相對於組合物之固形物成分為5質量%以下，則組合物之塗佈性不易降低。The content of the ionic compound is usually preferably from 0.01 to 5% by mass, more preferably from 0.05 to 4% by mass, and still more preferably from 0.1 to 3% by mass, based on the solid content of the composition. If the content of the ionic compound is 0.01% by mass or more in the solid content of the composition, the vertical alignment of the liquid crystal compound will be further improved. If the content of the ionic compound is 5% by mass relative to the solid content of the composition Below, the applicability of the composition is less likely to decrease.
[4.其他成分] 本發明之組合物亦可視需要進而包含例如溶劑、光聚合起始劑、聚合抑制劑、光增感劑、調平劑、密接性改善劑之類之添加劑作為其他成分。該等添加劑可單獨使用1種，或者亦可組合2種以上使用。[4. Other ingredients] The composition of the present invention may further contain additives such as a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and an adhesiveness improving agent as other components, if necessary. These additives may be used alone or in combination of two or more.
(溶劑) 本發明之組合物由於通常以溶解於溶劑中之狀態塗佈於基材等，故而較佳為包含溶劑。作為溶劑，例如可列舉水、甲醇、乙醇、乙二醇、異丙醇、丙二醇、乙二醇甲醚、乙二醇丁醚、1-甲氧基-2-丙醇、2-丁氧基乙醇、及丙二醇單甲醚之類之醇溶劑；乙酸乙酯、乙酸丁酯、乙二醇甲醚乙酸酯、γ-丁內酯、丙二醇甲醚乙酸酯及乳酸乙酯之類之酯溶劑；丙酮、甲基乙基酮、環戊酮、環己酮、2-庚酮、及甲基異丁基酮之類之酮溶劑；戊烷、己烷、及庚烷之類之脂肪族烴溶劑；乙基環己烷之類之脂環式烴溶劑；甲苯及二甲苯之類之芳香族烴溶劑；乙腈之類之腈溶劑；四氫呋喃及二甲氧基乙烷之類之醚溶劑；氯仿及氯苯之類之含氯溶劑；二甲基乙醯胺、二甲基甲醯胺、N-甲基-2-吡咯啶酮(NMP)、及1,3-二甲基-2-咪唑啶酮之類之醯胺系溶劑。該等溶劑可單獨使用1種，亦可組合2種以上使用。該等溶劑之中，較佳為醇溶劑、酯溶劑、酮溶劑、含氯溶劑、醯胺系溶劑、及芳香族烴溶劑。該等溶劑可單獨使用1種，或者亦可組合2種以上使用。(solvent) Since the composition of the present invention is usually applied to a substrate or the like in a state of being dissolved in a solvent, it is preferable to contain a solvent. Examples of solvents include water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxy Alcohol solvents such as ethanol and propylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate Solvents; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic solvents such as pentane, hexane, and heptane Hydrocarbon solvents; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorinated solvents such as chloroform and chlorobenzene; dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2- Amide-based solvents such as imidazolidinone. These solvents may be used alone or in combination of two or more. Among these solvents, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide-based solvents, and aromatic hydrocarbon solvents are preferable. These solvents may be used alone or in combination of two or more.
溶劑之含量相對於組合物100質量份，較佳為50～98質量份，更佳為70～95質量份。因此，組合物100質量份中固形物成分所占之含量較佳為2～50質量份。若組合物之固形物成分為50質量份以下，則組合物之黏度變低，故而有垂直配向液晶硬化膜之厚度大致變均一，不易於垂直配向液晶硬化膜產生不均之傾向。上述固形物成分可考慮欲製造之垂直配向液晶硬化膜之厚度而適當決定。The content of the solvent is preferably from 50 to 98 parts by mass, more preferably from 70 to 95 parts by mass, relative to 100 parts by mass of the composition. Therefore, the content of the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. If the solid content of the composition is 50 parts by mass or less, the viscosity of the composition becomes low, so the thickness of the vertically aligned liquid crystal cured film becomes substantially uniform, and the vertically aligned liquid crystal cured film tends to be less likely to be uneven. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be produced.
(光聚合起始劑) 本發明之組合物亦可以使聚合反應進行為目的而包含光聚合起始劑。於本說明書中，光聚合起始劑提供吸收活性能量線而使聚合反應開始之活性種。關於光聚合起始劑，於將利用自由基聚合而硬化之硬化性組合物、例如(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯用作硬化性材料之情形時，可使用光自由基聚合起始劑，於將利用陽離子聚合而硬化之硬化性組合物、例如環氧化合物、氧雜環丁烷化合物用作硬化性組合物之情形時，可使用光陽離子聚合起始劑。(photopolymerization initiator) The composition of the present invention may also contain a photopolymerization initiator for the purpose of advancing the polymerization reaction. In this specification, a photopolymerization initiator provides an active species that absorbs active energy rays to start a polymerization reaction. As a photopolymerization initiator, it can be used when a curable composition hardened by radical polymerization, such as (meth)acrylate, (meth)urethane acrylate, is used as a curable material Photoradical polymerization initiator, when using a curable composition hardened by cationic polymerization, such as epoxy compounds and oxetane compounds, a photocationic polymerization initiator can be used .
作為光聚合起始劑，可列舉光自由基聚合起始劑、及光陽離子聚合起始劑。作為光自由基聚合起始劑，例如可列舉安息香化合物、二苯甲酮化合物、苯偶醯縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、三𠯤化合物等。作為光陽離子聚合起始劑，例如可列舉芳香族重氮鎓鹽、芳香族錪鹽或芳香族鋶鹽等鎓鹽、及鐵-芳烴錯合物。作為光聚合起始劑，例如可列舉Irgacure(註冊商標)907、Irgacure 184、Irgacure 651、Irgacure 819、Irgacure 250、Irgacure 369、Irgacure 379、Irgacure 127、Irgacure 2959、Irgacure 754、及Irgacure 379EG之類之BASF Japan股份有限公司製造之光聚合起始劑；SEIKUOL BZ、SEIKUOL Z、及SEIKUOL BEE之類之精工化學股份有限公司製造之光聚合起始劑；Kayacure BP100(日本化藥股份有限公司製造)、及Kayacure UVI-6992之類之Dow公司製造之光聚合起始劑；Adeka Optomer SP-152、Adeka Optomer SP-170、Adeka Optomer N-1717、Adeka Optomer N-1919、Adeka Arkls NCI-831、Adeka Arkls NCI-930之類之ADEKA股份有限公司製造之光聚合起始劑；TAZ-A、及TAZ-PP之類之Nihon Siber Hegner公司製造之光聚合起始劑；TAZ-104之類之Sanwa Chemical公司製造之光聚合起始劑；Kayarad(註冊商標)系列之類之日本化藥股份有限公司製造之光聚合起始劑；Cyracure UVI系列之類之Dow Chemical公司製造之光聚合起始劑；CPI系列之類之San-Apro股份有限公司製造之光聚合起始劑；TAZ、BBI、及DTS之類之Midori Kagaku股份有限公司製造之光聚合起始劑；RHODORSIL(註冊商標)之類之Rhodia股份有限公司製造之光聚合起始劑。該等光聚合起始劑可單獨使用1種，或者亦可組合2種以上使用。光聚合起始劑可根據使用之材料適當選擇使用。As a photoinitiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned. Examples of photoradical polymerization initiators include benzoin compounds, benzophenone compounds, benzoyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and trimethoprim compounds. Examples of photocationic polymerization initiators include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic permeic acid salts, and iron-arene complexes. Examples of photopolymerization initiators include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 37. 9EG and the like A photopolymerization initiator manufactured by BASF Japan Co., Ltd.; a photopolymerization initiator manufactured by Seiko Chemical Co., Ltd. such as SEIKUOL BZ, SEIKUOL Z, and SEIKUOL BEE; Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Dow photopolymerization initiators such as Kayacure UVI-6992; Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arkls NCI-831, Adeka Arkls Photopolymerization initiators such as NCI-930 manufactured by ADEKA Co., Ltd.; photopolymerization initiators such as TAZ-A and TAZ-PP manufactured by Nihon Siber Hegner Co., Ltd.; TAZ-104 and other products manufactured by Sanwa Chemical Co., Ltd. Photopolymerization initiators manufactured by Nippon Kayaku Co., Ltd. such as the Kayarad (registered trademark) series; photopolymerization initiators produced by Dow Chemical Corporation such as the Cyracure UVI series; CPI series Photopolymerization initiators manufactured by San-Apro Co., Ltd. such as TAZ, BBI, and DTS such as photopolymerization initiators manufactured by Midori Kagaku Co., Ltd.; Rhodia Co., Ltd. such as RHODORSIL (registered trademark) A photopolymerization initiator manufactured by the company. These photopolymerization initiators may be used alone or in combination of two or more. A photopolymerization initiator can be suitably selected and used according to the material used.
光聚合起始劑就能夠充分地利用自光源發出之能量而生產性優異而言，光聚合起始劑之極大吸收波長較佳為300 nm～400 nm，更佳為300 nm～380 nm，該等光聚合起始劑之中，較佳為α-苯乙酮系聚合起始劑及肟系光聚合起始劑。As for the photopolymerization initiator, the maximum absorption wavelength of the photopolymerization initiator is preferably from 300 nm to 400 nm, and more preferably from 300 nm to 380 nm, in terms of being able to fully utilize the energy emitted from the light source and thus having excellent productivity. Among other photopolymerization initiators, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferable.
作為α-苯乙酮系聚合起始劑，例如可列舉2-甲基-2-𠰌啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-𠰌啉基苯基)-2-苄基丁烷-1-酮(2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮)、及2-二甲基胺基-1-(4-𠰌啉基苯基)-2-(4-甲基苯基甲基)丁烷-1-酮。α-苯乙酮系聚合起始劑較佳為2-甲基-2-𠰌啉基-1-(4-甲基硫基苯基)丙烷-1-酮、及2-二甲基胺基-1-(4-𠰌啉基苯基)-2-苄基丁烷-1-酮。作為α-苯乙酮化合物之市售品，可列舉Irgacure 369、379EG、及907之類之BASF Japan(股)製造之α-苯乙酮系聚合起始劑、及SEIKUOL BEE之類之精工化學公司製造之α-苯乙酮系聚合起始劑等。Examples of α-acetophenone-based polymerization initiators include 2-methyl-2-metholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamine Base-1-(4-𠰌linylphenyl)-2-benzylbutan-1-one (2-dimethylamino-2-benzyl-1-(4-𠰌linylphenyl)butyl alkan-1-one), and 2-dimethylamino-1-(4-alkolinylphenyl)-2-(4-methylphenylmethyl)butan-1-one. The α-acetophenone-based polymerization initiator is preferably 2-methyl-2-? -1-(4-𠰌linylphenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include α-acetophenone-based polymerization initiators manufactured by BASF Japan Co., Ltd. such as Irgacure 369, 379EG, and 907, and Seiko Chemical Co., Ltd. such as SEIKUOL BEE. α-acetophenone-based polymerization initiators manufactured by the company.
肟系光聚合起始劑可藉由照射光而生成自由基。藉由該自由基，塗佈膜之深部之組合物良好地進行聚合。又，就更有效率地進行塗佈膜之深部之聚合反應之觀點而言，較佳為使用能夠有效率地利用波長350 nm以上之紫外線之肟系光聚合起始劑。作為能夠有效率地利用波長350 nm以上之紫外線之肟系光聚合起始劑，例如較佳為列舉三𠯤化合物及肟酯型咔唑化合物，就感度之觀點而言，例如更佳為列舉肟酯型咔唑化合物。作為肟酯型咔唑化合物，例如可列舉1,2-辛二酮、1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、及1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮-1-(O-乙醯基肟)。作為肟酯型咔唑化合物之市售品，例如可列舉Irgacure OXE-01、Irgacure OXE-02、Irgacure OXE-03之類之BASF Japan股份有限公司製造之肟酯型咔唑化合物、及Adeka Optomer N-1919、Adeka Arkls NCI-831之類之ADEKA股份有限公司製造之肟酯型咔唑化合物。The oxime-based photopolymerization initiator can generate radicals by irradiating light. The composition in the deep part of the coating film is favorably polymerized by the radicals. Moreover, from the viewpoint of more efficiently advancing the polymerization reaction in the deep part of the coating film, it is preferable to use an oxime-based photopolymerization initiator that can efficiently utilize ultraviolet light having a wavelength of 350 nm or more. As an oxime-based photopolymerization initiator capable of efficiently utilizing ultraviolet light having a wavelength of 350 nm or more, for example, trioxane compounds and oxime ester-type carbazole compounds are preferable, and from the viewpoint of sensitivity, for example, oxime compounds are more preferable. Ester carbazole compound. Examples of oxime ester-type carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], and 1-[9-ethyl Base-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime). Examples of commercially available oxime ester carbazole compounds include oxime ester carbazole compounds manufactured by BASF Japan Co., Ltd. such as Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03, and Adeka Optomer N Oxime ester type carbazole compounds manufactured by ADEKA Co., Ltd. such as 1919 and Adeka Arkls NCI-831.
於將本發明之組合物中所包含之固形物成分(自組合物中去除溶劑之含量後)設為100質量份時，光聚合起始劑之含量通常較佳為0.1～20質量份，更佳為0.5～10質量份，進而較佳為1～7質量份。若光聚合起始劑相對於組合物100質量份為0.1～20質量份，則聚合反應容易充分進行。When the solid content contained in the composition of the present invention (after removing the solvent content from the composition) is set to 100 parts by mass, the content of the photopolymerization initiator is usually preferably 0.1 to 20 parts by mass, more preferably Preferably, it is 0.5-10 mass parts, More preferably, it is 1-7 mass parts. When the photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of compositions, a polymerization reaction will fully advance easily.
(調平劑) 調平劑亦可以調製本發明之組合物之塗佈性為目的、即以調整用於塗佈之組合物之流動性而使塗佈該組合物所獲得之層表面更平坦為目的而添加於組合物中。作為調平劑，例如可列舉矽烷偶合劑等聚矽氧系之調平劑、聚丙烯酸酯系之調平劑、及氟烷基系之調平劑。該等調平劑之中，就進一步提高液晶化合物之垂直配向性之觀點而言，較佳為聚矽氧系之調平劑及氟烷基系之調平劑。(leveling agent) The leveling agent can also be added for the purpose of adjusting the applicability of the composition of the present invention, that is, for the purpose of adjusting the fluidity of the composition used for coating and making the surface of the layer obtained by applying the composition more flat. composition. Examples of the leveling agent include silicone-based leveling agents such as silane coupling agents, polyacrylate-based leveling agents, and fluoroalkyl-based leveling agents. Among these leveling agents, silicone-based leveling agents and fluoroalkyl-based leveling agents are preferred from the viewpoint of further improving the vertical alignment of liquid crystal compounds.
作為市售之調平劑，例如可列舉DC3PA、SH7PA、DC11PA、SH28PA、SH29PA、SH30PA、ST80PA、ST86PA、SH8400、SH8700、及FZ2123之類之東麗道康寧(股)製造之調平劑；KP321、KP323、KP324、KP326、KP340、KP341、X22-161A、KF6001、KBM-1003、KBE-1003、KBM-303、KBM-402、KBM-403、KBE-402、KBE-403、KBM-1403、KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-602、KBM-603、KBM-903、KBE-903、KBE-9103、KBM-573、KBM-575、KBE-585、KBM-802、KBM-802、KBM-803、KBE-846、及KBE-9007之類之信越化學工業(股)製造之調平劑；TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、及TSF4460之類之Momentive Performance Materials Japan有限責任公司製造之調平劑；Fluorinert(註冊商標)FC-72、Fluorinert FC-40、Fluorinert FC-43、及Fluorinert FC-3283之類之住友3M(股)製造之調平劑；MEGAFAC(註冊商標)R-08、MEGAFAC R-30、MEGAFAC R-90、MEGAFAC F-410、MEGAFAC F-411、MEGAFAC F-443、MEGAFAC F-445、MEGAFAC F-470、MEGAFAC F-477、MEGAFAC F-479、MEGAFAC F-482、MEGAFAC F-483、MEGAFAC F-556之類之DIC(股)製造之調平劑；Eftop(商品名)EF301、Eftop EF303、Eftop EF351、及Eftop EF352之類之Mitsubishi Materials Electronic Chemicals(股)製造之調平劑；Surflon(註冊商標)S-381、Surflon S-382、Surflon S-383、Surflon S-393、Surflon SC-101、Surflon SC-105、KH-40、及SA-100之類之AGC SEIMI CHEMICAL(股)製造之調平劑；商品名E1830、商品名E5844之類之(股)大金精密化學研究所製造之調平劑；BM-1000、BM-1100、BYK-352、BYK-353、及BYK-361N之類之Chemie公司製造之調平劑(商品名均為BM)。該等調平劑可單獨使用1種，或者亦可組合2種以上使用。As a commercially available leveling agent, for example, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 are listed. Leveling agents manufactured by Toray Dow Corning Co., Ltd.; KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, Leveling agent manufactured by Shin-Etsu Chemical Co., Ltd. such as KBM-802, KBM-802, KBM-803, KBE-846, and KBE-9007; TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 Leveling agents manufactured by Momentive Performance Materials Japan Co., Ltd. such as , TSF4452, and TSF4460; Sumitomo 3M such as Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, and Fluorinert FC-3283 (Stock) manufactured leveling agent; MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F -470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-556 and other DIC leveling agents; Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 and other leveling agents manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101 , Surflon SC-105, KH-40, and SA-100, which are manufactured by AGC SEIMI CHEMICAL Co., Ltd.; trade names such as E1830 and trade name E5844, which are manufactured by Daikin Fine Chemical Research Institute Leveling agent; leveling agents manufactured by Chemie such as BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (the trade names are all BM). These leveling agents may be used alone or in combination of two or more.
調平劑之含有率通常相對於本發明之組合物之固形物成分，較佳為0.001～3質量%，更佳為0.01～3質量%，進而較佳為0.1～3質量%。若調平劑之含有率相對於組合物之固形物成分為0.001～3質量%，則組合物之塗佈性進一步提高。The content of the leveling agent is usually preferably from 0.001 to 3% by mass, more preferably from 0.01 to 3% by mass, and still more preferably from 0.1 to 3% by mass, based on the solid content of the composition of the present invention. When the content rate of a leveling agent is 0.001-3 mass % with respect to the solid content of a composition, the applicability of a composition will improve further.
(垂直配向液晶硬化膜形成用組合物之製備方法) 本發明之組合物例如可藉由將液晶化合物(I)-1、非離子性矽烷化合物或離子性化合物之任一者或兩者、及視需要添加之添加劑於特定之溫度下攪拌等，從而使該等成分大致均勻地分散或溶解而獲得。(Manufacturing method of composition for forming vertically aligned liquid crystal cured film) The composition of the present invention can be obtained by, for example, stirring any one or both of the liquid crystal compound (I)-1, the nonionic silane compound or the ionic compound, and additives added if necessary at a specific temperature. It is obtained by dispersing or dissolving these components substantially uniformly.
＜垂直配向液晶硬化膜＞ 垂直配向液晶硬化膜為本發明之組合物之硬化物，且液晶化合物相對於面內方向朝垂直方向配向。即，垂直配向液晶硬化膜包含相對於垂直配向液晶硬化膜之面內方向朝垂直方向配向之狀態的液晶化合物。又，垂直配向液晶硬化膜亦可包含相對於垂直配向液晶硬化膜之面內方向朝垂直方向配向之狀態的液晶化合物之聚合物。垂直配向液晶硬化膜所形成之三維折射率橢球可具有雙軸性，但較佳為具有單軸性。＜Vertical alignment liquid crystal cured film＞ The vertical alignment liquid crystal cured film is a cured product of the composition of the present invention, and the liquid crystal compound is aligned in the vertical direction with respect to the in-plane direction. That is, the vertical alignment liquid crystal cured film contains the liquid crystal compound in the state aligned to the vertical direction with respect to the in-plane direction of the vertical alignment liquid crystal cured film. In addition, the vertical alignment liquid crystal cured film may contain a polymer of a liquid crystal compound in a state aligned vertically with respect to the in-plane direction of the vertical alignment liquid crystal cured film. The three-dimensional refractive index ellipsoid formed by the vertically aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality.
就抑制具備包含垂直配向液晶硬化膜之橢圓偏光板的顯示器之斜向反射色相變差(例如於該顯示器之斜向之色相確認到紅及藍之類之著色的問題)之觀點而言，垂直配向液晶硬化膜較佳為滿足 下述關係式(1)： -150 nm≦RthC(550)≦-30 nm (1) [關係式(1)中，RthC(550)表示垂直配向液晶硬化膜於波長550 nm下之厚度方向之相位差值]。 垂直配向液晶硬化膜之厚度方向之相位差值RthC(550)就進一步抑制上述顯示器之斜向反射色相之變差之觀點而言，更佳為-100 nm以上-40 nm以下，進而較佳為-80 nm以上-40 nm以下。From the viewpoint of suppressing the deterioration of oblique reflection hue of a display equipped with an elliptical polarizer including a vertically aligned liquid crystal cured film (for example, the problem of coloring such as red and blue being confirmed in the oblique hue of the display), the vertical Alignment liquid crystal cured film is preferably to meet The following relationship (1): -150nm≦RthC(550)≦-30nm (1) [In relational formula (1), RthC(550) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm]. The retardation value RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film is more preferably -100 nm or more and -40 nm or less from the viewpoint of further suppressing the deterioration of the oblique reflection hue of the above-mentioned display, and more preferably is Above -80 nm - below 40 nm.
垂直配向液晶硬化膜之厚度方向之相位差值RthC(550)可藉由垂直配向液晶硬化膜之厚度dC而調整。由於面內相位差值可由下述式(1-2)： RthC(550)＝[(nxC(550)＋nyC(550))/2－nzC(550)]×dC (1-2) [式(1-2)中，nxC(550)表示垂直配向液晶硬化膜於膜面內之波長550 nm之主折射率，nyC(550)表示與nxC(550)於同一面內正交之方向之波長550 nm之折射率，nzC(550)表示垂直配向液晶硬化膜之厚度方向之波長550 nm之折射率，dC表示垂直配向液晶硬化膜之膜厚] 決定，故而為了獲得所需之厚度方向之相位差值RthC(550)，只要調整三維折射率與膜厚dC即可。再者，三維折射率取決於上述之液晶化合物之分子結構及配向性。又，於nxC(550)＝nyC(550)之情形時，nxC(550)可設為膜面內任意之方向之折射率。The retardation value RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film. Since the in-plane phase difference value can be obtained by the following formula (1-2): RthC(550)＝[(nxC(550)＋nyC(550))/2－nzC(550)]×dC (1-2) [In the formula (1-2), nxC(550) represents the main refractive index of the vertically aligned liquid crystal cured film at a wavelength of 550 nm in the film plane, and nyC(550) represents the direction perpendicular to nxC(550) in the same plane Refractive index at a wavelength of 550 nm, nzC(550) represents the refractive index of a vertically aligned liquid crystal cured film at a wavelength of 550 nm in the thickness direction, and dC represents the film thickness of a vertically aligned liquid crystal cured film] Therefore, in order to obtain the desired retardation value RthC (550) in the thickness direction, it is only necessary to adjust the three-dimensional refractive index and film thickness dC. Furthermore, the three-dimensional refractive index depends on the molecular structure and alignment of the above-mentioned liquid crystal compound. Also, in the case of nxC(550)=nyC(550), nxC(550) can be the refractive index in any direction within the film surface.
