TWI555826B - Polymerizable liquid crystal composition and alignment film - Google Patents

Polymerizable liquid crystal composition and alignment film Download PDF

Info

Publication number
TWI555826B
TWI555826B TW101133777A TW101133777A TWI555826B TW I555826 B TWI555826 B TW I555826B TW 101133777 A TW101133777 A TW 101133777A TW 101133777 A TW101133777 A TW 101133777A TW I555826 B TWI555826 B TW I555826B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
polymerizable liquid
compound
film
crystal composition
Prior art date
Application number
TW101133777A
Other languages
Chinese (zh)
Other versions
TW201326372A (en
Inventor
Daniel Antonio Sahade
Tadashi Hatanaka
Original Assignee
Nissan Chemical Ind Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Ind Ltd filed Critical Nissan Chemical Ind Ltd
Publication of TW201326372A publication Critical patent/TW201326372A/en
Application granted granted Critical
Publication of TWI555826B publication Critical patent/TWI555826B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polarising Elements (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

聚合性液晶組成物及配向膜 Polymeric liquid crystal composition and alignment film

本發明係有關一種聚合性液晶組成物、使用該物所得的聚合物、及配向膜。詳言之，係有關顯示裝置或具有記錄材料等之光學特性之材料，特別是適合利用於液晶顯示器用偏光板、相位差板等之光學補償膜之聚合性液晶組成物、使用該物所得的聚合物、及使用其所得的混合型配向薄膜。 The present invention relates to a polymerizable liquid crystal composition, a polymer obtained by using the same, and an alignment film. In particular, a display device or a material having optical characteristics such as a recording material, and a polymerizable liquid crystal composition suitable for use in an optical compensation film such as a polarizing plate for a liquid crystal display or a phase difference plate, and the like are used. A polymer, and a mixed alignment film obtained using the same.

為提高液晶顯示裝置之顯示品質或要求輕量化等時，提高對作為偏光板或相位差板等之光學補償薄膜的內部之分子配向構造被控制的高分子薄膜之要求。對應於該要求，開發利用聚合性液晶化合物具有的光學向異性之薄膜。 In order to improve the display quality of the liquid crystal display device or to reduce the weight of the liquid crystal display device, it is required to improve the molecular alignment structure in which the molecular alignment structure of the optical compensation film such as a polarizing plate or a retardation film is controlled. In response to this demand, a film utilizing optical anisotropy which is possessed by a polymerizable liquid crystal compound has been developed.

此處所使用的聚合性液晶化合物，一般而言具有聚合性基與液晶構造部位(具有間隔部與液晶質部之構造部位)的液晶化合物，廣泛使用丙烯基作為該聚合性基。 The polymerizable liquid crystal compound used herein generally has a polymerizable group and a liquid crystal compound (having a structure portion having a spacer portion and a liquid crystal portion), and a propylene group is widely used as the polymerizable group.

該聚合性液晶化合物，一般而言以照射紫外線等之放射線予以聚合的方法形成聚合物(薄膜)。 The polymerizable liquid crystal compound is generally formed into a polymer (thin film) by a method of polymerizing radiation such as ultraviolet rays.

例如已知有在支持體間載負具有丙烯基之特定的聚合性液晶化合物，且使該化合物保持於液晶狀態，照射放射線，製得聚合物之方法(專利文獻1)，或具有丙烯基之2種聚合性液晶化合物的混合物或在該混合物中混合有對掌 性液晶之組成物中添加光聚合引發劑，且照射紫外線，製得聚合物的方法(專利文獻2)。 For example, a method in which a specific polymerizable liquid crystal compound having a propenyl group is supported between a support, and the compound is maintained in a liquid crystal state, and radiation is irradiated to obtain a polymer (Patent Document 1) is known, or a propylene group is known. a mixture of two polymeric liquid crystal compounds or a mixture of the palms in the mixture A method of adding a photopolymerization initiator to a composition of a liquid crystal and irradiating ultraviolet rays to obtain a polymer (Patent Document 2).