就薄膜化之觀點而言，垂直配向液晶硬化膜之膜厚之上限較佳為3 μm以下，更佳為2.5 μm以下，進而較佳為2.0 μm以下，尤佳為1.5 μm以下。又，垂直配向液晶硬化膜之膜厚之下限較佳為0.1 μm以上，更佳為0.3 μm以上，進而較佳為0.4 μm以上。垂直配向液晶硬化膜之膜厚可使用橢偏計或接觸式膜厚計測定。From the viewpoint of thinning, the upper limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2.5 μm or less, further preferably 2.0 μm or less, especially preferably 1.5 μm or less. Also, the lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably at least 0.1 μm, more preferably at least 0.3 μm, and still more preferably at least 0.4 μm. The film thickness of the vertically aligned liquid crystal cured film can be measured using an ellipsometer or a contact film thickness meter.
又，就抑制包含垂直配向液晶硬化膜之橢圓偏光板於短波長側自斜向觀察之情形時橢圓率降低之觀點而言，垂直配向液晶硬化膜較佳為滿足 下述關係式(2)： RthC(450)/RthC(550)≦1 (2) [關係式(2)中，RthC(450)表示垂直配向液晶硬化膜於波長450 nm下之厚度方向之相位差值，RthC(550)表示垂直配向液晶硬化膜於波長550 nm下之厚度方向之相位差值]。 就進一步抑制上述橢圓率之降低之觀點而言，垂直配向液晶硬化膜之RthC(450)/RthC(550)更佳為0.95以下，進而較佳為0.90以下。又，垂直配向液晶硬化膜之厚度方向之相位差值RthC(450)與RthC(550)同樣地可藉由垂直配向液晶硬化膜之厚度dC而調整。Also, from the viewpoint of suppressing the decrease in ellipticity of an elliptically polarizing plate including a vertically aligned liquid crystal cured film viewed obliquely from the short wavelength side, the vertically aligned liquid crystal cured film preferably satisfies The following relationship (2): RthC(450)/RthC(550)≦1 (2) [In relational formula (2), RthC (450) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450 nm, and RthC (550) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm. phase difference]. RthC(450)/RthC(550) of the vertically aligned liquid crystal cured film is more preferably 0.95 or less, and more preferably 0.90 or less from the viewpoint of further suppressing the above-mentioned decrease in ellipticity. Also, the retardation value RthC(450) in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film similarly to RthC(550).
[垂直配向液晶硬化膜之製造方法] 垂直配向液晶硬化膜之製造方法包括：塗佈膜形成步驟，其將垂直配向液晶硬化膜形成用組合物塗佈於基材而於基材上形成塗佈膜；乾燥覆膜形成步驟，其使塗佈膜乾燥而形成乾燥覆膜；及硬化膜形成步驟，其對乾燥覆膜照射活性能量線而形成垂直配向液晶硬化膜。本製造方法中製造之積層體由基材與垂直配向液晶硬化膜構成。以液晶化合物具有1個以上聚合性基且該組合物進而包含光聚合起始劑之情形為例進行說明。[Manufacturing method of vertical alignment liquid crystal cured film] The method for producing a vertically aligned liquid crystal cured film includes: a coating film forming step of applying a composition for forming a vertically aligned liquid crystal cured film to a base material to form a coating film on the base material; and a dry coating film forming step of making The coating film is dried to form a dry film; and a cured film forming step of irradiating the dry film with active energy rays to form a vertical alignment liquid crystal cured film. The laminate manufactured in this manufacturing method is composed of a base material and a vertically aligned liquid crystal cured film. The case where a liquid crystal compound has one or more polymeric groups and this composition further contains a photoinitiator is demonstrated as an example.
(塗佈膜形成步驟) 於塗佈膜形成步驟中，例如使用印刷裝置將上述組合物塗佈於基材而於基材上形成塗佈膜。作為塗佈之方法，例如可列舉凹版塗佈法、模嘴塗佈法、及軟版法之類之印刷方法。(coating film forming step) In the coating film forming step, for example, the above-mentioned composition is applied to a base material using a printing device to form a coating film on the base material. As a coating method, printing methods, such as a gravure coating method, a die coating method, and a flexographic method, are mentioned, for example.
(乾燥覆膜形成步驟) 於乾燥覆膜形成步驟中，例如使用加熱裝置使塗佈膜乾燥而形成乾燥覆膜。塗佈膜於經加熱而去除了塗佈膜中之溶劑後，液晶化合物垂直地配向，轉化成乾燥覆膜。加熱溫度較佳為能夠去除溶劑，且為液晶化合物之相轉移溫度以上。(dry film forming step) In the dry film forming step, for example, the coating film is dried using a heating device to form a dry film. After the coating film is heated to remove the solvent in the coating film, the liquid crystal compounds are vertically aligned and converted into a dry coating film. The heating temperature is preferably such that the solvent can be removed, and is equal to or higher than the phase transition temperature of the liquid crystal compound.
(硬化膜形成步驟) 於硬化膜形成步驟中，例如使用光照射裝置對乾燥覆膜照射活性能量線(更具體而言為紫外線等)而形成垂直配向液晶硬化膜。於本發明中，垂直配向液晶硬化膜形成用組合物藉由包含非離子性矽烷化合物及/或離子性化合物而對液晶化合物表現垂直配向限制力，因此液晶化合物於乾燥覆膜中保持相對於基材平面垂直地配向之液晶狀態。藉由對乾燥覆膜照射活性能量線，液晶化合物保持垂直配向之液晶狀態進行光聚合。藉此，能夠於基材上直接形成垂直配向液晶硬化膜。(Cured film forming step) In the cured film forming step, for example, a dry film is irradiated with active energy rays (more specifically, ultraviolet rays or the like) using a light irradiation device to form a vertically aligned liquid crystal cured film. In the present invention, the composition for forming a vertically aligned liquid crystal cured film contains a nonionic silane compound and/or an ionic compound to express a vertical alignment restriction force on the liquid crystal compound, so that the liquid crystal compound maintains relative to the base in the dry film. The liquid crystal state in which the material plane is vertically aligned. By irradiating the dry film with active energy rays, the liquid crystal compound is photopolymerized while maintaining the liquid crystal state of vertical alignment. Thereby, a vertically aligned liquid crystal cured film can be directly formed on the substrate.
(其他步驟：垂直配向膜形成步驟) 如上文說明，本發明之垂直配向液晶硬化膜能夠不形成配向膜而直接形成於基材上。另一方面，垂直配向液晶硬化膜之製造方法亦可以進一步提高垂直配向液晶硬化膜之配向性為目的，進而包括形成垂直配向膜之垂直配向膜形成步驟。於該情形時，垂直配向液晶硬化膜介隔垂直配向膜而間接地形成於基材上。(Other steps: vertical alignment film forming step) As explained above, the vertical alignment liquid crystal cured film of the present invention can be directly formed on the substrate without forming an alignment film. On the other hand, the manufacturing method of the vertical alignment cured liquid crystal film can further improve the alignment of the vertical alignment cured liquid crystal film, and further includes the vertical alignment film forming step of forming the vertical alignment film. In this case, the vertical alignment liquid crystal cured film is indirectly formed on the base material through the vertical alignment film.
垂直配向膜形成步驟係於塗佈膜形成步驟之前執行之步驟，形成垂直配向膜。此處，對垂直配向膜之形成方法之例進行說明。配向膜形成步驟例如包括：形成垂直配向膜形成用組合物之塗佈膜之步驟、由上述塗佈膜形成乾燥覆膜之步驟、及視需要使上述乾燥覆膜硬化而形成配向膜之步驟。 於塗佈膜形成步驟中，例如使用印刷裝置於基材上塗佈垂直配向膜形成用組合物而形成塗佈膜。作為垂直配向膜形成用組合物，例如可使用包含如下文所述之配向性聚合物及溶劑之組合物。於乾燥覆膜形成步驟中，例如使用加熱裝置加熱上述塗佈膜使塗佈膜乾燥而形成乾燥覆膜。於進而需要藉由UV照射而硬化之步驟之情形時，使用UV照射裝置對第2乾燥覆膜照射UV進行硬化而形成垂直配向膜。於垂直配向液晶硬化膜之製造方法包括垂直配向膜形成步驟之情形時，於垂直配向膜上形成垂直配向液晶硬化膜。The vertical alignment film forming step is a step performed before the coating film forming step to form a vertical alignment film. Here, an example of a method for forming a vertical alignment film will be described. The step of forming an alignment film includes, for example, a step of forming a coating film of a composition for forming a vertical alignment film, a step of forming a dry film from the coating film, and a step of forming an alignment film by curing the dry film if necessary. In the coating film forming step, for example, the composition for forming a vertical alignment film is coated on a substrate using a printing device to form a coating film. As the composition for forming a vertical alignment film, for example, a composition including an alignment polymer and a solvent as described below can be used. In the dry film forming step, for example, the above-mentioned coating film is heated using a heating device to dry the coating film to form a dry film. When a step of curing by UV irradiation is further required, a UV irradiation device is used to irradiate the second dry film to cure and form a vertical alignment film. When the manufacturing method of the vertical alignment liquid crystal cured film includes a vertical alignment film forming step, the vertical alignment liquid crystal cured film is formed on the vertical alignment film.
＜積層體＞ 本發明之積層體具備上述垂直配向液晶硬化膜。積層體可進而具備基材、垂直配向膜、水平配向用之配向膜(以下，有時記載為水平配向膜)、黏著層、及/或下述相對於上述垂直配向液晶硬化膜之面內方向朝水平方向配向之膜(以下，有時記載為水平配向薄膜)。作為積層體之構成，例如可列舉具備上述垂直配向液晶硬化膜、水平配向膜、及水平配向薄膜之積層體、具備上述垂直配向液晶硬化膜及基材之積層體、以及具備上述垂直配向液晶硬化膜、水平配向膜、水平配向薄膜、及基材之積層體。但於本發明中，由於即便無垂直配向膜亦能夠形成垂直配向液晶硬化膜，故而積層體亦可不具備垂直配向膜。例如，於積層體具備基材及垂直配向液晶硬化膜之情形時，垂直配向液晶硬化膜可與基材鄰接。又，利用上述方法製作之與基材鄰接之垂直配向液晶硬化膜亦可經由黏著層僅轉印垂直配向液晶硬化膜，去除基材而製造積層體。＜Laminates＞ The laminate of the present invention includes the vertical alignment liquid crystal cured film described above. The laminate may further include a base material, a vertical alignment film, an alignment film for horizontal alignment (hereinafter, sometimes referred to as a horizontal alignment film), an adhesive layer, and/or the following in-plane directions relative to the above-mentioned vertical alignment liquid crystal cured film A film aligned in the horizontal direction (hereinafter sometimes referred to as a horizontally aligned film). As the structure of the laminate, for example, a laminate including the vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment thin film, a laminate including the above vertical alignment liquid crystal cured film and a substrate, and a laminate including the above vertical alignment liquid crystal cured film Laminates of films, horizontal alignment films, horizontal alignment films, and substrates. However, in the present invention, since a vertical alignment liquid crystal cured film can be formed even without a vertical alignment film, the laminate does not need to have a vertical alignment film. For example, when a laminate has a substrate and a cured vertical alignment liquid crystal film, the cured vertical alignment liquid crystal film may be adjacent to the substrate. In addition, the vertical alignment liquid crystal cured film adjacent to the base material produced by the above method can also be transferred to only the vertical alignment liquid crystal cured film through the adhesive layer, and the base material is removed to manufacture a laminate.
[基材] 作為基材，可列舉玻璃基材及膜基材，就加工性之觀點而言，較佳為膜基材，就能夠連續製造之方面而言，更佳為長條之捲筒狀膜。作為構成膜基材之樹脂，例如可列舉聚乙烯、聚丙烯、及降𦯉烯系聚合物之類之聚烯烴；環狀烯烴系樹脂；聚乙烯醇；聚對苯二甲酸乙二酯；聚甲基丙烯酸酯；聚丙烯酸酯；三乙醯纖維素、二乙醯纖維素、及乙酸丙酸纖維素之類之纖維素酯；聚萘二甲酸乙二酯；聚碳酸酯；聚碸；聚醚碸；聚醚酮；聚苯硫醚及聚苯醚之類之塑膠。於該基材之與黏著層之接合面可實施聚矽氧處理之類之脫模處理。作為市售之纖維素酯基材，例如可列舉FUJITAC膜之類之富士膠片股份有限公司製造之纖維素酯基材；「KC8UX2M」、「KC8UY」、及「KC4UY」之類之Konica Minolta Opto股份有限公司製造之纖維素酯基材。可將此種樹脂藉由溶劑流延法、溶融擠出法等公知之方法製膜而製成基材。[Substrate] Examples of the base material include a glass base material and a film base material, preferably a film base material from the viewpoint of processability, and more preferably a long roll-shaped film because continuous production is possible. As the resin constituting the film base material, for example, polyethylene, polypropylene, and polyolefins such as northylene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polyethylene terephthalate; Methacrylates; polyacrylates; cellulose esters such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; Ether ketone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene ether. Release treatment such as silicone treatment can be implemented on the joint surface of the base material and the adhesive layer. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fujifilm Co., Ltd. such as FUJITAC film, and Konica Minolta Opto stocks such as "KC8UX2M", "KC8UY", and "KC4UY". A cellulose ester substrate manufactured by Co., Ltd. Such a resin can be formed into a film by a known method such as a solvent casting method and a melt extrusion method to form a base material.
作為市售之環狀烯烴系樹脂，例如可列舉「Topas(註冊商標)」之類之Ticona公司(德)製造之環狀烯烴系樹脂；「ARTON(註冊商標)」之類之JSR股份有限公司製造之環狀烯烴系樹脂；「ZEONOR(註冊商標)」、及「ZEONEX(註冊商標)」之類之Zeon corporation股份有限公司製造之環狀烯烴系樹脂；「Apel」(註冊商標)之類之三井化學股份有限公司製造之環狀烯烴系樹脂。亦可使用市售之環狀烯烴系樹脂基材。作為市售之環狀烯烴系樹脂基材，可列舉「S-SINA(註冊商標)」及「SCA40(註冊商標)」之類之積水化學工業股份有限公司製造之環狀烯烴系樹脂基材；「ZeonorFilm(註冊商標)」之類之Optes股份有限公司製造之環狀烯烴系樹脂基材；「ARTON Film(註冊商標)」之類之JSR股份有限公司製造之環狀烯烴系樹脂基材。Examples of commercially available cyclic olefin-based resins include cyclic olefin-based resins manufactured by Ticona Corporation (Germany) such as "Topas (registered trademark)" and JSR Co., Ltd. such as "ARTON (registered trademark)". Cyclic olefin-based resins manufactured by Zeon Corporation Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; "Apel" (registered trademark) and the like Cyclic olefin-based resin manufactured by Mitsui Chemicals Co., Ltd. Commercially available cyclic olefin-based resin substrates can also be used. Examples of commercially available cyclic olefin-based resin substrates include Cyclic olefin-based resin substrates manufactured by Sekisui Chemical Industry Co., Ltd. such as "S-SINA (registered trademark)" and "SCA40 (registered trademark)"; Cyclic olefin-based resin substrates manufactured by Optes Co., Ltd. such as "Zeonor Film (registered trademark)"; Cyclic olefin-based resin substrates manufactured by JSR Co., Ltd. such as "ARTON Film (registered trademark)".
基材較佳為容易使各層積層且容易剝離之厚度。此種基材之厚度通常為5～300 μm，較佳為10～150 μm。The base material is preferably thick enough to allow easy lamination and peeling of each layer. The thickness of this substrate is usually 5-300 μm, preferably 10-150 μm.
[垂直配向膜] 配向膜係具有使液晶硬化膜之液晶化合物向特定方向配向之配向限制力的膜。關於配向膜之形成方法，可藉由配向膜材料之種類、摩擦條件或光照射條件實現垂直配向、水平配向、混合配向、及傾斜配向等各種配向之控制。將如此使配向限制力表現之處理稱為配向處理。其中，垂直配向膜為具有使液晶化合物朝垂直方向配向之配向限制力的配向膜。藉由使用垂直配向膜，能夠形成垂直配向液晶硬化膜。[Vertical Alignment Film] The alignment film is a film having an alignment restriction force to align the liquid crystal compound of the liquid crystal cured film in a specific direction. Regarding the formation method of the alignment film, various alignments such as vertical alignment, horizontal alignment, hybrid alignment, and oblique alignment can be controlled by the type of alignment film material, rubbing conditions, or light irradiation conditions. The treatment of expressing the alignment restriction force in this way is called alignment treatment. Wherein, the vertical alignment film is an alignment film having an alignment restriction force for aligning the liquid crystal compound in a vertical direction. By using a vertical alignment film, a vertical alignment liquid crystal cured film can be formed.
垂直配向膜較佳為具有不因垂直配向液晶硬化膜形成用組合物之塗佈等而溶解之溶劑耐性，且具有對用於溶劑之去除或液晶化合物之配向之加熱處理的耐熱性。The vertical alignment film preferably has solvent resistance not to be dissolved by coating of the composition for forming a vertical alignment cured liquid crystal film, etc., and has heat resistance to heat treatment for removing the solvent or aligning the liquid crystal compound.
垂直配向膜較佳為應用降低基材等之表面之表面張力的材料。作為此種材料，可列舉配向性聚合物、例如聚醯亞胺、聚醯胺、作為其水解物之聚醯胺酸、及全氟烷基之氟系聚合物、矽烷化合物、以及藉由該等之縮合反應而獲得之聚矽氧烷化合物。垂直配向膜可藉由將包含此種材料與溶劑、例如垂直配向液晶硬化膜之項中例示之溶劑的組合物塗佈於基材等之上，去除溶劑後對塗佈膜實施加熱等而獲得。The vertical alignment film is preferably applied with a material that reduces the surface tension of the surface of the substrate or the like. Such materials include alignment polymers such as polyimide, polyamide, polyamic acid as its hydrolyzate, and perfluoroalkyl fluorine-based polymers, silane compounds, and The polysiloxane compound obtained by condensation reaction. The vertical alignment film can be obtained by applying a composition containing such a material and a solvent, such as the solvent exemplified in the section of the vertical alignment liquid crystal cured film, to a substrate, etc., and heating the coated film after removing the solvent. .
於垂直配向膜使用矽烷化合物之情形時，就容易降低表面張力且容易提高與鄰接於垂直配向膜之層之密接性的觀點而言，垂直配向膜較佳為具有構成元素包含Si元素與C元素之化合物的膜，可良好地使用矽烷化合物。作為矽烷化合物，可使用前述非離子性矽烷化合物、或離子性化合物之項所例示之含矽烷之離子性化合物等，藉由使用該等矽烷化合物，能夠提高垂直配向限制力。該等矽烷化合物可單獨使用1種，亦可組合2種以上使用，亦可與其他材料混合使用。於矽烷化合物為非離子性矽烷化合物之情形時，就容易提高垂直配向限制力之觀點而言，較佳為分子末端具有烷基之矽烷化合物，更佳為具有碳數3～30之烷基之矽烷化合物。When a silane compound is used for the vertical alignment film, it is preferable that the vertical alignment film has constituent elements including Si element and C element from the viewpoint of easily reducing the surface tension and improving the adhesion with the layer adjacent to the vertical alignment film. Silane compounds can be favorably used for the film of the compound. As the silane compound, the aforementioned nonionic silane compound or the silane-containing ionic compound exemplified in the section of the ionic compound can be used, and vertical alignment confinement force can be improved by using such a silane compound. These silane compounds may be used alone or in combination of two or more, or mixed with other materials. When the silane compound is a nonionic silane compound, it is preferably a silane compound having an alkyl group at the end of the molecule, and more preferably a silane compound having an alkyl group having 3 to 30 carbon atoms, from the viewpoint of easily increasing the vertical alignment confinement force. Silane compounds.
就表現配向限制力之觀點而言，垂直配向膜之膜厚較佳為5 μm以下，更佳為3 μm以下，進而較佳為2 μm以下，且較佳為1 nm以上，更佳為5 nm以上，進而較佳為10 nm以上，尤佳為30 nm以上。垂直配向膜之膜厚可使用橢偏計或接觸式膜厚計進行測定。From the viewpoint of expressing the alignment restriction force, the film thickness of the vertical alignment film is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, and preferably 1 nm or more, more preferably 5 μm or less. nm or more, more preferably 10 nm or more, particularly preferably 30 nm or more. The film thickness of the vertical alignment film can be measured using an ellipsometer or a contact film thickness meter.
[水平配向用之配向膜] 水平配向膜具有使液晶化合物朝水平方向配向之配向限制力。於將水平配向液晶硬化膜形成用組合物於水平配向膜上製膜時，水平配向膜能夠形成水平配向液晶硬化膜之水平配向狀態。配向限制力例如能夠藉由配向膜之種類、表面狀態、及摩擦條件而任意地調整，於由光配向性聚合物形成之情形時，可藉由偏光照射條件等任意地調整。將如此使配向限制力表現之處理稱為配向處理。[Alignment film for horizontal alignment] The horizontal alignment film has an alignment restriction force for aligning the liquid crystal compound in the horizontal direction. When the composition for forming a horizontal alignment liquid crystal cured film is formed into a film on the horizontal alignment film, the horizontal alignment film can form a horizontal alignment state of the horizontal alignment liquid crystal cured film. The alignment restriction force can be arbitrarily adjusted by, for example, the type of alignment film, surface state, and rubbing conditions, and in the case of a photo-alignment polymer, it can be arbitrarily adjusted by polarized light irradiation conditions and the like. The treatment of expressing the alignment restriction force in this way is called alignment treatment.
水平配向膜較佳為具有不因液晶組合物之塗佈等而溶解之溶劑耐性，且具有對用於溶劑之去除或液晶化合物之配向之加熱處理的耐熱性。The horizontal alignment film preferably has solvent resistance not to be dissolved by application of the liquid crystal composition, etc., and has heat resistance to heat treatment for removal of the solvent or alignment of the liquid crystal compound.
作為水平配向膜，例如可列舉摩擦配向膜、光配向膜、及表面具有凹凸圖案或複數之槽的溝槽配向膜。例如於應用於長條之捲筒狀膜之情形時，就能夠容易地控制配向方向之方面而言，較佳為光配向膜。As the horizontal alignment film, for example, a rubbed alignment film, a photo-alignment film, and a trench alignment film having a concavo-convex pattern or a plurality of grooves on the surface are exemplified. For example, when applied to a long roll-shaped film, a photo-alignment film is preferable at the point that the alignment direction can be easily controlled.
摩擦配向膜通常可藉由將包含配向性聚合物與溶劑之組合物(以下，有時記載為摩擦配向膜形成用組合物)塗佈於基材，去除溶劑而形成塗佈膜，並對該塗佈膜進行摩擦而賦予配向限制力。A rubbed alignment film can generally be formed by applying a composition comprising an alignment polymer and a solvent (hereinafter, sometimes referred to as a composition for forming a rubbed alignment film) to a substrate, removing the solvent to form a coating film, and applying The coating film is rubbed to impart an alignment-regulating force.
作為配向性聚合物，例如可列舉具有醯胺鍵之聚醯胺或明膠類、具有醯亞胺鍵之聚醯亞胺及作為其水解物之聚醯胺酸、聚乙烯醇、烷基改性聚乙烯醇、聚丙烯醯胺、聚㗁唑、聚伸乙基亞胺、聚苯乙烯、聚乙烯基吡咯啶酮、聚丙烯酸、以及聚丙烯酸酯類。該等配向性聚合物可單獨使用1種，或者亦可組合2種以上使用。As the alignment polymer, for example, polyamide or gelatin having an amide bond, polyimide having an amide bond, and polyamic acid, polyvinyl alcohol, alkyl-modified Polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. These alignment polymers may be used alone or in combination of two or more.
關於摩擦配向膜形成用組合物中之配向性聚合物之濃度，只要為配向性聚合物完全溶解於溶劑中之範圍即可。配向性聚合物之含量相對於摩擦配向膜形成用組合物100質量份，較佳為0.1～20質量份，更佳為0.1～10質量份。The concentration of the alignment polymer in the composition for forming a rubbed alignment film may be within a range in which the alignment polymer is completely dissolved in the solvent. The content of the alignment polymer is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the composition for forming a rubbed alignment film.
作為摩擦配向膜形成用組合物之市售品，例如可列舉Sunever(註冊商標)之類之日產化學工業(股)製造之摩擦配向膜形成用組合物、及Optomer(註冊商標)之類之JSR(股)製造之摩擦配向膜形成用組合物。Examples of commercially available compositions for forming a frictional alignment film include compositions for forming a frictional alignment film manufactured by Nissan Chemical Industries Co., Ltd. such as Sunever (registered trademark), and JSR products such as Optomer (registered trademark). Composition for forming a rubbed alignment film produced by the company.
作為摩擦處理之方法，例如可列舉使上述塗佈膜接觸於捲繞有摩擦布且旋轉之摩擦輥的方法。於進行摩擦處理時，若進行遮蔽，則亦能夠於配向膜形成配向之方向不同之複數個區域(圖案)。As a method of a rubbing process, the method of bringing the said coating film into contact with the rubbing roll which wound the rubbing cloth and rotated is mentioned, for example. When performing the rubbing process, if masking is performed, a plurality of regions (patterns) having different alignment directions can also be formed on the alignment film.
光配向膜通常可藉由將包含具有光反應性基之聚合物或單體及溶劑之組合物(以下，有時記載為光配向膜形成用組合物)塗佈於基材，去除溶劑後照射偏光(較佳為偏光UV)而獲得。光配向膜可藉由選擇照射之偏光之偏光方向而任意地控制配向限制力之方向。A photo-alignment film can generally be prepared by applying a composition containing a polymer having a photoreactive group or a monomer and a solvent (hereinafter, sometimes referred to as a photo-alignment film-forming composition) to a substrate, removing the solvent, and then irradiating Obtained by polarized light (preferably polarized UV). The photo-alignment film can arbitrarily control the direction of the alignment restriction force by selecting the polarization direction of the irradiated polarized light.
光反應性基係指藉由光照射而產生配向能力之基。具體而言，可列舉參與藉由光照射而產生之分子之配向誘發反應、異構化反應、光二聚反應、光交聯反應、或光分解反應之類之成為配向能力之起源之光反應的基。作為光反應性基，較佳為具有不飽和鍵、尤其是雙鍵之基，尤佳為具有選自由碳-碳雙鍵(C=C鍵)、碳-氮雙鍵(C=N鍵)、氮-氮雙鍵(N=N鍵)、及碳-氧雙鍵(C=O鍵)所組成之群中之至少一個雙鍵的基。The photoreactive group refers to a group that produces alignment ability by light irradiation. Specifically, those that participate in photoreactions that are the origin of the alignment ability, such as an alignment-induced reaction of molecules generated by light irradiation, an isomerization reaction, a photodimerization reaction, a photocrosslinking reaction, or a photodecomposition reaction, can be cited. base. As the photoreactive group, it is preferably a group having an unsaturated bond, especially a double bond, especially a group selected from a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond) , nitrogen-nitrogen double bond (N=N bond), and carbon-oxygen double bond (C=O bond) is at least one double bond group.
作為具有C=C鍵之光反應性基，例如可列舉乙烯基、多烯基、茋基、茋唑基、茋唑鎓基、查耳酮基、及桂皮醯基。作為具有C=N鍵之光反應性基，例如可列舉具有芳香族希夫鹼、芳香族腙等結構之基。作為具有N=N鍵之光反應性基，例如可列舉偶氮苯基、偶氮萘基、芳香族雜環偶氮基、雙偶氮基、甲臢基、及具有氧偶氮苯結構之基。作為具有C=O鍵之光反應性基，例如可列舉二苯甲酮基、香豆素基、蒽醌基、及順丁烯二醯亞胺基。該等基可具有烷基、烷氧基、芳基、烯丙氧基、氰基、烷氧基羰基、羥基、磺酸基、及鹵化烷基之類之取代基。Examples of the photoreactive group having a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a stilazolyl group, a stilazolium group, a chalcone group, and a cinnamoyl group. As a photoreactive group which has a C=N bond, the group which has structures, such as an aromatic Schiff base and an aromatic hydrazone, is mentioned, for example. As a photoreactive group having an N=N bond, for example, azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, disazo group, formazan group, and those having an oxyazobenzene structure base. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group are mentioned, for example. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and halogenated alkyl.
參與光二聚反應或光交聯反應之基就配向性優異之方面而言較佳。其中，較佳為參與光二聚反應之光反應性基，就配向所需之偏光照射量相對較少、且容易獲得熱穩定性或經時穩定性優異之光配向膜之方面而言，較佳為桂皮醯基及查耳酮基。作為具有光反應性基之聚合物，尤佳為該聚合物側鏈之末端部成為桂皮酸結構或桂皮酸酯結構之具有桂皮醯基者。A group that participates in a photodimerization reaction or a photocrosslinking reaction is preferable in terms of being excellent in alignment. Among them, photoreactive groups that participate in the photodimerization reaction are preferred, and the amount of polarized light irradiation required for alignment is relatively small, and it is easy to obtain a photoalignment film with excellent thermal stability or stability over time. It is cinnamon-yl and chalcone-based. As a polymer having a photoreactive group, one having a cinnamoyl group having a cinnamic acid structure or a cinnamate ester structure at the end of the side chain of the polymer is particularly preferable.
具有光反應性基之聚合物或單體之含量可根據聚合物或單體之種類或目標之光配向膜之厚度而調節，相對於光配向膜形成用組合物100質量份，較佳為設為0.2質量份以上，更佳為0.3～10質量份。The content of polymers or monomers with photoreactive groups can be adjusted according to the type of polymers or monomers or the thickness of the target photo-alignment film, with respect to 100 parts by mass of the photo-alignment film-forming composition, preferably set at It is 0.2 mass parts or more, More preferably, it is 0.3-10 mass parts.
於照射偏光時，例如可為自塗佈於基材上之光配向膜形成用組合物去除溶劑後直接照射偏光之形式。又，該偏光若實質上為平行光則較佳。照射之偏光之波長較佳為具有光反應性基之聚合物或單體之光反應性基能夠吸收光能之波長區域者。具體而言，尤佳為波長250～400 nm之區域之UV(紫外線)。作為照射該偏光之光源，例如可列舉氙氣燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、以及KrF及ArF之類之紫外光雷射。該等光源之中，高壓水銀燈、超高壓水銀燈、及金屬鹵化物燈由於波長313 nm之紫外線之發光強度較大，故而較佳。藉由使來自上述光源之光通過適當之偏光元件進行照射，能夠照射偏光UV。作為偏光元件，例如可列舉偏光濾光片、格蘭-湯姆森、及格蘭-泰勒之類之偏光稜鏡、以及線柵。該等偏光元件之中，就大面積化及對熱之耐性之觀點而言，較佳為線柵。When irradiating polarized light, for example, a form in which polarized light is directly irradiated after the solvent is removed from the composition for forming a photoalignment film coated on a substrate may be used. Moreover, it is preferable that this polarized light is parallel light substantially. The wavelength of the polarized light to be irradiated is preferably in the wavelength range where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) in the wavelength region of 250 to 400 nm is particularly preferable. Examples of light sources for irradiating the polarized light include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF. Among these light sources, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because the luminous intensity of ultraviolet rays with a wavelength of 313 nm is relatively large. It is possible to irradiate polarized light UV by irradiating light from the above-mentioned light source through an appropriate polarizing element. Examples of the polarizing element include polarizing filters, polarizing filters such as Glan-Thomson and Glan-Taylor, and wire grids. Among these polarizing elements, a wire grid is preferable from the viewpoint of increasing the area and resistance to heat.
再者，於進行摩擦或偏光照射時，若進行遮蔽，則亦能夠形成液晶配向之方向不同之複數個區域(圖案)。In addition, when performing rubbing or polarized light irradiation, if masking is performed, it is also possible to form a plurality of regions (patterns) in which the directions of liquid crystal alignment are different.
溝槽(groove)配向膜係於膜表面具有凹凸圖案或複數個溝槽(槽)之膜。於將組合物塗佈於具有等間隔地排列之複數之直線狀之溝槽的膜之情形時，液晶化合物朝沿著該槽之方向配向。The groove (groove) alignment film is a film with a concave-convex pattern or a plurality of grooves (grooves) on the surface of the film. When the composition is applied to a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal compound is aligned in a direction along the grooves.
作為獲得溝槽配向膜之方法，可列舉：於感光性聚醯亞胺膜表面經由具有圖案形狀之狹縫之曝光用遮罩進行曝光後，進行顯影及沖洗處理而形成凹凸圖案的方法；於在表面具有槽之板狀之母盤形成硬化前之UV硬化樹脂之層，將形成之樹脂層轉移至基材後進行硬化的方法；及於形成於基材上之硬化前之UV硬化樹脂之膜按壓具有複數個槽之輥狀之母盤而形成凹凸，其後進行硬化之方法等。As a method for obtaining a trench alignment film, it is possible to enumerate: after exposing the surface of the photosensitive polyimide film through an exposure mask having a pattern-shaped slit, developing and rinsing are performed to form a concave-convex pattern; A method of forming a UV curable resin layer before hardening on a plate-shaped master having grooves on the surface, transferring the formed resin layer to a base material and then hardening it; and forming a UV curable resin layer on the base material before hardening A method in which the film is pressed against a roll-shaped master having a plurality of grooves to form concavities and convexities, and then hardened.
就實現薄膜化及表現配向限制力之觀點而言，水平配向膜之膜厚較佳為1 μm以下，更佳為0.5 μm以下，進而較佳為0.3 μm以下。又，水平配向膜之膜厚較佳為1 nm以上，更佳為5 nm以上，進而較佳為10 nm以上，尤佳為30 nm以上。水平配向膜之膜厚可使用橢偏計或接觸式膜厚計進行測定。From the viewpoint of thinning and expressing alignment confining force, the film thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. In addition, the film thickness of the horizontal alignment film is preferably at least 1 nm, more preferably at least 5 nm, further preferably at least 10 nm, especially preferably at least 30 nm. The film thickness of the horizontal alignment film can be measured using an ellipsometer or a contact film thickness meter.
[相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜] 構成本發明之積層體的相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜為相位差膜。作為水平配向薄膜，例如可列舉延伸膜及水平配向液晶硬化膜(以下亦稱為水平配向液晶硬化膜A)。水平配向薄膜之光學特性可藉由聚合性液晶化合物之配向狀態或延伸方法而調整。就水平配向薄膜之薄膜化之觀點而言，較佳為水平配向液晶硬化膜A。[Film aligned in the horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film] The film that is aligned in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film constituting the laminate of the present invention is a retardation film. As a horizontal alignment film, a stretched film and a horizontal alignment liquid crystal cured film (henceforth the horizontal alignment liquid crystal cured film A) are mentioned, for example. The optical properties of the horizontal alignment film can be adjusted by the alignment state of the polymerizable liquid crystal compound or the stretching method. From the viewpoint of thinning the horizontal alignment film, the horizontal alignment liquid crystal cured film A is preferable.
(水平配向液晶硬化膜A) 本說明書中，水平配向液晶硬化膜A係聚合性液晶化合物於相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之狀態下硬化而成的液晶硬化膜。水平配向液晶硬化膜A中，聚合性液晶化合物之光軸相對於垂直配向液晶硬化膜之面內方向朝水平方向配向。作為聚合性液晶化合物，例如可列舉具有至少1個聚合性基之液晶化合物(I)-1。再者，於本說明書中，將本發明之積層體所包含之水平配向液晶硬化膜稱為水平配向液晶硬化膜A，將下述偏光板之偏光膜所包含之水平配向液晶硬化膜稱為水平配向液晶硬化膜B而區分各者。(Horizontal Alignment Liquid Crystal Curing Film A) In this specification, the horizontal alignment liquid crystal cured film A is a liquid crystal cured film formed by curing a polymerizable liquid crystal compound in a state aligned horizontally with respect to the in-plane direction of the vertical alignment liquid crystal cured film. In the horizontal alignment cured liquid crystal film A, the optical axis of the polymerizable liquid crystal compound is aligned horizontally with respect to the in-plane direction of the vertical alignment cured liquid crystal film. As a polymeric liquid crystal compound, liquid crystal compound (I)-1 which has at least 1 polymeric group is mentioned, for example. Furthermore, in this specification, the horizontally aligned liquid crystal cured film contained in the laminate of the present invention is referred to as horizontally aligned liquid crystal cured film A, and the horizontally aligned liquid crystal cured film contained in the polarizing film of the following polarizing plate is referred to as horizontally aligned liquid crystal cured film A. Align liquid crystal cured film B and distinguish each one.
(水平配向液晶硬化膜A之製造方法) 水平配向液晶硬化膜A係組合物(以下，有時記載為水平配向液晶硬化膜A形成用組合物)之硬化物。作為水平配向液晶硬化膜A之製造方法之一例，包括：塗佈步驟，其於預先製作之水平配向膜上塗佈水平配向液晶硬化膜A形成用組合物而形成塗佈膜；乾燥覆膜形成步驟，其使塗佈膜乾燥而形成乾燥覆膜；及硬化膜形成步驟，其對乾燥覆膜照射活性能量線而形成水平配向液晶硬化膜。(Manufacturing method of horizontal alignment liquid crystal cured film A) Cured product of horizontal alignment liquid crystal cured film A-based composition (hereinafter, may be described as composition for forming horizontal alignment liquid crystal cured film A). As an example of the manufacturing method of the horizontal alignment liquid crystal cured film A, it includes: a coating step of coating the composition for forming the horizontal alignment liquid crystal cured film A on the horizontal alignment film prepared in advance to form a coating film; drying the film formation A step of drying the coating film to form a dry film; and a step of forming a cured film by irradiating the dry film with active energy rays to form a horizontally aligned liquid crystal cured film.
(延伸膜) 作為延伸膜，例如可列舉包含聚碳酸酯系樹脂之延伸膜。作為市售之延伸膜，例如可列舉「PURE-ACE(註冊商標)WR」之類之帝人股份有限公司製造之延伸膜。延伸膜通常可藉由對基材膜進行延伸而獲得。作為對基材膜進行延伸之方法，例如準備將基材膜捲繞成捲筒而得之捲繞體，自捲繞體連續地捲出基材膜，將捲出之基材膜搬送至加熱爐。加熱爐之設定溫度較佳為基材膜之玻璃轉移溫度附近～玻璃轉移溫度＋50℃之範圍。於加熱爐中，向基材膜之搬送方向、或與搬送方向正交之方向進行延伸。延伸時，調整搬送方向或張力，向任意之角度加以傾斜地進行單軸延伸、雙軸延伸、或斜向延伸之熱延伸處理。延伸膜之遲相軸方向根據延伸方法而不同，根據延伸方法而決定遲相軸或光軸。延伸膜與本發明之積層體可經由黏著層而接著。(stretch film) As a stretched film, the stretched film which consists of polycarbonate resin is mentioned, for example. Examples of commercially available stretched films include those made by Teijin Co., Ltd. such as "PURE-ACE (registered trademark) WR". Stretched films are generally obtained by stretching a base film. As a method of stretching the base film, for example, a roll body obtained by winding the base film into a roll is prepared, the base film is continuously unwound from the roll body, and the unwound base film is transported to a heated furnace. The set temperature of the heating furnace is preferably in the range from near the glass transition temperature of the substrate film to the glass transition temperature + 50°C. In the heating furnace, it stretches in the conveyance direction of a base film, or the direction orthogonal to a conveyance direction. When stretching, adjust the conveying direction or tension, and perform uniaxial stretching, biaxial stretching, or oblique stretching heat stretching at any angle. The direction of the slow axis of the stretched film differs depending on the stretching method, and the slow axis or the optical axis is determined by the stretching method. The stretched film and the laminate of the present invention can be bonded via an adhesive layer.
本發明之積層體就降低具備積層體之橢圓偏光板於短波長側之橢圓率之觀點而言，構成積層體之水平配向薄膜較佳為滿足下述關係式(3)： ReA(450)/ReA(550)≦1 (3) [關係式(3)中，ReA(450)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長450 nm下之面內相位差值，ReA(550)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長550 nm下之面內相位差值]。 就進一步抑制橢圓率降低之觀點而言，ReA(450)/ReA(550)更佳為0.95以下，進而較佳為0.90以下。 又，同樣地就提高具備積層體之橢圓偏光板之橢圓率之觀點而言，較佳為滿足以下(3)-2： 120 nm≦ReA(550)≦170 nm・・・(3)-2。 就提高具備積層體之橢圓偏光板之橢圓率之觀點而言，較佳為130 nm≦ReA(550)≦160 nm。From the viewpoint of reducing the ellipticity of the elliptically polarizing plate provided with the laminate on the short-wavelength side of the laminate of the present invention, the horizontal alignment film constituting the laminate preferably satisfies the following relational expression (3): ReA(450)/ReA(550)≦1 (3) [In the relational formula (3), ReA(450) represents the in-plane retardation value of the film aligned horizontally with respect to the in-plane direction of the vertical alignment liquid crystal cured film at a wavelength of 450 nm, and ReA(550) represents the above-mentioned relative The in-plane retardation value of the film aligned horizontally from the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]. From the viewpoint of further suppressing the decrease in ellipticity, ReA(450)/ReA(550) is more preferably 0.95 or less, further preferably 0.90 or less. Also, from the viewpoint of increasing the ellipticity of the elliptically polarizing plate provided with the laminate, it is preferable to satisfy the following (3)-2: 120 nm≦ReA(550)≦170 nm・・・(3)-2. From the viewpoint of increasing the ellipticity of the elliptically polarizing plate provided with the laminate, it is preferably 130 nm≦ReA(550)≦160 nm.
本發明所記載之積層體之中，包含垂直配向液晶硬化膜及相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的積層體就縮小正面方向之相位差值與自斜向之相位差值之差之觀點而言，即就抑制具備包含該積層體之橢圓偏光板之顯示器之斜向反射色相變差的觀點而言，較佳為滿足下述關係式(4)： |R0(550)－R40(550)|≦10 nm (4) [關係式(4)中，R0(550)表示波長550 nm下之積層體之面內相位差值，R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550 nm下之相位差值]。 就進一步抑制斜向反射色相變差之觀點而言，更佳為8 nm以下，進而較佳為4 nm以下。Among the laminates described in the present invention, a laminate comprising a vertically aligned liquid crystal cured film and a film aligned in the horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film reduces the retardation value in the front direction and the phase difference from the oblique direction. From the viewpoint of the difference in retardation value, that is, from the viewpoint of suppressing the oblique reflection hue deterioration of a display having an elliptically polarizing plate including the laminate, it is preferable to satisfy the following relational expression (4): |R0(550)－R40(550)|≦10 nm (4) [In relational formula (4), R0 (550) represents the in-plane retardation value of the laminated body at a wavelength of 550 nm, and R40 (550) represents the horizontal orientation around the in-plane direction of the vertically aligned liquid crystal cured film. The retardation value at a wavelength of 550 nm when the film advance axis direction is rotated by 40°]. From the viewpoint of further suppressing deterioration of oblique reflection hue, the thickness is more preferably 8 nm or less, and further preferably 4 nm or less.
本發明所記載之積層體之中，包含垂直配向液晶硬化膜與相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的積層體就抑制具備包含該積層體之橢圓偏光板之顯示器之斜向反射色相變差的觀點而言，較佳為滿足下述關係式(5)： |R0(450)－R40(450)|≦10 nm (5) [關係式(5)中，R0(450)表示波長450 nm下之積層體之面內相位差值，R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450 nm下之相位差值]。 就進一步抑制斜向反射色相變差之觀點而言，更佳為8 nm以下，進而較佳為4 nm以下。Among the laminates described in the present invention, a laminate comprising a vertically aligned liquid crystal cured film and a film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film inhibits a display including an elliptically polarizing plate comprising the laminate. From the point of view of the oblique reflection hue deterioration, it is preferable to satisfy the following relationship (5): |R0(450)－R40(450)|≦10 nm (5) [In relational formula (5), R0 (450) represents the in-plane retardation value of the laminated body at a wavelength of 450 nm, and R40 (450) represents the horizontal orientation around the in-plane direction of the vertically aligned liquid crystal cured film. The phase difference value at a wavelength of 450 nm when the phase axis direction of the film is rotated by 40°]. From the viewpoint of further suppressing deterioration of oblique reflection hue, the thickness is more preferably 8 nm or less, and further preferably 4 nm or less.