藉由上述各方法所得的聚合物(薄膜)，作為偏光板或相位差板用薄膜等，不僅可搭載於顯示器或電視等之顯示裝置，且可搭載於如汽車內等之高溫環境中所使用的顯示裝置。因此，在高溫環境中維持透明性，於作為顯示裝置用材料時極為重要。 The polymer (film) obtained by the above-described methods can be used not only in a display device such as a display or a television, but also in a high-temperature environment such as an automobile, as a polarizing plate or a film for a phase difference plate. Display device. Therefore, maintaining transparency in a high-temperature environment is extremely important as a material for a display device.

然而，由聚合性液晶化合物所得的薄膜，其玻璃轉移溫度(以下稱為Tg)為使用環境之溫度以下時，特別是在高溫環境中，由於會產生分子之微視搖晃情形，導致配向混亂且光學向異性顯著降低的問題。 However, when the glass transition temperature (hereinafter referred to as Tg) of the film obtained from the polymerizable liquid crystal compound is below the temperature of the use environment, particularly in a high-temperature environment, the microscopic sway of the molecules may occur, resulting in disorder of alignment. The problem of significantly decreasing optical anisotropy.

另外，在顯示器之領域中，近年來積極進檢討此等材料作為In Cell相位差薄膜使用的製程簡單化。該In Cell技術中使用的材料，更為要求高的熱安定性及耐藥品性。 In addition, in the field of displays, in recent years, it has been actively reviewed to make these materials simple as a process for using In Cell retardation films. The materials used in the In Cell technology require higher thermal stability and chemical resistance.

此外，亦報告有視聚合性液晶化合物之配向型式不同而定，可得水平、垂直、混合配向等之各種配向薄膜，具有各種平均傾斜角度之混合型配向薄膜(專利文獻3)。 In addition, it has been reported that various alignment films such as horizontal, vertical, and mixed alignment can be obtained, and various types of alignment films having various average tilt angles can be obtained (Patent Document 3).

此處，不僅在液晶組成物中少量添加特定的化合物，且可簡單地控制所得薄膜之配向型式(例如水平、混合型)，可廣泛地應用於液晶顯示器領域。 Here, not only a specific compound is added in a small amount in the liquid crystal composition, but also an alignment pattern (for example, a horizontal type or a mixed type) of the obtained film can be simply controlled, and it can be widely applied to the field of liquid crystal displays.

而且，藉由使用一種材料來改變製程，可簡單地製作水平或混合型配向薄膜時，期待可廣泛地應用於液晶顯示器領域。 Further, when a horizontal or hybrid alignment film can be easily produced by using a material to change the process, it is expected to be widely used in the field of liquid crystal displays.

於專利文獻4中記載，可在使用具有丙烯基之聚合性 液晶性化合物的液晶組成物中添加不具液晶性之多官能性聚合性化合物(0~20%)。然而，添加多官能性聚合性化合物係為提高薄膜之耐熱性，沒有記載有關藉此可得控制配向型式之效果。 It is described in Patent Document 4 that polymerization having a propylene group can be used. A polyfunctional polymerizable compound (0 to 20%) having no liquid crystallinity is added to the liquid crystal composition of the liquid crystal compound. However, the addition of the polyfunctional polymerizable compound is to improve the heat resistance of the film, and there is no description about the effect of controlling the alignment pattern.

而且，報告有藉由組合垂直及水平配向薄膜用聚合性液晶化合物，可控制傾斜角度。其中，雖報告有可得控制O-平板薄膜之傾斜角度，惟沒有報告傾斜角度以外之數據(△nd、霧度值)(專利文獻3)。 Further, it has been reported that the tilt angle can be controlled by combining a polymerizable liquid crystal compound for a vertical and horizontal alignment film. Among them, although it is reported that the inclination angle of the O-plate film can be controlled, data other than the inclination angle (Δnd, haze value) is not reported (Patent Document 3).

[習知技術文獻] [Practical Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開昭62-70407號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 62-70407

[專利文獻2]日本特開平9-208957號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 9-208957

[專利文獻3]國際公開第2008/052376號 [Patent Document 3] International Publication No. 2008/052376

[專利文獻4]國際公開第98/04651號 [Patent Document 4] International Publication No. 98/04651

本發明係有鑑於該情形者，以提供一種具有優異的光學向異性，同時即使於高溫下仍可安定地保持阻滯值及透明性，提供耐藥品性及耐熱性優異的聚合物，以及容易控制配向型式之聚合性液晶組成物，使用該物所得的聚合物、及使用此等所得的混合型配向薄膜為目的。 The present invention has been made in view of the circumstances to provide a polymer which has excellent optical anisotropy and which can stably maintain a retardation value and transparency even at a high temperature, and which is excellent in chemical resistance and heat resistance, and is easy to provide. The polymerizable liquid crystal composition of the alignment type is controlled, and a polymer obtained by using the product and a mixed alignment film obtained by using the above are used.