本發明所記載之積層體之中，包含垂直配向液晶硬化膜及相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的積層體就抑制具備包含該積層體之橢圓偏光板之顯示器之斜向反射色相變差的觀點而言，較佳為滿足下述關係式(6)： |{R0(450)－R40(450)}－{R0(550)－R40(550)}|≦3 nm (6) [關係式(6)中，R0(450)表示波長450 nm下之積層體之面內相位差值，R0(550)表示波長550 nm下之積層體之面內相位差值，R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450 nm下之相位差值，R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550 nm下之相位差值]。 就進一步抑制斜向反射色相變差之觀點而言，更佳為2 nm以下，進而較佳為1 nm以下。Among the laminates described in the present invention, a laminate comprising a vertically aligned liquid crystal cured film and a film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film inhibits a display including an elliptically polarizing plate comprising the laminate. From the point of view of the oblique reflection hue deterioration, it is preferable to satisfy the following relationship (6): |{R0(450)－R40(450)}－{R0(550)－R40(550)}|≦3 nm (6) [In relational formula (6), R0(450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, R40(450) Indicates the retardation value at a wavelength of 450 nm when the film is rotated 40° around the in-plane direction of the vertically aligned liquid crystal cured film toward the phase axis direction of the horizontally aligned film, and R40 (550) represents the phase difference value around the above-mentioned relative to the vertically aligned liquid crystal The retardation value at a wavelength of 550 nm when the in-plane direction of the cured film is oriented toward the horizontal direction and the phase axis direction of the film is rotated by 40°]. From the viewpoint of further suppressing the deterioration of oblique reflection hue, it is more preferably 2 nm or less, and further preferably 1 nm or less.
[積層體之製造方法] 本發明之積層體之製造方法包括垂直配向液晶硬化膜形成步驟。垂直配向液晶硬化膜形成步驟可為上述垂直配向液晶硬化膜之製造方法。藉由已說明之垂直配向液晶硬化膜之製造方法，能夠製造由基材及垂直配向液晶硬化膜構成之積層體、以及由基材、配向膜、及垂直配向液晶硬化膜構成之積層體。 於積層體具備相對於垂直配向液晶硬化膜之面內方向朝水平配向進行配向之膜之情形時，積層體之製造方法進而包括延伸膜貼合步驟或水平配向液晶硬化膜A形成步驟。延伸膜貼合步驟係使用黏接著劑將延伸膜貼合於例如垂直配向液晶硬化膜。具備水平配向液晶硬化膜A之積層體之製造方法例如可經由黏著層將垂直配向液晶硬化膜與水平配向液晶硬化膜貼合而進行製造，亦可將水平配向膜及水平配向液晶硬化膜A形成於垂直配向液晶硬化膜上。又，亦可於延伸膜上或水平配向液晶硬化膜A形成垂直配向液晶硬化膜。[Manufacturing method of laminated body] The manufacturing method of the laminated body of the present invention includes the step of forming a vertically aligned liquid crystal cured film. The step of forming the vertically aligned liquid crystal cured film may be the above-mentioned manufacturing method of the vertically aligned liquid crystal cured film. According to the production method of the vertically aligned liquid crystal cured film described above, a laminate composed of a substrate and a vertically aligned liquid crystal cured film, and a laminate composed of a substrate, an alignment film, and a vertically aligned liquid crystal cured film can be manufactured. When the laminate has a film aligned horizontally with respect to the in-plane direction of the vertically aligned cured liquid crystal film, the method of manufacturing the laminate further includes a stretched film lamination step or a horizontally aligned cured liquid crystal film A forming step. The stretched film bonding step is to use an adhesive to bond the stretched film to, for example, a vertical alignment liquid crystal cured film. The method of manufacturing a laminate with a horizontally aligned liquid crystal cured film A can be produced by, for example, laminating a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film through an adhesive layer, or forming a horizontally aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film A On the vertically aligned liquid crystal cured film. Moreover, the vertical alignment liquid crystal cured film can also be formed on the stretched film or the horizontal alignment liquid crystal cured film A.
[黏接著劑] 作為黏接著劑，例如可列舉感壓式黏著劑、乾燥固化型接著劑、及化學反應型接著劑。作為化學反應型接著劑，例如可列舉活性能量線硬化型接著劑。[adhesive] Examples of adhesives include pressure-sensitive adhesives, dry-curable adhesives, and chemical reaction adhesives. As a chemical reaction type adhesive agent, an active energy ray hardening type adhesive agent is mentioned, for example.
感壓式黏著劑通常包含聚合物，亦可包含溶劑。作為聚合物，例如可列舉丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、及聚醚。該等感壓式黏著劑之中，包含丙烯酸系聚合物之感壓式黏著劑由於光學透明性優異，具有適度之潤濕性或凝集力，接著性優異，進而耐候性或耐熱性等較高，且加熱或加濕之條件下不易產生鼓起或剝離等，故而較佳。Pressure-sensitive adhesives usually contain polymers, and may also contain solvents. Examples of polymers include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among these pressure-sensitive adhesives, pressure-sensitive adhesives containing acrylic polymers have excellent optical transparency, moderate wettability or cohesive force, excellent adhesion, and high weather resistance and heat resistance. , and it is not easy to bulge or peel off under the condition of heating or humidification, so it is better.
作為丙烯酸系聚合物，例如較佳為酯部分之烷基為甲基、乙基或丁基之類之碳數1～20之烷基之(甲基)丙烯酸酯與(甲基)丙烯酸或(甲基)丙烯酸羥基乙酯等具有官能基之(甲基)丙烯酸系單體的共聚物。As an acrylic polymer, for example, (meth)acrylic acid ester and (meth)acrylic acid or (meth)acrylic acid or ( Copolymer of (meth)acrylic monomers having functional groups such as hydroxyethyl methacrylate.
包含此種共聚物之感壓式黏著劑由於黏著性優異，即便於貼合於被轉印體後移除，亦能夠不於被轉印體產生糊劑殘留等而相對容易地移除，故而較佳。丙烯酸系聚合物之玻璃轉移溫度較佳為25℃以下，更佳為0℃以下。此種丙烯酸系聚合物之質量平均分子量較佳為10萬以上。The pressure-sensitive adhesive containing such a copolymer has excellent adhesiveness and can be removed relatively easily without leaving paste residue on the transferred object even after being attached to the transferred object. better. The glass transition temperature of the acrylic polymer is preferably at most 25°C, more preferably at most 0°C. The mass average molecular weight of such acrylic polymer is preferably more than 100,000.
作為溶劑，例如可列舉作為上述溶劑而列舉之溶劑。感壓式黏著劑亦可含有光擴散劑。光擴散劑係對感壓式黏著劑賦予光擴散性之添加劑，只要為具有與感壓式黏著劑所包含之聚合物之折射率不同之折射率的微粒子即可。作為光擴散劑，可列舉包含無機化合物之微粒子、及包含有機化合物(聚合物)之微粒子。包括丙烯酸系聚合物在內，感壓式黏著劑作為有效成分所包含之聚合物大多具有1.4～1.6左右之折射率，因此較佳為自其折射率為1.2～1.8之光擴散劑適當選擇。感壓式黏著劑作為有效成分所包含之聚合物與光擴散劑之折射率差通常為0.01以上，就顯示裝置之亮度與顯示性之觀點而言，較佳為0.01～0.2。用作光擴散劑之微粒子較佳為球形之微粒子、尤其是接近單分散之微粒子，更佳為平均粒徑為2～6 μm之微粒子。折射率係藉由一般之最小偏角法或阿貝折射計進行測定。As a solvent, the solvent mentioned as said solvent is mentioned, for example. The pressure-sensitive adhesive may also contain a light diffusing agent. The light-diffusing agent is an additive that imparts light-diffusing properties to the pressure-sensitive adhesive, and may be fine particles having a different refractive index from that of the polymer contained in the pressure-sensitive adhesive. As a light-diffusion agent, the fine particle containing an inorganic compound, and the fine particle containing an organic compound (polymer) are mentioned. Including acrylic polymers, most of the polymers contained in pressure-sensitive adhesives as active ingredients have a refractive index of about 1.4 to 1.6, so it is preferable to appropriately select from light diffusing agents whose refractive index is 1.2 to 1.8. The difference in refractive index between the polymer contained in the pressure-sensitive adhesive as an active ingredient and the light diffusing agent is usually 0.01 or more, and preferably 0.01 to 0.2 from the viewpoint of the brightness and displayability of the display device. The microparticles used as the light diffusing agent are preferably spherical microparticles, especially close to monodisperse microparticles, more preferably microparticles with an average particle diameter of 2-6 μm. The refractive index is measured by the general minimum declination method or Abbe refractometer.
作為包含無機化合物之微粒子，例如可列舉氧化鋁(折射率1.76)及氧化矽(折射率1.45)。作為包含有機化合物(聚合物)之微粒子，例如可列舉三聚氰胺顆粒(折射率1.57)、聚甲基丙烯酸甲酯顆粒(折射率1.49)、甲基丙烯酸甲酯/苯乙烯共聚物樹脂顆粒(折射率1.50～1.59)、聚碳酸酯顆粒(折射率1.55)、聚乙烯顆粒(折射率1.53)、聚苯乙烯顆粒(折射率1.6)、聚氯乙烯顆粒(折射率1.46)、及聚矽氧樹脂顆粒(折射率1.46)。光擴散劑之含量通常相對於聚合物100質量份為3～30質量份。Examples of fine particles containing an inorganic compound include aluminum oxide (refractive index: 1.76) and silicon oxide (refractive index: 1.45). As fine particles containing organic compounds (polymers), for example, melamine particles (refractive index 1.57), polymethyl methacrylate particles (refractive index 1.49), methyl methacrylate/styrene copolymer resin particles (refractive index 1.50～1.59), polycarbonate particles (refractive index 1.55), polyethylene particles (refractive index 1.53), polystyrene particles (refractive index 1.6), polyvinyl chloride particles (refractive index 1.46), and silicone resin particles (refractive index 1.46). Content of a light-diffusion agent is 3-30 mass parts normally with respect to 100 mass parts of polymers.
感壓式黏著劑之厚度係根據其密接力等而決定，故而並無特別限制，通常為1 μm～40 μm。就加工性或耐久性等方面而言，該厚度較佳為3 μm～25 μm，更佳為5 μm～20 μm。藉由將由感壓式黏著劑形成之黏著層之厚度設為5 μm～20 μm，能夠保持自正面觀察顯示裝置之情形或自斜向觀察之情形之亮度，不易產生顯示圖像之暈染或模糊。The thickness of the pressure-sensitive adhesive is determined according to its adhesion, etc., so there is no special limitation, and it is usually 1 μm to 40 μm. From the viewpoint of processability and durability, the thickness is preferably 3 μm to 25 μm, more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed by the pressure-sensitive adhesive to 5 μm to 20 μm, it is possible to maintain the brightness of the display device when viewed from the front or when viewed from an oblique direction, and it is difficult to cause blooming or blurring of the displayed image. Vague.
乾燥固化型接著劑亦可包含溶劑。作為乾燥固化型接著劑，例如可列舉如下組合物，其含有具有羥基、羧基、或胺基之類之質子性官能基與乙烯性不飽和基之單體之聚合物、或胺基甲酸酯聚合物作為主成分，且進而含有多元醛、環氧化合物、環氧樹脂、三聚氰胺化合物、氧化鋯化合物、及鋅化合物之類之交聯劑或硬化性化合物。作為具有羥基、羧基或胺基等質子性官能基與乙烯性不飽和基之單體之聚合物，例如可列舉乙烯-順丁烯二酸共聚物、伊康酸共聚物、丙烯酸共聚物、丙烯醯胺共聚物、聚乙酸乙烯酯之皂化物、及聚乙烯醇系樹脂。The dry-curable adhesive may also contain a solvent. Examples of dry-curable adhesives include compositions containing polymers of monomers having protonic functional groups such as hydroxyl groups, carboxyl groups, or amine groups, and ethylenically unsaturated groups, or urethanes. A polymer is used as a main component, and further contains crosslinking agents such as polyaldehydes, epoxy compounds, epoxy resins, melamine compounds, zirconium oxide compounds, and zinc compounds or hardening compounds. Examples of polymers of monomers having protic functional groups such as hydroxyl groups, carboxyl groups, or amine groups and ethylenically unsaturated groups include ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, acrylic acid copolymers, and acrylic acid copolymers. Amide copolymer, saponified product of polyvinyl acetate, and polyvinyl alcohol-based resin.
作為聚乙烯醇系樹脂，例如可列舉聚乙烯醇、部分皂化聚乙烯醇、完全皂化聚乙烯醇、羧基改性聚乙烯醇、乙醯乙醯基改性聚乙烯醇、羥甲基改性聚乙烯醇、及胺基改性聚乙烯醇。水系之黏接著劑中之聚乙烯醇系樹脂之含量相對於水100質量份，通常為1～10質量份，較佳為1～5質量份。Examples of polyvinyl alcohol-based resins include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, and methylol-modified polyvinyl alcohol. Vinyl alcohol, and amino-modified polyvinyl alcohol. The content of the polyvinyl alcohol-based resin in the water-based adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass, relative to 100 parts by mass of water.
作為胺基甲酸酯樹脂，例如可列舉聚酯系離子聚合物型胺基甲酸酯樹脂。此處所謂聚酯系離子聚合物型胺基甲酸酯樹脂，係具有聚酯骨架之胺基甲酸酯樹脂，且係於其中導入有少量之離子性成分(親水成分)之樹脂。該離子聚合物型胺基甲酸酯樹脂由於不使用乳化劑，於水中乳化而成為乳液，故而可製成水系之黏接著劑。於使用聚酯系離子聚合物型胺基甲酸酯樹脂之情形時，有效的是調配水溶性之環氧化合物作為交聯劑。As a urethane resin, a polyester ionomer type urethane resin is mentioned, for example. Here, the polyester-based ionomer type urethane resin is a urethane resin having a polyester skeleton, and a resin into which a small amount of ionic components (hydrophilic components) is introduced. Since the ionomer type urethane resin does not use an emulsifier and is emulsified in water to form an emulsion, it can be made into a water-based adhesive. When using a polyester-based ionomer type urethane resin, it is effective to prepare a water-soluble epoxy compound as a crosslinking agent.
作為環氧樹脂，可列舉使表氯醇與藉由二伸乙基三胺或三伸乙基四胺等聚伸烷基聚胺與己二酸等二羧酸之反應而獲得之聚醯胺聚胺進行反應而獲得的聚醯胺環氧樹脂等。作為該聚醯胺環氧樹脂之市售品，例如可列舉Sumika Chemtex股份有限公司製造之「Sumirez Resin(註冊商標)650」及「Sumirez Resin 675」、以及日本PMC股份有限公司製造之「WS-525」。於調配環氧樹脂之情形時，其含量相對於聚乙烯醇系樹脂100質量份，通常為1～100質量份，較佳為1～50質量份。Examples of epoxy resins include polyamides obtained by reacting epichlorohydrin with polyalkylene polyamines such as diethylenetriamine or triethylenetetramine and dicarboxylic acids such as adipic acid. Polyamide epoxy resin obtained by reacting polyamine, etc. Commercially available polyamide epoxy resins include, for example, "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" manufactured by Sumika Chemtex Co., Ltd., and "WS- 525". When preparing an epoxy resin, its content is usually 1-100 mass parts with respect to 100 mass parts of polyvinyl alcohol-type resins, Preferably it is 1-50 mass parts.
就抑制外觀不良之產生之觀點而言，由乾燥固化型接著劑形成之黏接著劑層之厚度通常為0.001～5 μm，較佳為0.01～2 μm，進而較佳為0.01～0.5 μm。From the viewpoint of suppressing appearance defects, the thickness of the adhesive layer formed of a dry-curable adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm.
活性能量線硬化型接著劑亦可包含溶劑。活性能量線硬化型接著劑係指受到活性能量線之照射而硬化之黏接著劑。作為活性能量線硬化型接著劑，例如可列舉含有環氧化合物與陽離子聚合起始劑之陽離子聚合性之接著劑、含有丙烯酸系硬化成分與自由基聚合起始劑之自由基聚合性之接著劑、含有環氧化合物之類之陽離子聚合性之硬化成分與丙烯酸系化合物等自由基聚合性之硬化成分兩者且進而含有陽離子聚合起始劑與自由基聚合起始劑之接著劑、及不含該等聚合起始劑而藉由照射電子束而硬化之接著劑。The active energy ray-curable adhesive may also contain a solvent. The active energy ray-curing adhesive refers to an adhesive that hardens upon exposure to active energy rays. Examples of active energy ray-curable adhesives include cationically polymerizable adhesives containing epoxy compounds and cationic polymerization initiators, and radically polymerizable adhesives containing acrylic curing components and radical polymerization initiators. , an adhesive containing both a cationically polymerizable hardening component such as an epoxy compound and a radically polymerizable hardening component such as an acrylic compound, and further contains a cationic polymerization initiator and a radical polymerization initiator, and does not contain An adhesive that hardens by irradiating electron beams with these polymerization initiators.
該等活性能量線硬化型接著劑之中，較佳為含有丙烯酸系硬化成分與光自由基聚合起始劑之自由基聚合性之活性能量線硬化型接著劑、及含有環氧化合物與光陽離子聚合起始劑之陽離子聚合性之活性能量線硬化型接著劑。作為丙烯酸系硬化成分，例如可列舉(甲基)丙烯酸甲酯及(甲基)丙烯酸羥基乙酯之類之(甲基)丙烯酸酯、以及(甲基)丙烯酸。含有環氧化合物之活性能量線硬化型接著劑亦可進而含有環氧化合物以外之化合物。作為環氧化合物以外之化合物，例如可列舉氧雜環丁烷化合物及丙烯酸系化合物。Among these active energy ray-curable adhesives, radically polymerizable active energy ray-curable adhesives containing acrylic curing components and photoradical polymerization initiators, and epoxy compounds and photocations are preferred. Cationic polymerizable active energy ray hardening adhesive of polymerization initiator. Examples of the acrylic curing component include (meth)acrylates such as methyl (meth)acrylate and hydroxyethyl (meth)acrylate, and (meth)acrylic acid. The active energy ray-curable adhesive containing an epoxy compound may further contain compounds other than an epoxy compound. Examples of compounds other than epoxy compounds include oxetane compounds and acrylic compounds.
作為光自由基聚合起始劑及光陽離子聚合起始劑，例如可列舉上述光自由基聚合起始劑及光陽離子聚合起始劑。自由基聚合起始劑及陽離子聚合起始劑之含量相對於活性能量線硬化型接著劑100質量份，通常為0.5～20質量份，較佳為1～15質量份。As a photoradical polymerization initiator and a photocationic polymerization initiator, the said photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass relative to 100 parts by mass of the active energy ray-curable adhesive.
於活性能量線硬化型接著劑中亦可進而含有離子捕捉劑、抗氧化劑、鏈轉移劑、黏著賦予劑、熱塑性樹脂、填充劑、流動調整劑、塑化劑、及消泡劑。The active energy ray-curable adhesive may further contain ion scavengers, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, and defoamers.
＜橢圓偏光板＞ 橢圓偏光板包含上述積層體與偏光膜。橢圓偏光板亦可視需要進而包含任意之層(更具體而言為保護層及黏接著劑等)。積層體及偏光膜例如係經由黏接著劑而接著。＜Elliptical Polarizer＞ The elliptically polarizing plate includes the above-mentioned laminate and a polarizing film. The elliptically polarizing plate may further include an arbitrary layer (more specifically, a protective layer, an adhesive, etc.) as needed. The laminated body and the polarizing film are bonded via an adhesive, for example.
圖1係表示橢圓偏光板之層構成之一例的概略剖視圖。圖1所示之橢圓偏光板20由積層體15、黏接著劑7、偏光膜11、及保護層13構成。積層體15由基材1、水平配向膜3、水平配向液晶硬化膜A 5、黏接著劑7、及垂直配向液晶硬化膜9構成。水平配向液晶硬化膜A 5之遲相軸與偏光膜11之吸收軸所成之角較佳為45±5°。FIG. 1 is a schematic cross-sectional view showing an example of the layer configuration of an elliptically polarizing plate. The elliptically
(偏光膜) 偏光膜係具有偏光功能之膜。作為偏光膜，例如可列舉包含二色性色素且相對於偏光膜之膜表面朝水平方向配向之膜(更具體而言為吸附有二色性色素之延伸膜(以下，有時記載為偏光膜A)、及包含二色性色素之水平配向液晶硬化膜(以下，有時將構成偏光膜之上述水平配向液晶硬化膜記載為水平配向液晶硬化膜B、將由水平配向液晶硬化膜B構成之偏光膜記載為偏光膜B)等)。就橢圓偏光板之薄膜化之觀點而言，較佳為包含二色性色素之水平配向液晶硬化膜B。二色性色素意指顯示吸收各向異性，具有二色性色素之分子之長軸方向上之吸光度與短軸方向上之吸光度不同之性質的色素。(polarizing film) Polarizing film is a film with polarizing function. As the polarizing film, for example, a film that includes a dichroic dye and is aligned horizontally with respect to the film surface of the polarizing film (more specifically, a stretched film to which a dichroic dye is adsorbed (hereinafter sometimes referred to as a polarizing film) A), and a horizontally aligned liquid crystal cured film comprising a dichroic dye (hereinafter, the above-mentioned horizontally aligned liquid crystal cured film constituting a polarizing film is sometimes referred to as a horizontally aligned liquid crystal cured film B, and a polarized film composed of a horizontally aligned liquid crystal cured film B is used. The film is described as polarizing film B) etc.). From the viewpoint of thinning the elliptically polarizing plate, the horizontal alignment liquid crystal cured film B containing a dichroic dye is preferable. The dichroic dye means a dye that exhibits absorption anisotropy, and has a property in which the absorbance in the long-axis direction and the absorbance in the short-axis direction of molecules of the dichroic dye are different.
(水平配向液晶硬化膜B) 水平配向液晶硬化膜B係含有二色性色素與聚合性液晶化合物(以下，有時將形成水平配向液晶硬化膜B之聚合性液晶化合物記載為聚合性液晶化合物(B))之組合物(以下，有時記載為偏光膜B形成用組合物)之硬化物。水平配向液晶硬化膜B包含二色性色素，且係聚合性液晶化合物(B)於相對於面內方向朝水平方向配向之狀態下硬化而成的液晶硬化膜。(Horizontal Alignment Liquid Crystal Curing Film B) The horizontal alignment liquid crystal cured film B is a composition containing a dichroic dye and a polymerizable liquid crystal compound (hereinafter, the polymerizable liquid crystal compound forming the horizontal alignment liquid crystal cured film B is sometimes described as a polymerizable liquid crystal compound (B)) (hereinafter , It is sometimes described as a cured product of the composition for forming a polarizing film B). The horizontal alignment liquid crystal cured film B contains a dichroic dye, and is a liquid crystal cured film cured in a state where the polymerizable liquid crystal compound (B) is aligned in the horizontal direction with respect to the in-plane direction.
水平配向液晶硬化膜B較佳為聚合性液晶化合物(B)於相對於膜之面內方向朝水平方向配向之層列相之狀態下硬化而成的硬化膜。即，於聚合性液晶化合物(B)為熱致液晶之情形時，可為顯示向列液晶相之熱致性液晶化合物，亦可為顯示層列液晶相之熱致性液晶化合物。於藉由聚合反應而作為硬化膜表現偏光功能時，聚合性液晶化合物所顯示之液晶狀態較佳為層列相，若為高次層列相則就高性能化之觀點而言更佳。其中，更佳為形成層列B相、層列D相、層列E相、層列F相、層列G相、層列H相、層列I相、層列J相、層列K相或層列L相之高次層列液晶化合物，進而較佳為形成層列B相、層列F相或層列I相之高次層列液晶化合物。若聚合性液晶化合物(B)所形成之液晶相為該等高次層列相，則能夠製造偏光性能更高之偏光膜。又，偏光性能如上所述較高之偏光膜於X射線繞射測定中，可獲得源自六相或結晶相等高次結構之布勒格波峰。該布勒格波峰係源自分子配向之週期結構之波峰，可獲得其週期間隔為3～6 Å之膜。就獲得更高之偏光特性之觀點而言，水平配向液晶硬化膜B較佳為包含於層列相之狀態下聚合之聚合性液晶化合物(B)之聚合物。再者，聚合性液晶化合物(B)所具有之下述聚合性基於水平配向液晶硬化膜B中可為未聚合之狀態，亦可為已聚合之狀態。即，水平配向液晶硬化膜B可於聚合性液晶化合物(B)(單體)、聚合性液晶化合物(B)之低聚物、聚合性液晶化合物(B)之聚合物、及該等之組合之任一狀態下含有。聚合性液晶化合物(B)所具有之聚合性基於水平配向液晶硬化膜B中較佳為未聚合之狀態。The horizontal alignment liquid crystal cured film B is preferably a cured film obtained by curing the polymerizable liquid crystal compound (B) in a state of a smectic phase aligned horizontally with respect to the in-plane direction of the film. That is, when the polymerizable liquid crystal compound (B) is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase, or may be a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. When expressing a polarizing function as a cured film by a polymerization reaction, the liquid crystal state exhibited by the polymerizable liquid crystal compound is preferably a smectic phase, and a higher-order smectic phase is more preferable from the viewpoint of high performance. Among them, it is more preferable to form a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, and a smectic K phase. Or a higher order smectic liquid crystal compound of a smectic L phase, and more preferably a higher order smectic liquid crystal compound forming a smectic B phase, a smectic F phase, or a smectic I phase. If the liquid crystal phase formed by the polymerizable liquid crystal compound (B) is such a higher order smectic phase, a polarizing film with higher polarizing performance can be produced. In addition, a polarizing film with a high polarizing performance as described above can obtain Buhlerg peaks derived from a hexaphase or crystal equivalent high-order structure in X-ray diffraction measurement. The Bragg peak is derived from the peak of the periodic structure of molecular alignment, and a film with a periodic interval of 3-6 Å can be obtained. From the viewpoint of obtaining higher polarization characteristics, the horizontal alignment liquid crystal cured film B is preferably a polymer containing a polymerizable liquid crystal compound (B) polymerized in a smectic state. Furthermore, the following polymerizability of the polymerizable liquid crystal compound (B) may be in an unpolymerized state or a polymerized state in the horizontal alignment liquid crystal cured film B. That is, the horizontal alignment liquid crystal cured film B can be made of a polymerizable liquid crystal compound (B) (monomer), an oligomer of a polymerizable liquid crystal compound (B), a polymer of a polymerizable liquid crystal compound (B), and combinations thereof contained in either state. The polymerizability of the polymerizable liquid crystal compound (B) is based on the fact that in the horizontally aligned liquid crystal cured film B, it is preferably in an unpolymerized state.
作為聚合性液晶化合物(B)，具體而言，可列舉下述式(B1)所表示之化合物(以下，亦稱為聚合性液晶化合物(B1))等。該聚合性液晶可單獨使用，亦可組合2種以上使用。As a polymeric liquid crystal compound (B), the compound (henceforth also referred to as a polymeric liquid crystal compound (B1)) etc. which are represented by following formula (B1) is mentioned specifically,. These polymerizable liquid crystals may be used alone or in combination of two or more.
U1
-V1
-W1
-X1
-Y1
-X2
-Y2
-X3
-W2
-V2
-U2
(B1)
[式(B1)中，
X1
、X2
、及X3
分別獨立表示2價芳香族基或2價脂環式烴基，此處，該2價芳香族基或該2價脂環式烴基所包含之氫原子可被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基、或硝基，構成該2價芳香族基或該2價脂環式烴基之碳原子可被取代為氧原子、硫原子、或氮原子。其中，X1
、X2
、及X3
中之至少1個表示可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基。
Y1
、Y2
、W1
、及W2
分別獨立表示單鍵或二價連結基。
V1
及V2
分別獨立表示可具有取代基之碳數1～20之烷二基，構成該烷二基之-CH2
-可被取代為-O-、-CO-、-S-或NH-。
U1
及U2
分別獨立表示聚合性基或氫原子，U1
及U2
中之至少1個表示聚合性基。U 1 -V 1 -W 1 -X 1 -Y 1 -X 2 -Y 2 -X 3 -W 2 -V 2 -U 2 (B1) [In formula (B1), X 1 , X 2 , and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, where the hydrogen atoms contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be replaced by halogen atoms,
於聚合性液晶化合物(B1)中，X1 、X2 、及X3 中之至少1個表示可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基。特別是X1 及X3 較佳為表示可具有取代基之環己烷-1,4-二基，該環己烷-1,4-二基進而較佳為反式環己烷-1,4-二基。作為可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基任意地具有之取代基，例如可列舉甲基、乙基、及丁基之類之碳數1～4之烷基、氰基、以及氯原子及氟原子之類之鹵素原子。可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基較佳為1,4-伸苯基及環己烷-1,4-二基。又，於Y1 及Y2 為同一結構之情形時，較佳為X1 、X2 及X3 中之至少1個為不同之結構。於X1 、X2 及X3 中之至少1個為不同之結構之情形時，有容易表現層列液晶性之傾向。In the polymerizable liquid crystal compound (B1), at least one of X 1 , X 2 , and X 3 represents 1,4-phenylene that may have a substituent, or cyclohexane-1 that may have a substituent, 4-diradical. In particular, X 1 and X 3 preferably represent cyclohexane-1,4-diyl which may have substituents, and the cyclohexane-1,4-diyl is further preferably trans-cyclohexane-1, 4-diradical. As the substituent which the 1,4-phenylene which may have a substituent or the cyclohexane-1,4-diyl which may have a substituent may have, for example, methyl, ethyl, and butyl are mentioned Such as alkyl groups having 1 to 4 carbon atoms, cyano groups, and halogen atoms such as chlorine atoms and fluorine atoms. 1,4-phenylene which may have a substituent, or cyclohexane-1,4-diyl which may have a substituent is preferably 1,4-phenylene and cyclohexane-1,4-diyl . Also, when Y 1 and Y 2 have the same structure, at least one of X 1 , X 2 and X 3 is preferably a different structure. When at least one of X 1 , X 2 and X 3 has a different structure, smectic liquid crystallinity tends to be easily expressed.
Y1 及Y2 較佳為分別獨立表示單鍵、-CH2 CH2 -、-CH2 O-、-CH2 CH2 O-、-COO-、-OCO-、-N=N-、-CRa =CRb -、-C≡C-或CRa =N-，Ra 及Rb 分別獨立表示氫原子或碳數1～4之烷基。Y1 及Y2 更佳為分別獨立表示-CH2 CH2 -、-COO-、-OCO-、或單鍵。又，於X1 、X2 及X3 全部為同一結構之情形時，較佳為Y1 及Y2 為互不相同之鍵結方式。於Y1 及Y2 為互不相同之鍵結方式之情形時，有容易表現層列液晶性之傾向。Y 1 and Y 2 preferably independently represent a single bond, -CH 2 CH 2 -, -CH 2 O-, -CH 2 CH 2 O-, -COO-, -OCO-, -N=N-, - CR a =CR b -, -C≡C- or CR a =N-, R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons. More preferably, Y 1 and Y 2 each independently represent -CH 2 CH 2 -, -COO-, -OCO-, or a single bond. Also, when X 1 , X 2 and X 3 all have the same structure, it is preferable that Y 1 and Y 2 have different bonding modes. When Y 1 and Y 2 have different bonding methods, smectic liquid crystallinity tends to be easily exhibited.
W1 及W2 較佳為分別獨立表示單鍵、-O-、-S-、-COO-、或OCO-，更佳為分別獨立表示單鍵或-O-。W 1 and W 2 preferably independently represent a single bond, -O-, -S-, -COO-, or OCO-, more preferably independently represent a single bond or -O-.
作為V1 及V2 所表示之碳數1～20之烷二基，例如可列舉亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、癸烷-1,10-二基、十四烷-1,14-二基、及二十烷-1,20-二基。V1 及V2 較佳為表示碳數2～12之烷二基，更佳為表示直鏈狀之碳數6～12之烷二基。於V1 及V2 表示直鏈狀之碳數6～12之烷二基之情形時，有聚合性液晶化合物(B1)之配向性提高，容易表現層列液晶性之傾向。 作為可具有取代基之碳數1～20之烷二基任意地具有之取代基，例如可列舉氰基、以及氯原子及氟原子之類之鹵素原子，但該烷二基較佳為未經取代，更佳為未經取代且直鏈狀之烷二基。Examples of alkanediyl groups having 1 to 20 carbon atoms represented by V1 and V2 include methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,3-diyl, butane Alkane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane Alkane-1,10-diyl, tetradecane-1,14-diyl, and eicosane-1,20-diyl. V 1 and V 2 preferably represent an alkanediyl group having 2 to 12 carbon atoms, and more preferably represent a linear alkanediyl group having 6 to 12 carbon atoms. When V 1 and V 2 represent a straight-chain alkanediyl group having 6 to 12 carbon atoms, the alignment of the polymerizable liquid crystal compound (B1) tends to be improved, and smectic liquid crystallinity tends to be easily exhibited. Examples of substituents that may be optionally substituted by an alkanediyl group having 1 to 20 carbon atoms include a cyano group and a halogen atom such as a chlorine atom or a fluorine atom, but the alkanediyl group is preferably untreated. Substituted, more preferably unsubstituted, straight-chain alkanediyl.
U1 及U2 較佳為均表示聚合性基，更佳為均表示光聚合性基。具有光聚合性基之聚合性液晶化合物(B1)由於能夠於較熱聚合性基低溫之條件下進行聚合，故而能夠於液晶之秩序度更高之狀態下形成聚合物，就該方面而言有利。Both U1 and U2 preferably represent a polymerizable group, more preferably both represent a photopolymerizable group. Since the polymerizable liquid crystal compound (B1) having a photopolymerizable group can be polymerized at a lower temperature than the thermally polymerizable group, it is advantageous in that it can form a polymer in a state with a higher degree of liquid crystal order. .
U1 及U2 所表示之聚合性基可相互相同亦可不同，較佳為相同。作為聚合性基，例如可列舉乙烯基、乙烯氧基、1-氯乙烯基、異丙烯基、4-乙烯基苯基、丙烯醯氧基、甲基丙烯醯氧基、環氧乙烷基、及氧雜環丁基。該等光聚合性基之中，較佳為丙烯醯氧基、甲基丙烯醯氧基、乙烯氧基、環氧乙烷基、及氧雜環丁基，更佳為甲基丙烯醯氧基、及丙烯醯氧基。The polymerizable groups represented by U1 and U2 may be the same or different from each other, and are preferably the same. Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl, and oxetanyl. Among these photopolymerizable groups, preferred are acryloxy, methacryloxy, vinyloxy, oxiranyl, and oxetanyl, more preferably methacryloxy , and acryloxy.
作為此種聚合性液晶化合物(B1)，例如可列舉以下之式(1-1)～(1-23)所表示之聚合性液晶化合物。
[化17]
[化18]
[化19]
[化20]
例示之上述聚合性液晶化合物(B1)之中，較佳為選自由式(1-2)、式(1-3)、式(1-4)、式(1-6)、式(1-7)、式(1-8)、式(1-13)、式(1-14)及式(1-15)所表示之化合物所組成之群中之至少1種。聚合性液晶化合物可單獨使用1種，亦可組合2種以上使用。Among the exemplified above-mentioned polymerizable liquid crystal compounds (B1), those selected from formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1- 7), at least one of the group consisting of compounds represented by formula (1-8), formula (1-13), formula (1-14) and formula (1-15). The polymerizable liquid crystal compound may be used alone or in combination of two or more.
聚合性液晶化合物(B1)例如可藉由Lub等、Recl. Trav. Chim. Pays-Bas、115、321-328(1996)、或日本專利第4719156號等所記載之公知之方法製造。The polymerizable liquid crystal compound (B1) can be produced, for example, by a known method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.
偏光膜B形成用組合物只要無損本發明之效果，則亦可含有聚合性液晶化合物(B)以外之其他液晶化合物，就獲得配向秩序度較高之偏光膜之觀點而言，聚合性液晶化合物(B)相對於偏光膜B形成用組合物中所含之所有液晶化合物之總質量的比率較佳為51質量%以上，更佳為70質量%以上，進而較佳為90質量%以上。The composition for forming the polarizing film B may contain liquid crystal compounds other than the polymerizable liquid crystal compound (B) as long as the effects of the present invention are not impaired. From the viewpoint of obtaining a polarizing film with a high degree of alignment order, the polymerizable liquid crystal compound The ratio of (B) to the total mass of all liquid crystal compounds contained in the composition for forming a polarizing film B is preferably at least 51% by mass, more preferably at least 70% by mass, and still more preferably at least 90% by mass.
又，於偏光膜B形成用組合物包含2種以上之聚合性液晶化合物(B)之情形時，可其中至少1種為聚合性液晶化合物(B1)，亦可其全部為聚合性液晶化合物(B1)。藉由組合複數種聚合性液晶化合物，有於液晶-結晶相轉移溫度以下之溫度下亦能夠暫時地保持液晶性之情況。Also, when the composition for forming the polarizing film B contains two or more polymerizable liquid crystal compounds (B), at least one of them may be the polymerizable liquid crystal compound (B1), or all of them may be the polymerizable liquid crystal compound ( B1). By combining a plurality of polymerizable liquid crystal compounds, liquid crystallinity may be temporarily maintained even at a temperature lower than the liquid crystal-crystal phase transition temperature.
偏光膜B形成用組合物中之聚合性液晶化合物(B)之含量相對於偏光膜B形成用組合物之固形物成分，較佳為40～99.9質量%，更佳為60～99質量%，進而較佳為70～99質量%。若聚合性液晶化合物(B)之含量為上述範圍內，則有液晶化合物之配向性變高之傾向。再者，固形物成分係指自偏光膜B形成用組合物去除溶劑後之成分之合計量。The content of the polymerizable liquid crystal compound (B) in the composition for forming a polarizing film B is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, based on the solid content of the composition for forming a polarizing film B, More preferably, it is 70-99 mass %. When content of a polymerizable liquid crystal compound (B) exists in the said range, there exists a tendency for the orientation of a liquid crystal compound to become high. In addition, the solid content means the total amount of the component which removed the solvent from the composition for polarizing film B formation.
(二色性色素) 二色性色素係指具有分子之長軸方向上之吸光度與短軸方向上之吸光度不同之性質之色素。作為二色性色素，較佳為具有吸收可見光之特性，更佳為於380～680 nm之波長範圍具有吸收極大波長(λMAX )。作為二色性色素，例如可列舉碘及二色性之有機染料。作為二色性之有機染料，例如可列舉吖啶色素、㗁𠯤色素、花青色素、萘色素、偶氮色素、及蒽醌色素。該等二色性之有機染料之中，較佳為偶氮色素。作為偶氮色素，例如可列舉單偶氮色素、雙偶氮色素、三偶氮色素、四偶氮色素、及茋偶氮色素。該等偶氮色素之中，較佳為雙偶氮色素及三偶氮色素。二色性之有機染料可單獨使用1種，亦可組合2種以上使用，為了於可見光全域獲得吸收，較佳為組合3種以上之二色性色素使用，更佳為組合3種以上之偶氮色素使用。聚乙烯醇系樹脂膜較佳為於染色處理前實施向水中之浸漬處理。(Dichroic Dye) A dichroic dye is a dye having a property in which the absorbance in the long-axis direction and the absorbance in the short-axis direction of the molecule are different. As a dichroic dye, it is preferable to have a characteristic of absorbing visible light, and it is more preferable to have a maximum absorption wavelength (λ MAX ) in the wavelength range of 380 to 680 nm. Examples of dichroic dyes include iodine and dichroic organic dyes. Examples of dichroic organic dyes include acridine dyes, cyanine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes. Among these dichroic organic dyes, azo dyes are preferred. Examples of the azo dyes include monoazo dyes, disazo dyes, trisazo dyes, tetrazo dyes, and stilbene azo dyes. Among these azo dyes, disazo dyes and trisazo dyes are preferable. Dichroic organic dyes can be used alone or in combination of two or more. In order to obtain absorption in the entire range of visible light, it is preferable to use a combination of three or more dichroic dyes, and more preferably a combination of three or more. Nitrogen used. It is preferable that the polyvinyl alcohol-type resin film implements the immersion process in water before a dyeing process.
作為偶氮色素，例如可列舉式(I)所表示之化合物。 T1 -A1 (-N=N-A2 )p -N=N-A3 -T2 (I) [式(I)中， A1 、A2 、及A3 分別獨立表示可具有取代基之1,4-伸苯基、萘-1,4-二基、或可具有取代基之2價雜環基，T1 及T2 分別獨立表示拉電子基或推電子基，位於相對於偶氮鍵面內實質上為180°之位置；p表示0～4之整數；於p表示2以上之整數之情形時，複數個A2 相互可相同亦可不同。於偶氮色素在可見光區域顯示吸收之範圍內，-N=N-鍵可被取代為-C=C-鍵、-COO-鍵、-NHCO-鍵、或-N=CH-鍵]As an azo dye, the compound represented by formula (I) is mentioned, for example. T 1 -A 1 (-N=NA 2 ) p -N=NA 3 -T 2 (I) [In formula (I), A 1 , A 2 , and A 3 independently represent 1 which may have a substituent, 4-phenylene, naphthalene-1,4-diyl, or a divalent heterocyclic group that may have a substituent, T 1 and T 2 independently represent an electron-withdrawing group or an electron-pushing group, and are located on the surface relative to the azo bond The position within is substantially 180°; p represents an integer of 0 to 4; when p represents an integer of 2 or more, the plurality of A 2 may be the same or different from each other. In the range where the azo pigment shows absorption in the visible light region, the -N=N-bond can be replaced by a -C=C-bond, -COO-bond, -NHCO-bond, or -N=CH-bond]
作為A1 、A2 、及A3 所表示之1,4-伸苯基、萘-1,4-二基、及2價雜環基任意地具有之取代基，例如可列舉：甲基、乙基、及丁基之類之碳數1～4之烷基；甲氧基、乙氧基、及丁氧基之類之碳數1～4之烷氧基；三氟甲基之類之碳數1～4之氟烷基；氰基；硝基；氯原子及氟原子之類之鹵素原子；胺基、二乙胺基及吡咯啶基之類之經取代之胺基或未經取代之胺基(經取代之胺基係指具有1個或2個碳數1～6之烷基之胺基、或者2個取代烷基相互鍵結而形成碳數2～8之烷二基之胺基；未經取代之胺基為-NH2 )。再者，作為碳數1～6之烷基，例如可列舉甲基、乙基、及己基。作為碳數2～8之烷二基，例如可列舉伸乙基、丙烷-1,3-二基、丁烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、及辛烷-1,8-二基。為了包含在層列液晶之類之高秩序液晶結構中，A1 、A2 及A3 較佳為表示未經取代或氫原子被取代為甲基或甲氧基之1,4-伸苯基、或2價雜環基，p較佳為表示0～2之整數。其中，p為1且A1 、A2 及A3 之3個結構中之至少2個為1,4-伸苯基就兼具分子合成之簡便性與較高之性能之方面而言更佳。Examples of substituents optionally contained in the 1,4-phenylene group, naphthalene-1,4-diyl group, and divalent heterocyclic group represented by A 1 , A 2 , and A 3 include methyl, Alkyl groups with 1 to 4 carbons such as ethyl and butyl; alkoxy groups with 1 to 4 carbons such as methoxy, ethoxy, and butoxy; trifluoromethyl and the like Fluoroalkyl groups with 1 to 4 carbon atoms; cyano groups; nitro groups; halogen atoms such as chlorine atoms and fluorine atoms; substituted amino groups such as amine groups, diethylamino groups, and pyrrolidinyl groups or unsubstituted The amine group (the substituted amino group refers to the amine group having 1 or 2 alkyl groups with 1 to 6 carbons, or the amine group with 2 substituted alkyl groups bonded to each other to form an alkanediyl group with 2 to 8 carbons Amine group; unsubstituted amino group is -NH 2 ). In addition, as a C1-6 alkyl group, a methyl group, an ethyl group, and a hexyl group are mentioned, for example. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,3-diyl, 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl. In order to be included in high-order liquid crystal structures such as smectic liquid crystals, A 1 , A 2 and A 3 preferably represent 1,4-phenylene groups that are unsubstituted or hydrogen atoms are substituted with methyl or methoxy groups , or a divalent heterocyclic group, p is preferably an integer representing 0-2. Among them, p is 1 and at least two of the three structures of A 1 , A 2 and A 3 are 1,4-phenylene groups, which is more preferable in terms of both the simplicity of molecular synthesis and higher performance .
作為2價雜環基，例如可列舉自喹啉、噻唑、苯并噻唑、噻吩并噻唑、咪唑、苯并咪唑、㗁唑、及苯并㗁唑之類之雜環分別去除2個氫原子所得之基。於A2 表示2價雜環基之情形時，較佳為分子鍵角度實質上成為180°之結構，具體而言，更佳為兩個5員環縮合而成之苯并噻唑結構、苯并咪唑結構、及苯并㗁唑結構。Examples of divalent heterocyclic groups include those obtained by removing two hydrogen atoms from heterocycles such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. foundation. When A represents a divalent heterocyclic group, it is preferably a structure in which the molecular bond angle becomes substantially 180°, specifically, a benzothiazole structure formed by condensation of two 5-membered rings, a benzo Imidazole structure, and benzoxazole structure.
T1 及T2 分別獨立表示拉電子基或推電子基，較佳為表示互不相同之結構之拉電子基或推電子基，進而較佳為T1 表示拉電子基且T2 表示推電子基之情形、或T1 表示推電子基且T2 表示拉電子基之情形。具體而言，T1 及T2 較佳為分別獨立為碳數1～8之烷基、碳數1～8之烷氧基、氰基、硝基、具有1個或2個碳數1～6之烷基之經取代之胺基、2個該取代烷基相互鍵結而形成碳數2～8之烷二基之胺基、及三氟甲基。其中，為了包含在層列液晶之類之高秩序液晶結構中，必須為分子之排斥體積更小之結構體，故而較佳為碳數1～6之烷基、碳數1～6之烷氧基、氰基、具有1個或2個碳數1～6之烷基之經取代之胺基、2個該取代烷基相互鍵結而形成碳數2～8之烷二基之胺基。T 1 and T 2 independently represent an electron-pulling group or an electron-pushing group, preferably representing an electron-pulling group or an electron-pushing group of mutually different structures, and further preferably T 1 represents an electron-pulling group and T 2 represents an electron-pushing group The case of the group, or the case where T 1 represents the electron-pushing group and T 2 represents the case of the electron-withdrawing group. Specifically, T1 and T2 are preferably each independently an alkyl group with 1 to 8 carbons, an alkoxy group with 1 to 8 carbons, a cyano group, a nitro group, and one or two groups with 1 to 8 carbons. A substituted amino group of 6 alkyl groups, an amino group in which two of the substituted alkyl groups are bonded to form an alkanediyl group having 2 to 8 carbon atoms, and a trifluoromethyl group. Among them, in order to be included in a high-order liquid crystal structure such as smectic liquid crystals, it must be a structure with a smaller molecular exclusion volume, so it is preferably an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons. A cyano group, a cyano group, a substituted amino group having one or two alkyl groups having 1 to 6 carbon atoms, and an amino group in which two substituted alkyl groups are bonded to form an alkanediyl group having 2 to 8 carbon atoms.
作為此種偶氮色素，例如可列舉以下之式(2-1)～(2-8)所表示之偶氮色素。As such an azo dye, the azo dye represented by following formula (2-1) - (2-8) is mentioned, for example.
[化21]
[化22]
式(2-1)～(2-8)中， B1 ～B30 分別獨立表示氫原子、碳數1～6之烷基、碳數1～6之烷氧基、氰基、硝基、經取代或未經取代之胺基(經取代之胺基及未經取代之胺基之定義如上所述)、氯原子、或三氟甲基。又，就於與層列液晶組合之情形時獲得較高之偏光性能之觀點而言，B2 、B6 、B9 、B14 、B18 、B19 、B22 、B23 、B24 、B27 、B28 、及B29 較佳為分別獨立表示氫原子或甲基，進而較佳為表示氫原子。 n1～n4分別獨立表示0～2之整數。 於n1表示2之情形時，複數個B2 相互可相同亦可不同， 於n2表示2之情形時，複數個B6 相互可相同亦可不同， 於n3表示2之情形時，複數個B9 相互可相同亦可不同， 於n4表示2之情形時，複數個B14 相互可相同亦可不同。In formulas (2-1) to (2-8), B 1 to B 30 independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a cyano group, a nitro group, A substituted or unsubstituted amino group (the definitions of the substituted amino group and the unsubstituted amino group are as defined above), a chlorine atom, or a trifluoromethyl group. Also, from the viewpoint of obtaining high polarizing performance when combined with smectic liquid crystals, B 2 , B 6 , B 9 , B 14 , B 18 , B 19 , B 22 , B 23 , B 24 , B 27 , B 28 , and B 29 preferably independently represent a hydrogen atom or a methyl group, and more preferably represent a hydrogen atom. n1 to n4 each independently represent an integer of 0 to 2. When n1 represents 2, the plurality of B 2 may be the same or different from each other; when n2 represents 2, the plurality of B 6 may be the same or different; when n3 represents 2, the plurality of B 9 They may be the same or different from each other, and when n4 represents 2, a plurality of B 14 may be the same or different from each other.
作為上述蒽醌色素，較佳為式(2-9)所表示之化合物。The above-mentioned anthraquinone dye is preferably a compound represented by the formula (2-9).
[化24]
[式(2-9)中， R1 ～R8 分別獨立表示氫原子、-Rx 、-NH2 、-NHRx 、-NRx 2 、-SRx 、或鹵素原子； Rx 表示碳數1～4之烷基或碳數6～12之芳基][In formula (2-9), R 1 to R 8 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x , or a halogen atom; R x represents a carbon number 1-4 alkyl or aryl with 6-12 carbons]
作為上述㗁𠯤色素，較佳為式(2-10)所表示之化合物。The above-mentioned 㗁𠯤 pigment is preferably a compound represented by the formula (2-10).
[化25]
[式(2-10)中， R9 ～R15 分別獨立表示氫原子、-Rx 、-NH2 、-NHRx 、-NRx 2 、-SRx 、或鹵素原子； Rx 表示碳數1～4之烷基或碳數6～12之芳基][In formula (2-10), R 9 to R 15 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x , or a halogen atom; R x represents a carbon number 1-4 alkyl or aryl with 6-12 carbons]
作為上述吖啶色素，較佳為式(2-11)所表示之化合物。The acridine dye is preferably a compound represented by formula (2-11).
[化26]
[式(2-11)中， R16 ～R23 分別獨立表示氫原子、-Rx 、-NH2 、-NHRx 、-NRx 2 、-SRx 、或鹵素原子； Rx 表示碳數1～4之烷基或碳數6～12之芳基][In formula (2-11), R 16 to R 23 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x , or a halogen atom; R x represents a carbon number 1-4 alkyl or aryl with 6-12 carbons]
式(2-9)、式(2-10)及式(2-11)中，作為Rx 所表示之碳數1～4之烷基，例如可列舉甲基、乙基、丙基、丁基、戊基、及己基。式(2-9)、式(2-10)及式(2-11)中，作為Rx 所表示之碳數6～12之芳基，例如可列舉苯基、甲苯甲醯基、二甲苯基、及萘基。In formula (2-9), formula (2-10) and formula (2-11), the alkyl group having 1 to 4 carbon atoms represented by R x includes, for example, methyl, ethyl, propyl, butyl, base, pentyl, and hexyl. In formula (2-9), formula (2-10) and formula (2-11), the aryl group having 6 to 12 carbon atoms represented by R x includes, for example, phenyl, toluyl, xylene base, and naphthyl.
作為上述花青色素，較佳為式(2-12)所表示之化合物及式(2-13)所表示之化合物。As the above-mentioned cyanine dye, compounds represented by formula (2-12) and compounds represented by formula (2-13) are preferable.
[化27]
[式(2-12)中，
D1
及D2
分別獨立表示式(2-12a)～式(2-12d)之任一者所表示之基；
[化28]
[化29]
[式(2-13)中，
D3
及D4
分別獨立表示式(2-13a)～式(2-13h)之任一者所表示之基；
[化30]
就獲得良好之光吸收特性之觀點而言，二色性之有機染料之含量(於包含複數種之情形時為其合計量)相對於聚合性液晶化合物(B)100質量份，通常為0.1～30質量份，較佳為1～20質量份，更佳為3～15質量份。若二色性之有機染料之含量相對於聚合性液晶化合物(B)100質量份為0.1質量份以上，則有二色性之有機染料之光吸收變充分而獲得充分之偏光性能的傾向。若二色性之有機染料之含量相對於聚合性液晶化合物(B)100質量份為30質量份以下，則聚合性液晶化合物之配向不易被妨礙。From the viewpoint of obtaining good light-absorbing properties, the content of the dichroic organic dye (the total amount when plural kinds are included) is usually 0.1 to 100 parts by mass of the polymerizable liquid crystal compound (B). 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass. When the content of the dichroic organic dye is 0.1 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound (B), the light absorption of the dichroic organic dye becomes sufficient and sufficient polarizing performance tends to be obtained. When the content of the dichroic organic dye is 30 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound (B), alignment of the polymerizable liquid crystal compound is less likely to be hindered.
(吸附有二色性色素之延伸膜) 於吸附有二色性色素之延伸膜之至少一側亦可具備透明保護膜。包含吸附有二色性色素之延伸膜作為偏光元件的膜通常係藉由在偏光元件之至少一面經由接著劑被透明保護膜夾入而製作，該偏光元件係經由如下步驟而製造：將聚乙烯醇系樹脂膜進行單軸延伸之步驟、藉由利用二色性色素對聚乙烯醇系樹脂膜進行染色而吸附該二色性色素之步驟、利用硼酸水溶液對吸附有二色性色素之聚乙烯醇系樹脂膜進行處理之步驟、及於利用硼酸水溶液進行處理後進行水洗之步驟。(Extended film adsorbed with dichroic pigment) A transparent protective film may also be provided on at least one side of the stretched film on which the dichroic dye is adsorbed. A film comprising a stretched film adsorbed with a dichroic pigment as a polarizing element is usually produced by sandwiching at least one side of the polarizing element with a transparent protective film through an adhesive. The polarizing element is manufactured through the following steps: Polyethylene A step of uniaxially stretching an alcohol-based resin film, a step of adsorbing a dichroic dye by dyeing a polyvinyl alcohol-based resin film with a dichroic dye, using an aqueous solution of boric acid to a polyvinyl alcohol-based resin film adsorbed with a dichroic dye A step of treating the alcohol-based resin film, and a step of washing with water after the treatment with a boric acid aqueous solution.
聚乙烯醇系樹脂係藉由使聚乙酸乙烯酯系樹脂皂化而獲得。作為聚乙酸乙烯酯系樹脂，例如除了可使用乙酸乙烯酯之均聚物即聚乙酸乙烯酯以外，亦可使用乙酸乙烯酯與能夠與其共聚之其他單體的共聚物。作為能夠與乙酸乙烯酯共聚之其他單體，例如可列舉不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、及具有銨基之丙烯醯胺類。Polyvinyl alcohol-based resins are obtained by saponifying polyvinyl acetate-based resins. As the polyvinyl acetate resin, for example, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers that can be copolymerized therewith can also be used. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having ammonium groups.
聚乙烯醇系樹脂之皂化度通常為85～100莫耳%左右，較佳為98莫耳%以上。聚乙烯醇系樹脂可經改性，例如亦可使用經醛類改性之聚乙烯醇縮甲醛或聚乙烯醇縮乙醛。聚乙烯醇系樹脂之聚合度通常為1,000～10,000左右，較佳為1,500～5,000之範圍。The degree of saponification of the polyvinyl alcohol-based resin is usually about 85-100 mole%, preferably more than 98 mole%. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.
將此種聚乙烯醇系樹脂製膜而成者係用作偏光膜之坯膜。將聚乙烯醇系樹脂製膜之方法並無特別限定，可使用公知之方法製膜。聚乙烯醇系坯膜之膜厚例如可設為10～150 μm左右。Those made of such polyvinyl alcohol-based resins are used as base films for polarizing films. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be used to form a film. The film thickness of a polyvinyl-alcohol-type base film can be made into about 10-150 micrometers, for example.
聚乙烯醇系樹脂膜之單軸延伸可於利用二色性色素進行染色之前、與染色同時、或於染色之後進行。於染色之後進行單軸延伸之情形時，該單軸延伸可於硼酸處理之前進行，亦可於硼酸處理中進行。又，亦可於該等複數個階段中進行單軸延伸。於進行單軸延伸時，可於周速不同之輥間單軸地進行延伸，亦可使用熱輥單軸地進行延伸。又，單軸延伸可為於大氣中進行延伸之乾式延伸，亦可為使用溶劑而於使聚乙烯醇系樹脂膜膨潤之狀態下進行延伸之濕式延伸。延伸倍率通常為3～8倍左右。The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. When performing uniaxial stretching after dyeing, the uniaxial stretching may be performed before or during boric acid treatment. In addition, uniaxial stretching can also be performed in these plural stages. In the case of uniaxial stretching, it may be uniaxially stretched between rolls having different circumferential speeds, or may be uniaxially stretched using a heated roll. In addition, the uniaxial stretching may be a dry stretching in which stretching is performed in the air, or a wet stretching in which a polyvinyl alcohol-based resin film is stretched in a state in which a polyvinyl alcohol-based resin film is swollen. The elongation ratio is usually about 3 to 8 times.
聚乙烯醇系樹脂膜之利用二色性色素進行之染色例如係藉由將聚乙烯醇系樹脂膜浸漬於含有二色性色素之水溶液中之方法而進行。The dyeing of a polyvinyl-alcohol-type resin film with a dichroic dye is performed by the method of immersing a polyvinyl-alcohol-type resin film in the aqueous solution containing a dichroic dye, for example.
於將碘用作二色性色素之情形時，通常採用將聚乙烯醇系樹脂膜浸漬於含有碘及碘化鉀之水溶液中進行染色之方法。該水溶液中之碘之含量相對於水100質量份，通常為0.01～1質量份左右。又，碘化鉀之含量相對於水100質量份，通常為0.5～20質量份左右。用於染色之水溶液之溫度通常為20～40℃左右。又，向該水溶液之浸漬時間(染色時間)通常為20～1,800秒左右。When iodine is used as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing iodine and potassium iodide is employ|adopted normally. Content of the iodine in this aqueous solution is about 0.01-1 mass part normally with respect to 100 mass parts of water. Moreover, content of potassium iodide is about 0.5-20 mass parts normally with respect to 100 mass parts of water. The temperature of the aqueous solution used for dyeing is usually about 20-40°C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 20 to 1,800 seconds.
另一方面，於使用二色性之有機染料作為二色性色素之情形時，通常採用將聚乙烯醇系樹脂膜浸漬於包含水溶性二色性染料之水溶液進行染色之方法。該水溶液中之二色性有機染料之含量相對於水100質量份，通常為1×10-4 ～10質量份左右，較佳為1×10-3 ～1質量份，進而較佳為1×10-3 ～1×10-2 質量份。該水溶液亦可包含硫酸鈉等無機鹽作為染色助劑。用於染色之二色性染料水溶液之溫度通常為20～80℃左右。又，向該水溶液之浸漬時間(染色時間)通常為10～1,800秒左右。On the other hand, when using a dichroic organic dye as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye for dyeing is generally employed. The content of the dichroic organic dye in the aqueous solution is usually about 1×10 -4 to 10 parts by mass, preferably 1×10 -3 to 1 part by mass, more preferably 1×10 -3 to 1 part by mass relative to 100 parts by mass of water 10 -3 to 1×10 -2 parts by mass. The aqueous solution may also contain inorganic salts such as sodium sulfate as dyeing aids. The temperature of the dichroic dye aqueous solution used for dyeing is about 20-80 degreeC normally. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.
利用二色性色素進行染色後之硼酸處理通常可藉由將經染色之聚乙烯醇系樹脂膜浸漬於硼酸水溶液之方法而進行。該硼酸水溶液中之硼酸之含量相對於水100質量份，通常為2～15質量份左右，較佳為5～12質量份。於使用碘作為二色性色素之情形時，該硼酸水溶液較佳為含有碘化鉀，該情形時之碘化鉀之含量相對於水100質量份，通常為0.1～15質量份左右，較佳為5～12質量份。向硼酸水溶液之浸漬時間通常為60～1,200秒左右，較佳為150～600秒，進而較佳為200～400秒。硼酸處理之溫度通常為50℃以上，較佳為50～85℃，進而較佳為60～80℃。The boric acid treatment after dyeing with a dichroic dye can be generally performed by a method of immersing a dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. Content of the boric acid in this boric-acid aqueous solution is about 2-15 mass parts normally with respect to 100 mass parts of water, Preferably it is 5-12 mass parts. When using iodine as a dichroic dye, the boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. parts by mass. The immersion time in the boric acid aqueous solution is about 60 to 1,200 seconds normally, Preferably it is 150 to 600 seconds, More preferably, it is 200 to 400 seconds. The temperature of the boric acid treatment is usually above 50°C, preferably 50-85°C, more preferably 60-80°C.
硼酸處理後之聚乙烯醇系樹脂膜通常進行水洗處理。水洗處理例如可藉由將經硼酸處理之聚乙烯醇系樹脂膜浸漬於水中之方法進行。水洗處理中之水之溫度通常為5～40℃左右。又，浸漬時間通常為1～120秒左右。The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by a method of immersing a boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of water in the washing process is usually about 5 to 40°C. Moreover, immersion time is about 1 to 120 seconds normally.
於水洗後實施乾燥處理而獲得偏光元件。乾燥處理例如可使用熱風乾燥機或遠紅外線加熱器進行。乾燥處理之溫度通常為30～100℃左右，較佳為50～80℃。乾燥處理之時間通常為60～600秒左右，較佳為120～600秒。藉由乾燥處理，偏光元件之水分率降低至實用程度。該水分率通常為5～20質量%左右，較佳為8～15質量%。若水分率低於5質量%，則有失去偏光元件之可撓性，偏光元件於其乾燥後損傷或破斷之情況。又，若水分率高於20質量%，則有偏光元件之熱穩定變差之可能性。After washing with water, drying treatment was performed to obtain a polarizing element. The drying treatment can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30-100°C, preferably 50-80°C. The drying time is usually about 60-600 seconds, preferably 120-600 seconds. By drying, the moisture content of the polarizer is reduced to a practical level. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is less than 5% by mass, the flexibility of the polarizing element may be lost, and the polarizing element may be damaged or broken after drying. Moreover, when the moisture content exceeds 20 mass %, there exists a possibility that the thermal stability of a polarizing element may deteriorate.
如此對聚乙烯醇系樹脂膜進行單軸延伸、利用二色性色素之染色、硼酸處理、水洗及乾燥而獲得之偏光元件之厚度較佳為5～40 μm。The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol-based resin film in this way, dyeing with a dichroic dye, treating with boric acid, washing with water, and drying is preferably 5 to 40 μm.
＜有機EL顯示裝置＞ 有機EL顯示裝置包含上述橢圓偏光板。作為有機EL顯示裝置之較佳之態樣，例如可列舉經由黏著劑將橢圓偏光板貼合於有機EL面板而成之裝置。 [實施例]＜Organic EL display device＞ An organic EL display device includes the above-mentioned elliptically polarizing plate. As a preferred aspect of the organic EL display device, for example, a device in which an elliptically polarizing plate is bonded to an organic EL panel via an adhesive is mentioned. [Example]
以下，藉由實施例對本發明更具體地進行說明。再者，例中之「%」及「份」只要無特別記載，則分別意指質量%及質量份。Hereinafter, the present invention will be described more specifically with reference to examples. In addition, "%" and "part" in an example mean % by mass and parts by mass, respectively, unless otherwise specified.
[液晶化合物之製備] 液晶化合物A係依據日本專利特開2010-31223號公報所記載之方法製造。又，液晶化合物B係依據日本專利特開2009-173893號公報所記載之方法製造。以下，分別表示液晶化合物A及液晶化合物B之分子結構。[Preparation of Liquid Crystal Compounds] Liquid crystal compound A is produced according to the method described in Japanese Patent Laid-Open No. 2010-31223. In addition, the liquid crystal compound B was produced according to the method described in JP-A-2009-173893. The molecular structures of liquid crystal compound A and liquid crystal compound B are shown below, respectively.
(液晶化合物A)
[化31]
(液晶化合物B)
[化32]
[測定方法] (極大吸收波長及最大吸光度之比之算出方法) 製備液晶化合物A之1 mg/50 mL四氫呋喃溶液，作為測定用試樣。將測定用試樣放入至光程長1 cm之測定用單元。將測定用試樣設置於紫外可見分光光度計(島津製作所股份有限公司製造之「UV-2450」)，測定吸收光譜。再者，對照係設為僅測定用試樣之溶劑。自獲得之吸收光譜讀取成為極大吸收度之波長，將其設為極大吸收波長λmax 。進而，自獲得之吸收光譜讀取波長260 nm以上400 nm以下之區域中之液晶化合物A之極大吸收波長。再者，於在波長260 nm以上400 nm以下之區域存在複數之極大吸收波長之情形時，將複數之極大吸收波長之中吸光度最高之波長設為λmax 。將獲得之極大吸收波長示於表1。[Measurement method] (Calculation method of ratio between maximum absorption wavelength and maximum absorbance) A 1 mg/50 mL tetrahydrofuran solution of liquid crystal compound A was prepared as a measurement sample. Put the sample for measurement into the cell for measurement with an optical path length of 1 cm. The measurement sample was set in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), and the absorption spectrum was measured. In addition, as a control, only the solvent of the measurement sample was used. The wavelength at which the maximum absorbance is obtained is read from the obtained absorption spectrum, and this is set as the maximum absorption wavelength λ max . Furthermore, the maximum absorption wavelength of the liquid crystal compound A in the region of wavelength 260 nm to 400 nm is read from the obtained absorption spectrum. Furthermore, when there are multiple maximum absorption wavelengths in the range of wavelengths from 260 nm to 400 nm, the wavelength with the highest absorbance among the multiple maximum absorption wavelengths is set to λ max . Table 1 shows the obtained maximum absorption wavelengths.
[離子性化合物之製備] 離子性化合物(1)係依據日本專利特願2016-514802號公報所記載之方法製造。又，離子性化合物(2)及離子性化合物(3)係依據日本專利特開2013-28586號公報或日本專利特開2013-199509號公報所記載之方法製造。以下，分別表示離子性化合物(1)～(3)之結構式。[Preparation of ionic compounds] The ionic compound (1) is manufactured according to the method described in Japanese Patent Application No. 2016-514802. In addition, the ionic compound (2) and the ionic compound (3) were produced according to the method described in JP-A-2013-28586 or JP-A-2013-199509. Structural formulas of ionic compounds (1) to (3) are shown below, respectively.
(離子性化合物(1))
[化33]
＜實施例1＞ [垂直配向液晶硬化膜形成用組合物(A-1)之製備] 以質量比90：10混合液晶化合物A及液晶化合物B，獲得混合物。相對於獲得之混合物100質量份，添加調平劑(DIC公司製造之「F-556」)1.5質量份、及作為光聚合起始劑之2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮(BASF Japan股份有限公司製造之「Irgacure(註冊商標)369(Irg369)」)6質量份。又，進而以成為0.5%之方式添加作為矽烷化合物之3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺(信越化學工業股份有限公司製造之「KBE-9103」)，以成為2.0%之方式添加離子性化合物(1)。<Example 1> [Preparation of vertically aligned liquid crystal cured film-forming composition (A-1)] Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 1.5 parts by mass of a leveling agent ("F-556" manufactured by DIC Corporation) and 2-dimethylamino-2-benzyl-1 as a photopolymerization initiator were added -6 parts by mass of (4-𠰌linylphenyl)butan-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.). Further, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine (manufactured by Shin-Etsu Chemical Co., Ltd. KBE-9103"), the ionic compound (1) was added so as to become 2.0%.
以固形物成分濃度成為13%之方式添加N-甲基-2-吡咯啶酮(NMP)。於80℃下攪拌1小時，藉此獲得垂直配向液晶硬化膜形成用組合物(A-1)(以下，有時記載為組合物(A-1))。再者，確認矽烷化合物(信越化學工業股份有限公司製造之「KBE-9103」)於組合物(A-1)中與溶劑或環境中之水分反應而進行水解，生成作為極性基之胺基。N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. It stirred at 80 degreeC for 1 hour, and obtained the composition (A-1) for vertical alignment liquid crystal cured film formation (it may describe hereafter as composition (A-1)). Furthermore, it was confirmed that the silane compound ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) reacts with the solvent or moisture in the environment in the composition (A-1) to undergo hydrolysis and generate an amine group as a polar group.
[垂直配向液晶硬化膜(A-1)之製作方法] 使用電暈處理裝置(春日電機股份有限公司製造之「AGF-B10」)對作為基材之非晶質環烯烴聚合物膜(COP膜)(Zeon corporation股份有限公司「ZF-14-23」)於輸出0.3 kW及處理速度3 m/分鐘之條件下實施1次電暈處理。使用棒式塗佈機於實施過電暈處理之基材之表面塗佈組合物(A-1)而形成塗佈膜。將塗佈膜於120℃下乾燥1分鐘而形成乾燥覆膜。繼而，使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」)，於氮氣氛圍下及波長365 nm下之累計光量500 mJ/cm2 之條件下，對乾燥覆膜照射紫外線。其結果，形成垂直配向液晶硬化膜(A-1)(膜厚：1.0 μm)。[Manufacturing method of vertically aligned liquid crystal cured film (A-1)] Using a corona treatment device ("AGF-B10" manufactured by Kasuga Electric Co., Ltd.) ) (Zeon Corporation Co., Ltd. "ZF-14-23") was subjected to corona treatment once under the conditions of an output of 0.3 kW and a treatment speed of 3 m/min. A coating film was formed by coating the composition (A-1) on the surface of the corona-treated substrate using a bar coater. The coating film was dried at 120° C. for 1 minute to form a dry coating film. Then, using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.), irradiate the dry film with ultraviolet rays under the conditions of a nitrogen atmosphere and a cumulative light intensity of 500 mJ/ cm2 at a wavelength of 365 nm. . As a result, a vertical alignment liquid crystal cured film (A-1) (film thickness: 1.0 μm) was formed.
[垂直配向液晶硬化膜(A-1)之光學特性] 將獲得之垂直配向液晶硬化膜(A-1)經由黏著劑(LINTEC公司製造之感壓式黏著劑 15 μm)與玻璃進行貼合，製作光學特性測定用樣品。[Optical properties of vertical alignment liquid crystal cured film (A-1)] The obtained vertically aligned liquid crystal cured film (A-1) was bonded to glass via an adhesive (pressure-sensitive adhesive manufactured by LINTEC Co., Ltd., 15 μm) to prepare a sample for measuring optical characteristics.
(相位差值之測定) 確認作為基材之ZF-14-23係波長550 nm下之相位差值RF (550)為1 nm以下之光學各向同性膜，對光學特性測定用樣品之測定值不產生影響。繼而，使用測定機(王子計測公司製造之「KOBRA-WPR」)，改變光對光學特性測定用樣品之入射角，測定相位差值。(Measurement of Retardation Value) ZF-14-23 is an optically isotropic film whose retardation value R F (550) at a wavelength of 550 nm is confirmed to be 1 nm or less as a base material, and is measured for a sample for measuring optical characteristics Value has no effect. Next, using a measuring machine ("KOBRA-WPR" manufactured by Oji Scientific Corporation), the incident angle of light on the sample for optical characteristic measurement was changed, and the retardation value was measured.
(平均折射率之測定) 波長λ＝450 nm及550 nm下之平均折射率係使用折射率計(Atago股份有限公司製造之「多波長阿貝折射計DR-M4」)進行測定。根據獲得之膜厚、平均折射率、及測定機(王子計測機器股份有限公司製造之「KOBRA-WPR」)之測定結果算出之Rth分別為Rth(450)＝-60 nm、Rth(550)＝-70 nm，Rth(450)/Rth(550)＝0.85。(Measurement of average refractive index) The average refractive index at wavelength λ = 450 nm and 550 nm was measured using a refractometer ("multi-wavelength Abbe refractometer DR-M4" manufactured by Atago Co., Ltd.). Rth calculated from the obtained film thickness, average refractive index, and the measurement results of the measuring machine ("KOBRA-WPR" manufactured by Oji Scientific Instruments Co., Ltd.) are Rth(450)=-60 nm, Rth(550)= -70 nm, Rth(450)/Rth(550)=0.85.
(配向液晶硬化膜之配向性評價) 使用偏光顯微鏡(Olympus股份有限公司製造之「BX-51」)，於倍率200倍之條件下進行觀察，對視野480 μm×320 μm下之配向缺陷數進行計數。此處，僅對起因於測定用樣品之配向缺陷數進行計數，起因於光學特性樣品以外之環境異物等之缺陷數被排除而不進行計數。根據利用偏光顯微鏡進行觀察之結果，基於以下之評價基準對垂直配向液晶硬化膜(A-1)之配向性進行評價。將A、B及C判斷為配向性優異。如表1所示，利用組合物(A-1)所製作之垂直配向液晶硬化膜(A-1)之配向性為A。 (評價基準) A(極為良好)：配向缺陷數為0個以上3個以下。 B(非常良好)：配向缺陷數為4個以上10個以下。 C(良好)：配向缺陷數為11個以上50個以下。 D(差)：配向缺陷數為51個以上或完全未配向。(Alignment Evaluation of Alignment Liquid Crystal Cured Film) Using a polarizing microscope ("BX-51" manufactured by Olympus Co., Ltd.), observation was performed at a magnification of 200 times, and the number of alignment defects in a field of view of 480 μm×320 μm was counted. Here, only the number of alignment defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign matter other than the optical characteristic sample was excluded and not counted. Based on the result of observation with a polarizing microscope, the orientation of the vertical alignment liquid crystal cured film (A-1) was evaluated based on the following evaluation criteria. A, B, and C were judged to be excellent in alignment. As shown in Table 1, the orientation of the vertical alignment liquid crystal cured film (A-1) produced by using the composition (A-1) is A. (evaluation criteria) A (extremely good): The number of alignment defects is 0 or more and 3 or less. B (very good): The number of alignment defects is 4 or more and 10 or less. C (good): The number of alignment defects is 11 or more and 50 or less. D (poor): The number of alignment defects is 51 or more or there is no alignment at all.
＜實施例2～9、實施例20、實施例21、及比較例1＞ 將實施例1之基材、矽烷化合物0.5%、及離子性化合物(2)2%變更為表1所記載之基材之種類、矽烷化合物之種類及添加量、以及離子性化合物之種類及添加量，除此以外，以與實施例1之組合物(A-1)之製備方法相同之方式分別製備實施例2～9及實施例20、實施例21、比較例1之組合物(A-2)～(A-9)、(A-20)、(A-21)、及(B-1)。將組合物(A-1)變更為組合物(A-2)～(A-9)、(A-20)、(A-21)、及(B-1)，進而變更塗佈膜之膜厚，以成為表1所示之相位差值之方式進行變更，除此以外，以與實施例1之垂直配向液晶硬化膜(A-1)之製作方法相同之方式，分別製作實施例2～9、實施例20、實施例21、及比較例1之垂直配向液晶硬化膜(A-2)～(A-9)、(A-20)、(A-21)、及(B-1)。又，以與實施例1相同之方法，製作光學特性測定用樣品，並評價相位差值、平均折射率及配向性。將結果示於表1。<Examples 2 to 9, Example 20, Example 21, and Comparative Example 1> Change the substrate, silane compound 0.5%, and ionic compound (2) 2% of Example 1 to the type of substrate, the type and amount of silane compound, and the type and addition of ionic compound as listed in Table 1. amount, except that, prepare the compositions (A- 2)～(A-9), (A-20), (A-21), and (B-1). Change the composition (A-1) to the composition (A-2) to (A-9), (A-20), (A-21), and (B-1), and then change the film of the coating film thickness, and change it so that the retardation value shown in Table 1 is obtained, except that, in the same manner as the production method of the vertically aligned liquid crystal cured film (A-1) of Example 1, Examples 2 to 3 were prepared respectively. 9. Vertically aligned liquid crystal cured films (A-2) to (A-9), (A-20), (A-21), and (B-1) of Example 20, Example 21, and Comparative Example 1 . Also, in the same manner as in Example 1, a sample for optical characteristic measurement was produced, and the retardation value, average refractive index, and alignment were evaluated. The results are shown in Table 1.
＜實施例10＞ 將基材自COP膜(Zeon corporation股份有限公司製造之「ZF-14-23」)變更為附保護層之聚對苯二甲酸乙二酯(以下，有時記載為附保護層之PET)，且於光學特性測定時剝離PET基材而製作樣品，除此以外，以與實施例1之垂直配向液晶硬化膜(A-1)之製備方法相同之方式，製備垂直配向液晶硬化膜(A-10)。又，以與實施例1相同之方法，製作光學特性測定用樣品，並評價相位差值、平均折射率及配向性。將結果示於表1。以下，對附保護層之PET之製備方法進行說明。<Example 10> The base material was changed from COP film ("ZF-14-23" manufactured by Zeon Corporation Co., Ltd.) to polyethylene terephthalate with a protective layer (hereinafter sometimes referred to as PET with a protective layer), And when measuring optical properties, the PET substrate was peeled off to make a sample. In addition, in the same manner as the preparation method of the vertical alignment liquid crystal cured film (A-1) of Example 1, a vertical alignment liquid crystal cured film (A-1) was prepared. 10). Also, in the same manner as in Example 1, a sample for optical characteristic measurement was produced, and the retardation value, average refractive index, and alignment were evaluated. The results are shown in Table 1. Hereinafter, a method for producing PET with a protective layer will be described.
[保護層形成用組合物之製備] 將二季戊四醇六丙烯酸酯(東亞合成股份有限公司製造之「ARONIX(註冊商標)M-403」多官能丙烯酸酯)50份、丙烯酸酯樹脂(Daicel - UCB股份有限公司製造之「Ebecryl 4858」)50份、及2-甲基-1[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮(Ciba Specialty Chemicals公司製造之「Irgacure(註冊商標)907」)3份溶解於異丙醇250份中，製備溶液。將獲得之溶液設為保護層形成用組合物。[Preparation of protective layer forming composition] 50 parts of dipentaerythritol hexaacrylate ("ARONIX (registered trademark) M-403" multifunctional acrylate manufactured by Toa Gosei Co., Ltd.), 50 parts of acrylate resin ("Ebecryl 4858" manufactured by Daicel-UCB Co., Ltd.) and 3 parts of 2-methyl-1[4-(methylthio)phenyl]-2-?olinylpropan-1-one ("Irgacure (registered trademark) 907" manufactured by Ciba Specialty Chemicals Co., Ltd.) In 250 parts of isopropanol, a solution was prepared. The obtained solution was used as the composition for protective layer formation.
[附保護層之PET之製造] 使用棒式塗佈機，於PET膜(膜厚38 μm)上塗佈保護層形成用組合物而形成塗佈膜。將塗佈膜於50℃下乾燥1分鐘，形成乾燥覆膜。使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」)，於氮氣氛圍下及波長365 nm下之累計光量400 mJ/cm2 之條件下，對乾燥覆膜照射紫外線。其結果，形成包含丙烯酸系樹脂之附保護層之PET。再者，依據實施例1所記載之光學特性測定方法，經由黏著劑貼合於玻璃，剝離PET膜後，測定保護層於波長550 nm下之相位差值，結果為1 nm以下，確認為光學各向同性膜。又，利用橢偏計測定形成之保護層之膜厚，結果為2 μm。[Manufacture of PET with Protective Layer] Using a bar coater, the composition for forming a protective layer was applied on a PET film (38 μm in film thickness) to form a coating film. The coated film was dried at 50° C. for 1 minute to form a dry film. Using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.), irradiate the dried film with ultraviolet rays under the conditions of a nitrogen atmosphere and a cumulative light intensity of 400 mJ/ cm2 at a wavelength of 365 nm. As a result, PET with a protective layer comprising an acrylic resin was formed. Furthermore, according to the optical characteristic measurement method described in Example 1, after bonding the glass with an adhesive, peeling off the PET film, and measuring the retardation value of the protective layer at a wavelength of 550 nm, the result is less than 1 nm, which is confirmed to be optical. isotropic membrane. Also, the film thickness of the formed protective layer was measured with an ellipsometer and found to be 2 µm.
＜實施例11＞
將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B＝90%/10%變更為液晶化合物(A)-2 100%，除此以外，以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式，分別製作實施例11之組合物(A-11)及垂直配向液晶硬化膜(A-11)。液晶化合物(A)-2係參考日本專利特開2016-81035號公報而製備。液晶化合物(A)-2係由下述式(A)-2所表示。又，以與實施例1相同之方法，製作測定用樣品，並評價相位差值、平均折射率及配向性。進而，以與實施例1相同之方式亦算出液晶化合物(A)-2之極大吸收波長及最大吸光度之比。將結果示於表1。
[化36]
＜實施例12＞
將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B＝90%/10%變更為液晶化合物(A)-3 100%，除此以外，以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式，分別製作實施例12之組合物(A-12)及垂直配向液晶硬化膜(A-12)。液晶化合物(A)-3係參考國際專利公開2015/025793號公報進行製備。液晶化合物(A)-3係由下述式(A)-3所表示。又，利用與實施例1相同之方法，製作光學特性測定用樣品，並評價相位差值、平均折射率及配向性。進而，以與實施例1相同之方式亦算出液晶化合物(A)-3之極大吸收波長及最大吸光度之比。將結果示於表1。
[化37]
＜實施例13＞
將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B＝90%/10%變更為液晶化合物(A)-4 100%，除此以外，以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式，分別製作實施例11之組合物(A-13)及垂直配向液晶硬化膜(A-13)。液晶化合物(A)-4係參考日本專利特開2011-207765號公報進行製備。液晶化合物(A)-4係由下述式(A)-4所表示。又，以與實施例1相同之方法，製作光學特性測定用樣品，並評價相位差值、平均折射率及配向性。進而，以與實施例1相同之方式亦算出液晶化合物(A)-4之極大吸收波長及最大吸光度之比。將結果示於表1。
[化38]
＜實施例14＞
將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B＝90%/10%變更為液晶化合物(A)-5 100%，除此以外，以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式，分別製作實施例14之組合物(A-14)及垂直配向液晶硬化膜(A-14)。液晶化合物(A)-5係參考日本專利特開2010-31223號公報進行製備。液晶化合物(A)-5係由下述式(A)-5所表示。又，以與實施例1相同之方法，製作光學特性測定用樣品，並評價相位差值、平均折射率及配向性。進而，以與實施例1相同之方式亦算出液晶化合物(A)-5之極大吸收波長及最大吸光度之比。將結果示於表1。
[化39]
＜實施例15＞ 將實施例1之矽烷化合物自3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺(信越化學工業股份有限公司製造之「KBE-9103」)變更為3-縮水甘油氧基丙基三乙氧基矽烷(信越化學工業股份有限公司製造之「KBE-403」)，除此以外，以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式，分別製作實施例15之組合物(A-15)及垂直配向液晶硬化膜(A-15)。又，以與實施例1相同之方法，製作光學特性測定用樣品，並評價相位差值、平均折射率及配向性。將結果示於表1。<Example 15> The silane compound in Example 1 was changed from 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) It is 3-glycidyloxypropyltriethoxysilane ("KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.), in addition to the composition (A-1) and vertical alignment of Example 1 Preparation method of liquid crystal cured film (A-1) In the same manner, the composition (A-15) of Example 15 and the vertically aligned liquid crystal cured film (A-15) were prepared respectively. Also, in the same manner as in Example 1, a sample for optical characteristic measurement was produced, and the retardation value, average refractive index, and alignment were evaluated. The results are shown in Table 1.
＜實施例16＞ [偏光膜A之製造] 將聚乙烯醇膜(平均聚合度約2,400、皂化度99.9莫耳%以上、厚度75 μm)浸漬於30℃之純水後，於30℃下浸漬於碘/碘化鉀/水之質量比為0.02/2/100之水溶液進行碘染色(碘染色步驟)。將經過碘染色步驟之聚乙烯醇膜於56.5℃下浸漬於碘化鉀/硼酸/水之質量比為12/5/100之水溶液進行硼酸處理(硼酸處理步驟)。將經過硼酸處理步驟之聚乙烯醇膜利用8℃之純水洗淨後，於65℃下乾燥，獲得碘吸附配向於聚乙烯醇而成之偏光元件(延伸後之厚度27 μm)。此時，於碘染色步驟與硼酸處理步驟中進行延伸。該延伸中之總延伸倍率為5.3倍。將獲得之偏光元件與經皂化處理之三乙醯纖維素膜(Konica Minolta製造之「KC4UYTAC」40 μm)經由水系接著劑利用夾輥進行貼合。將所獲得之貼合物之張力保持於430 N/m，並於60℃下乾燥2分鐘，獲得單面具有三乙醯纖維素膜作為保護膜之偏光膜A。再者，上述水系接著劑係於水100份中添加羧基改性聚乙烯醇(Kuraray製造之「Kuraray Poval KL318」)3份、及水溶性聚醯胺環氧樹脂(Sumika Chemtex製造之「Sumirez Resin 650」、固形物成分濃度30%之水溶液)1.5份而製備。<Example 16> [Manufacture of Polarizing Film A] After immersing polyvinyl alcohol film (average degree of polymerization about 2,400, degree of saponification over 99.9 mol%, thickness 75 μm) in pure water at 30°C, soak in iodine/potassium iodide/water at 30°C with a mass ratio of 0.02/ The aqueous solution of 2/100 was subjected to iodine staining (iodine staining step). The polyvinyl alcohol film after the iodine dyeing step was immersed in an aqueous solution with a mass ratio of potassium iodide/boric acid/water of 12/5/100 at 56.5° C. for boric acid treatment (boric acid treatment step). The polyvinyl alcohol film after the boric acid treatment step was washed with pure water at 8°C, and then dried at 65°C to obtain a polarizing element (thickness after stretching: 27 μm) in which iodine was adsorbed and aligned to the polyvinyl alcohol. At this time, extension is performed in the iodine staining step and the boric acid treatment step. The total extension ratio in this extension was 5.3 times. The obtained polarizing element and a saponified triacetyl cellulose film ("KC4UYTAC" 40 μm manufactured by Konica Minolta) were bonded together with a nip roller through a water-based adhesive. The tension of the obtained laminate was kept at 430 N/m, and dried at 60° C. for 2 minutes to obtain a polarizing film A having a triacetyl cellulose film as a protective film on one side. Furthermore, the above-mentioned water-based adhesive is 3 parts of carboxyl-modified polyvinyl alcohol (“Kuraray Poval KL318” manufactured by Kuraray) and water-soluble polyamide epoxy resin (“Sumirez Resin manufactured by Sumika Chemtex”) are added to 100 parts of water. 650", an aqueous solution with a solid content concentration of 30%) was prepared by 1.5 parts.
[偏光膜A之光學特性之測定] 對獲得之偏光膜A進行光學特性之測定。測定係將上述所獲得之偏光膜A之偏光元件面作為入射面，利用分光光度計(日本分光製造之「V7100」)實施。偏光膜之吸收軸與聚乙烯醇之延伸方向一致，所獲得之偏光膜之視感度補正單體透過率為42.1%，視感度補正偏光度為99.996%，單體色相a為-1.1、單體色相b為3.7。[Measurement of Optical Properties of Polarizing Film A] The optical characteristics of the obtained polarizing film A were measured. The measurement was implemented with a spectrophotometer ("V7100" manufactured by JASCO Corporation) using the polarizer surface of the polarizing film A obtained above as the incident surface. The absorption axis of the polarizing film is consistent with the extension direction of polyvinyl alcohol. The transmittance of the obtained polarizing film is 42.1%. Hue b is 3.7.
[水平配向膜形成用組合物之製備]
將下述結構之光配向性材料(重量平均分子量：30000)5份與作為溶劑之環戊酮95份混合，將獲得之混合物於80℃下攪拌1小時，藉此獲得水平配向膜形成用組合物。
[化40]
[水平配向液晶硬化膜A形成用組合物之製備] 以質量比90：10混合液晶化合物A及液晶化合物B，獲得混合物。相對於獲得之混合物100質量份，添加調平劑(DIC公司製造之「F-556」)1.0份、及作為聚合起始劑之2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮(BASF Japan股份有限公司製造之「Irgacure(註冊商標)369(Irg369)」)6份。又，以固形物成分濃度成為13%之方式添加N-甲基-2-吡咯啶酮(NMP)。於80℃下攪拌1小時，藉此獲得水平配向液晶硬化膜A形成用組合物。[Preparation of composition for forming horizontal alignment liquid crystal cured film A] Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 1.0 parts of a leveling agent ("F-556" manufactured by DIC Corporation) and 2-dimethylamino-2-benzyl-1-( 6 parts of 4-𠰌linylphenyl)butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Co., Ltd.). Moreover, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. By stirring at 80 degreeC for 1 hour, the composition for horizontal alignment liquid crystal cured film A formation was obtained.
[水平配向液晶硬化膜A之製造] 於COP膜(Zeon corporation股份有限公司製造之「ZF-14-50」)上實施電暈處理。其後，使用棒式塗佈機塗佈水平配向膜形成用組合物，形成塗佈膜。將塗佈膜於80℃下乾燥1分鐘，形成乾燥覆膜。使用偏光UV照射裝置(牛尾電機股份有限公司製造之「SPOT CURE SP-9」)，於波長313 nm下之累計光量100 mJ/cm2 及軸角度45°之條件下實施偏光UV曝光而獲得水平配向膜。利用橢偏計測定獲得之水平配向膜之膜厚，結果為100 nm。[Manufacture of Horizontal Alignment Liquid Crystal Cured Film A] A corona treatment was performed on a COP film ("ZF-14-50" manufactured by Zeon Corporation Co., Ltd.). Thereafter, the composition for forming a horizontal alignment film was applied using a bar coater to form a coated film. The coated film was dried at 80° C. for 1 minute to form a dry film. Using a polarized UV irradiation device ("SPOT CURE SP-9" manufactured by Ushio Electric Co., Ltd.), the polarized UV exposure was carried out under the conditions of a wavelength of 313 nm, an accumulated light amount of 100 mJ/cm 2 and an axial angle of 45° to obtain a level Alignment film. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer and found to be 100 nm.
繼而，使用棒式塗佈機，於水平配向膜塗佈水平配向液晶硬化膜A形成用組合物而形成塗佈膜。將塗佈膜於120℃下乾燥1分鐘，形成乾燥覆膜。使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」)，於氮氣氛圍下及波長365 nm下之累計光量500 mJ/cm2 之條件下，對乾燥覆膜照射紫外線，藉此形成水平配向液晶硬化膜A。獲得包含基材、水平配向膜及水平配向液晶硬化膜A之積層體。利用橢偏計測定水平配向液晶硬化膜A之膜厚，結果為2.3 μm。Then, the composition for forming a horizontal alignment liquid crystal cured film A was applied to the horizontal alignment film using a bar coater to form a coating film. The coated film was dried at 120° C. for 1 minute to form a dry film. Using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.), irradiate the dry film with ultraviolet rays under the conditions of a nitrogen atmosphere and a cumulative light intensity of 500 mJ/ cm2 at a wavelength of 365 nm. This forms the horizontal alignment liquid crystal cured film A. A laminate including a substrate, a horizontal alignment film, and a horizontal alignment liquid crystal cured film A was obtained. The film thickness of the horizontally aligned liquid crystal cured film A was measured with an ellipsometer and found to be 2.3 μm.
[水平配向液晶硬化膜A之Re測定] 將包含基材、水平配向膜及水平配向液晶硬化膜A之積層體經由黏著劑貼合於玻璃之後，剝離作為基材之COP膜。藉此，獲得Re測定用之水平配向液晶硬化膜A。使用測定機(王子計測機器股份有限公司製造之「KOBRA-WPR」)，測定水平配向液晶硬化膜A之面內相位差值ReA(λ)。測定各波長(450 nm、550 nm、及650 nm)下之相位差值ReA(λ)之結果為，ReA(450)＝121 nm、ReA(550)＝142 nm、ReA(650)＝146 nm、及ReA(450)/ReA(550)＝0.85。[Measurement of Re of Horizontal Alignment Liquid Crystal Cured Film A] After the laminate including the substrate, the horizontal alignment film and the horizontal alignment liquid crystal cured film A is bonded to the glass via an adhesive, the COP film as the substrate is peeled off. Thereby, the horizontal alignment liquid crystal cured film A for Re measurement was obtained. The in-plane retardation value ReA(λ) of the horizontal alignment liquid crystal cured film A was measured using a measuring machine (“KOBRA-WPR” manufactured by Oji Scientific Instruments Co., Ltd.). The results of measuring the phase difference ReA(λ) at each wavelength (450 nm, 550 nm, and 650 nm) are: ReA(450)=121 nm, ReA(550)=142 nm, ReA(650)=146 nm , and ReA(450)/ReA(550)=0.85.
[包含水平配向液晶硬化膜A與垂直配向液晶硬化膜之積層體之R0、及R40之測定] 將利用上述方法所製造之水平配向液晶硬化膜A、及利用實施例1之方法所製作之垂直配向液晶硬化膜(A-1)經由黏著劑(LINTEC公司製造之感壓式黏著劑 15 μm)貼合，製作包含水平配向液晶硬化膜A與垂直配向液晶硬化膜(A-1)之積層體。進而，自該積層體剝離1片用作基材之COP膜，經由黏著劑與玻璃貼合，獲得相位差值測定用之積層體。在確認COP膜及水平配向膜無相位差之基礎上，使用測定機(王子計測機器股份有限公司製造之「KOBRA-WPR」)測定相位差值測定用之積層體之正面方向之相位差值R0(λ)、及以水平配向液晶硬化膜A之進相軸為中心傾斜40°時之相位差值R40(λ)(λ＝450 nm及550 nm)。將測定結果示於表2。根據所獲得之R0(λ)及R40(λ)(λ＝450 nm及550 nm)之值，算出|R0(550)－R40(550)|、|R0(450)－R40(450)|、及|{R0(450)－R40(450)}－{R0(550)－R40(550)}|。將結果示於表3。[Measurement of R0 and R40 of the laminate including horizontal alignment liquid crystal cured film A and vertical alignment liquid crystal cured film] The horizontal alignment liquid crystal cured film A manufactured by the above method and the vertical alignment liquid crystal cured film (A-1) manufactured by the method of Example 1 were passed through an adhesive (pressure-sensitive adhesive manufactured by LINTEC, 15 μm) Paste together to make a laminate including the horizontal alignment liquid crystal cured film A and the vertical alignment liquid crystal cured film (A-1). Furthermore, one COP film used as a base material was peeled off from this laminated body, and it bonded to glass via an adhesive agent, and obtained the laminated body for retardation value measurement. After confirming that there is no phase difference between the COP film and the horizontal alignment film, use a measuring machine ("KOBRA-WPR" manufactured by Oji Scientific Instruments Co., Ltd.) to measure the phase difference R0 in the front direction of the laminate for phase difference measurement. (λ), and the retardation value R40(λ) (λ=450 nm and 550 nm) when the phase axis of the horizontally aligned liquid crystal cured film A is tilted by 40°. The measurement results are shown in Table 2. Calculate |R0(550)-R40(550)|, |R0(450)-R40(450)|, And |{R0(450)－R40(450)}－{R0(550)－R40(550)}|. The results are shown in Table 3.
[斜向反射色相之評價] 將利用上述方法所製作之積層體(包含水平配向液晶硬化膜A與垂直配向液晶硬化膜(A-1)之積層體)與偏光膜A以偏光膜A之吸收軸與水平配向液晶硬化膜A之遲相軸所成之角度成為45°之方式經由黏著劑進行貼合，剝離基材，製作附光學補償功能之橢圓偏光板。其後，經由黏著劑貼合於鋁箔，自仰角45°、方位角0～360°方向利用目視觀察橢圓偏光板之斜向反射色相。根據利用目視觀察之結果，基於下述評價基準評價斜向反射色相。將結果示於表3。 (評價基準) A(良好)：利用目視確認到黑色。 B(差)：利用目視確認到明顯之著色。[Evaluation of oblique reflection hue] The laminate produced by the above method (a laminate comprising the horizontally aligned liquid crystal cured film A and the vertically aligned liquid crystal cured film (A-1)) and the polarizing film A is aligned with the absorption axis of the polarizing film A and the horizontally aligned liquid crystal cured film A The angle formed by the retardation axis is 45°, and the adhesive is used to bond, and the base material is peeled off to produce an elliptically polarizing plate with optical compensation function. Thereafter, it was bonded to aluminum foil via an adhesive, and the oblique reflection hue of the elliptical polarizer was visually observed from the direction of elevation angle 45° and azimuth angle 0-360°. From the result of visual observation, oblique reflection hue was evaluated based on the following evaluation criteria. The results are shown in Table 3. (evaluation criteria) A (good): Black was confirmed visually. B (poor): Conspicuous coloring was confirmed visually.
＜實施例17及18＞ 藉由變更垂直配向液晶硬化膜之膜厚，而如表2所記載般變更RthC(450)、及RthC(550)之值，除此以外，以與實施例16相同之方式實施相位差值測定、斜向反射色相確認。將結果示於表2及表3。<Examples 17 and 18> By changing the film thickness of the vertically aligned liquid crystal cured film, the values of RthC(450) and RthC(550) were changed as described in Table 2, except that the phase difference measurement was carried out in the same manner as in Example 16 , Oblique reflection hue confirmation. The results are shown in Table 2 and Table 3.
＜實施例19＞ 將偏光膜A變更為利用以下所示之方法所製作之包含朝水平方向配向之水平配向液晶硬化膜B與二色性色素之偏光膜B，除此以外，與實施例16同樣地實施相位差值之測定、及斜向反射色相之評價。將結果示於表2及表3。<Example 19> The polarizing film A was changed to a polarizing film B including a horizontally aligned liquid crystal cured film B and a dichroic dye produced by the method shown below, and the phase difference was implemented in the same manner as in Example 16. Determination of value, and evaluation of oblique reflection hue. The results are shown in Table 2 and Table 3.
[偏光膜B形成用組合物之製備]
混合下述之成分，於80℃下攪拌1小時，藉此獲得包含聚合性液晶化合物(B)與二色性色素之偏光膜B形成用組合物。二色性色素係使用日本專利特開2013-101328號公報之實施例所記載之偶氮系色素。作為聚合性液晶化合物(B)之式(1-6)及(1-7)所表示之聚合性液晶化合物係依據lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996)所記載之方法製造。
聚合性液晶化合物(B)：
[化41]
[偏光膜B之製造] (水平配向膜之製作) 於三乙醯纖維素膜(TAC)(Konica Minolta公司製造之「KC4UY」)上實施電暈處理。繼而，使用棒式塗佈機，於實施過電暈處理之TAC表面塗佈水平配向膜形成用組合物而形成塗佈膜。使塗佈膜於80℃下乾燥1分鐘，形成乾燥覆膜。使用偏光UV照射裝置(牛尾電機股份有限公司製造之「SPOT CURE SP-7」)，於累計光量100 mJ/cm2 及軸角度90°之條件下對乾燥覆膜實施偏光UV曝光而獲得水平配向膜。利用橢偏計對獲得之水平配向膜之膜厚進行測定，結果為150 nm。[Production of Polarizing Film B] (Production of Horizontal Alignment Film) A corona treatment was performed on a triacetyl cellulose film (TAC) ("KC4UY" manufactured by Konica Minolta). Next, the composition for forming a horizontal alignment film was coated on the corona-treated TAC surface using a bar coater to form a coating film. The coating film was dried at 80° C. for 1 minute to form a dry film. Using a polarized UV irradiation device ("SPOT CURE SP-7" manufactured by Ushio Electric Co., Ltd.), under the conditions of a cumulative light intensity of 100 mJ/cm 2 and an axial angle of 90°, polarized UV exposure was performed on the dry film to obtain horizontal alignment membrane. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer, and the result was 150 nm.
(水平配向液晶硬化膜B之製作) 進而，使用棒式塗佈機，將偏光膜B形成用組合物塗佈於水平配向膜而形成塗佈膜。其後，利用設定為120℃之乾燥烘箱使塗佈膜乾燥1分鐘。其結果，獲得聚合性液晶化合物(B)及二色性色素經配向之乾燥塗膜。將該乾燥塗膜自然冷卻至室溫(25℃)後，使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」)，於氮氣氛圍下、波長365 nm、及波長365 nm下之累計光量1000 mJ/cm2 之條件下照射紫外線，藉此使聚合性液晶化合物(B)聚合而製作具有包含二色性色素之水平配向液晶硬化膜B的偏光膜B。(Preparation of horizontal alignment liquid crystal cured film B) Furthermore, using the bar coater, the composition for polarizing film B formation was apply|coated to the horizontal alignment film, and the coating film was formed. Thereafter, the coating film was dried for 1 minute in a drying oven set at 120°C. As a result, a dry coating film in which the polymerizable liquid crystal compound (B) and the dichroic dye were aligned was obtained. After naturally cooling the dried coating film to room temperature (25°C), use a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) under a nitrogen atmosphere at a wavelength of 365 nm and a wavelength of 365 nm The polymerizable liquid crystal compound (B) was polymerized by irradiating ultraviolet light under the condition of the accumulated light amount of 1000 mJ/cm 2 to prepare a polarizing film B having a horizontally aligned liquid crystal cured film B containing a dichroic dye.
[偏光膜B之偏光度、及單體透過率之測定] 所獲得之偏光膜B之偏光度及單體透過率係以如下方式測定。使用於分光光度計(島津製作所股份有限公司製造之「UV-3150」)中放置有附偏光元件之支座的裝置，藉由雙光束法以2 nm步進於380～680 nm之波長範圍內測定透過軸方向之透過率(T1 )及吸收軸方向之透過率(T2 )。使用下述式(p)及(q)，算出各波長下之單體透過率及偏光度。進而，藉由日本工業標準JIS Z 8701之2度視野(C光源)進行視感度補正，算出視感度補正單體透過率(Ty)及視感度補正偏光度(Py)，結果單體透過率為42%，偏光度為97%，確認係作為偏光膜有用之值。 單體透過率(%)＝(T1 ＋T2 )/2 (p) 偏光度(%)＝{(T1 －T2 )/(T1 ＋T2 )}×100 (q)[Measurement of Degree of Polarization and Single Transmittance of Polarizing Film B] The degree of polarization and single transmittance of the obtained polarizing film B were measured as follows. Using a spectrophotometer ("UV-3150" manufactured by Shimadzu Corporation) with a holder with a polarizing element placed in the wavelength range of 380 to 680 nm in steps of 2 nm by the double-beam method The transmittance (T 1 ) in the direction of the transmission axis and the transmittance (T 2 ) in the direction of the absorption axis were measured. Using the following formulas (p) and (q), the single transmittance and degree of polarization at each wavelength were calculated. Furthermore, according to the Japanese Industrial Standard JIS Z 8701's 2-degree field of view (C light source), the sensitivity correction is performed, and the sensitivity correction single transmittance (Ty) and the light sensitivity correction polarization degree (Py) are calculated. The result is that the single transmittance 42%, and the degree of polarization is 97%, which is confirmed to be a value useful as a polarizing film. Single transmittance (%)=(T 1 +T 2 )/2 (p) Polarization degree (%)={(T 1 -T 2 )/(T 1 +T 2 )}×100 (q)
＜比較例2＞ 製作以下所示之垂直配向膜及垂直配向液晶硬化膜，除此以外，以與實施例16相同之方式製作樣品，實施相位差值之測定及斜向反射色相之評價。將結果示於表2及表3。＜Comparative example 2＞ Except for producing the vertical alignment film and the vertical alignment liquid crystal cured film shown below, samples were produced in the same manner as in Example 16, and the measurement of the retardation value and the evaluation of the oblique reflection hue were implemented. The results are shown in Table 2 and Table 3.
(垂直配向膜形成用組合物(B)之製作) 混合0.5%之聚醯亞胺(日產化學工業股份有限公司製造之「Sunever SE-610」)、72.3%之N-甲基-2-吡咯啶酮、18.1%之2-丁氧基乙醇、9.1%之乙基環己烷、及0.01%之DPHA(dipentaerythritol hexaacrylate，二季戊四醇六丙烯酸酯)(新中村化學製造)，製作垂直配向膜形成用組合物(B)。(Production of Vertical Alignment Film Forming Composition (B)) Mix 0.5% of polyimide ("Sunever SE-610" manufactured by Nissan Chemical Industry Co., Ltd.), 72.3% of N-methyl-2-pyrrolidone, 18.1% of 2-butoxyethanol, 9.1 % of ethylcyclohexane, and 0.01% of DPHA (dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate) (manufactured by Shin-Nakamura Chemical Co., Ltd.), to prepare a composition (B) for forming a vertical alignment film.
(垂直配向液晶硬化膜形成用組合物(B)之製備)
相對於下述式(LC242)所示之液晶化合物LC242：PaliocolorLC242(BASF公司 註冊商標)，添加調平劑(DIC公司製造之「F-556」)0.1份及聚合起始劑Irg369 3份，以固形物成分濃度成為13%之方式添加環戊酮，將該等混合而獲得垂直配向液晶硬化膜形成用組合物(B)。
液晶化合物LC242：PaliocolorLC242(BASF公司 註冊商標)
[化46]
(垂直配向液晶硬化膜之製作) 對作為基材之COP膜(Zeon corporation股份有限公司「ZF-14-23」)實施電暈處理。使用棒式塗佈機，於實施過電暈處理之COP膜使用棒式塗佈機，塗佈垂直配向膜形成用組合物(B)而形成塗佈膜。將塗佈膜於80℃下乾燥1分鐘，獲得垂直配向膜。利用橢偏計測定獲得之垂直配向膜之膜厚，結果為0.2 μm。繼而，於製作之垂直配向膜上塗佈垂直配向液晶硬化膜形成用組合物(B)而形成塗佈膜。將塗佈膜於80℃下乾燥1分鐘，形成乾燥覆膜。其後，使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」)於氮氣氛圍下、及波長365 nm下之累計光量500 mJ/cm2 之條件下對乾燥覆膜照射紫外線，形成垂直配向液晶硬化膜。獲得之垂直配向液晶硬化膜之膜厚為0.5 μm。(Production of Vertically Aligned Liquid Crystal Cured Film) Corona treatment was performed on a COP film (Zeon Corporation Co., Ltd. "ZF-14-23") as a base material. Using a bar coater, the composition (B) for forming a vertical alignment film was apply|coated on the corona-treated COP film using a bar coater, and the coating film was formed. The coated film was dried at 80° C. for 1 minute to obtain a vertical alignment film. The film thickness of the obtained vertical alignment film was measured by an ellipsometer and found to be 0.2 μm. Then, the composition (B) for forming a vertical alignment liquid crystal cured film was apply|coated on the produced vertical alignment film, and the coating film was formed. The coated film was dried at 80° C. for 1 minute to form a dry film. Thereafter, the dry film was irradiated with ultraviolet rays under a nitrogen atmosphere using a high-pressure mercury lamp (“UNICURE VB-15201BY-A” manufactured by Ushio Electric Co., Ltd.) under the conditions of a cumulative light intensity of 500 mJ/cm 2 at a wavelength of 365 nm. , forming a vertically aligned liquid crystal cured film. The film thickness of the obtained vertical alignment liquid crystal cured film was 0.5 μm.
表1中，矽烷化合物之「添加量」及離子性化合物之「添加量」一欄分別表示相對於垂直配向液晶硬化膜形成用組合物之添加量(單位：重量%)。液晶化合物之比一欄之數字及括弧內之字母表示添加之液晶化合物之添加量之比率。例如，90/10(A/B)表示質量比(液晶化合物A/液晶化合物B)90/10。In Table 1, the columns of the "addition amount" of the silane compound and the "addition amount" of the ionic compound represent the addition amount (unit: weight %) to the composition for vertical alignment liquid crystal cured film formation, respectively. The numbers in the column of the liquid crystal compound ratio and the letters in brackets indicate the ratio of the added amount of the liquid crystal compound to be added. For example, 90/10(A/B) means that the mass ratio (liquid crystal compound A/liquid crystal compound B) is 90/10.
[表1]
實施例1～15之組合物(A-1)～(A-15)含有液晶化合物A、(A)-2、(A)-3、(A)-4、及(A)-5中之至少1種、矽烷化合物KBE-9103或KBE-403、以及離子性化合物(1)～(3)中之任1種。液晶化合物A、(A)-2、(A)-3、(A)-4、及(A)-5係包含於式(I)-1所表示之液晶化合物中之液晶化合物。矽烷化合物KBE-9103及KBE-403係非離子性矽烷化合物。實施例1～15之垂直配向液晶硬化膜(A-1)～(A-15)之配向性評價為A及B之任一種。實施例20之組合物(A-20)包含液晶化合物A與離子性化合，實施例21之組合物(A-21)包含液晶化合物A與非離子性之矽烷性化合物。實施例(20)之垂直配向液晶硬化膜(A-20)、及實施例(21)之垂直配向液晶硬化膜(A-21)之配向性評價均為C。Compositions (A-1) to (A-15) of Examples 1 to 15 contain liquid crystal compounds A, (A)-2, (A)-3, (A)-4, and (A)-5 At least one kind, silane compound KBE-9103 or KBE-403, and any one of ionic compounds (1) to (3). Liquid crystal compounds A, (A)-2, (A)-3, (A)-4, and (A)-5 are liquid crystal compounds contained in liquid crystal compounds represented by formula (I)-1. Silane compounds KBE-9103 and KBE-403 are non-ionic silane compounds. The orientation evaluation of the vertically aligned liquid crystal cured films (A-1) to (A-15) of Examples 1 to 15 was any one of A and B. The composition (A-20) of Example 20 includes liquid crystal compound A and an ionic compound, and the composition (A-21) of Example 21 includes liquid crystal compound A and a nonionic silane compound. The orientation evaluations of the vertically aligned liquid crystal cured film (A-20) of Example (20) and the vertically aligned liquid crystal cured film (A-21) of Example (21) were both C.
比較例1之組合物(B-1)不含非離子性矽烷化合物及離子性化合物。比較例1之垂直配向液晶硬化膜(B-1)之配向性評價為D。The composition (B-1) of Comparative Example 1 does not contain a nonionic silane compound and an ionic compound. The orientation evaluation of the vertical alignment liquid crystal cured film (B-1) of Comparative Example 1 was D.
根據以上，可知實施例1～15之垂直配向液晶硬化膜(A-1)～(A-15)、(A-20)、及(A-21)與比較例1之配向液晶硬化膜(B-1)相比，配向性優異。可知實施例1～15、實施例20、及實施例21之組合物(A-1)～(A-15)、(A-20)、及(A-21)與比較例1之組合物(B-1)相比，能夠形成即便無垂直配向膜，配向性亦優異之垂直配向液晶硬化膜。Based on the above, it can be seen that the vertically aligned liquid crystal cured films (A-1) to (A-15), (A-20), and (A-21) of Examples 1 to 15 are different from the aligned liquid crystal cured film of Comparative Example 1 (B Compared with -1), the alignment property is excellent.
實施例16～19之橢圓偏光板包含使用組合物(A-1)所製作之垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜A、及偏光膜。實施例16～19之橢圓偏光板之斜向反射色相均為A。The elliptically polarizing plates of Examples 16-19 include a vertical alignment liquid crystal cured film, a horizontal alignment film, a horizontal alignment liquid crystal cured film A, and a polarizing film produced by using the composition (A-1). The oblique reflection hues of the elliptically polarizing plates of Examples 16-19 are all A.
比較例2之橢圓偏光板包含使用組合物(B-2)所製作之垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜A、及偏光膜。組合物(B-2)包含液晶化合物LC242。液晶化合物之Ar為具有1個環結構之2價基，不為包含於式(I)-1所表示之液晶化合物中之化合物。比較例2之橢圓偏光板之斜向反射色相為B。The elliptically polarizing plate of Comparative Example 2 includes a vertical alignment liquid crystal cured film, a horizontal alignment film, a horizontal alignment liquid crystal cured film A, and a polarizing film produced by using the composition (B-2). Composition (B-2) contains liquid crystal compound LC242. Ar of the liquid crystal compound is a divalent group having one ring structure, and is not included in the liquid crystal compound represented by formula (I)-1. The oblique reflection hue of the elliptically polarizing plate of Comparative Example 2 is B.
根據以上，可知實施例16～19之橢圓偏光板與比較例2之橢圓偏光板相比，斜向反射色相優異。From the above, it can be seen that the elliptically polarizing plates of Examples 16 to 19 are superior in oblique reflection hue compared to the elliptically polarizing plate of Comparative Example 2.
[表2]
[表3]
1‧‧‧基材
3‧‧‧水平配向膜
5‧‧‧水平配向液晶硬化膜A
7‧‧‧黏著層
9‧‧‧垂直配向液晶硬化膜
11‧‧‧偏光膜
13‧‧‧保護層
15‧‧‧積層體
20‧‧‧橢圓偏光板1‧‧‧
圖1係表示本發明之橢圓偏光板之層構成之一例的概略剖視圖。FIG. 1 is a schematic cross-sectional view showing an example of the layer configuration of an elliptically polarizing plate of the present invention.
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