本發明人等為解決上述課題時，再三深入研究檢討的結果，發現藉由在含有一種聚合性液晶化合物之水平配向 薄膜用聚合物液晶組成物中少量添加一種多價丙烯酸酯化合物，變得可容易控制配向型式。另外，可製得安定的聚合性液晶性組合物、由其聚合性液晶性組成物所得的聚合物或薄膜具有優異的光學向異性及耐熱性，以及可製得混合型配向薄膜，遂而完成本發明。 In order to solve the above problems, the present inventors have further studied the results of the review and found that the level is aligned by containing a polymerizable liquid crystal compound. A small amount of a polyvalent acrylate compound is added to the polymer liquid crystal composition for a film, and the alignment type can be easily controlled. Further, a stable polymerizable liquid crystal composition can be obtained, and a polymer or film obtained from the polymerizable liquid crystal composition can have excellent optical anisotropy and heat resistance, and a mixed alignment film can be obtained. this invention.

換言之，本發明係有關 In other words, the invention is related

1.一種聚合性液晶組成物，其特徵為含有(A)選自以下述式[1]表示之聚合性液晶化合物中之至少1種、(B)選自以下述式[2]表示的聚合性液晶化合物中之至少1種，及(C)選自由具有選自三羥甲基丙烷構造、季戊四醇構造及乙二醇構造中之至少一種的構造或選自此等中之至少1種予以縮合的構造、全體具有3個以上50個以下之氧原子的多元醇與丙烯酸或其衍生物所得的多元丙烯酸酯化合物中之至少1種， [式中，R1、R3及R4係各獨立為以下述式[3]或[4]表示的 有機基， (式中，X係表示氫原子或甲基；虛線係鍵結鍵) 1. A polymerizable liquid crystal composition comprising (A) at least one selected from the group consisting of polymerizable liquid crystal compounds represented by the following formula [1], and (B) selected from the group consisting of the polymerization represented by the following formula [2] At least one of the liquid crystal compounds, and (C) is selected from the group consisting of at least one selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or at least one selected from the group consisting of At least one of a polyol having three or more oxygen atoms and 50 or less polyacrylate compounds obtained by using acrylic acid or a derivative thereof, [wherein R 1 , R 3 and R 4 are each independently an organic group represented by the following formula [3] or [4], (wherein X is a hydrogen atom or a methyl group; a dotted line is a bonding bond)

R2係表示氫原子、鹵素原子、氰基或甲氧基；n1、n2及n3係各獨立表示2~10之整數；q係表示0或1；p係q為0時為1，q為1時為0或1；r係表示1或2；s係r為1時為1，r為2時為0]。 R 2 represents a hydrogen atom, a halogen atom, a cyano group or a methoxy group; n1, n2 and n3 each independently represent an integer of 2 to 10; q represents 0 or 1; and when p is q, it is 1, q is 1 is 0 or 1; r is 1 or 2; s is 1 when r is 1, and 0 when r is 2.

2.1記載之聚合性液晶組成物，其中上述多元丙烯酸酯化合物(C)係以下述式[5]或[6]表示， (式中，R5係表示甲基、或以下述式[7]或[8]表示的有機基， n4~n10係各獨立為0~10之整數；n11係4~10之整數；虛線係鍵結鍵)。 The polymerizable liquid crystal composition according to the item 2.1, wherein the polybasic acrylate compound (C) is represented by the following formula [5] or [6]. (wherein R 5 represents a methyl group or an organic group represented by the following formula [7] or [8], N4~n10 are each an integer of 0~10; n11 is an integer of 4~10; the dotted line is a key bond).

3. 1或2記載之聚合性液晶組成物，其中前述聚合性液晶化合物(B)係以下述式[9]表示， (式中，n2、n3、r及s係與上述相同)。 3. The polymerizable liquid crystal composition according to 1 or 2, wherein the polymerizable liquid crystal compound (B) is represented by the following formula [9]. (wherein n2, n3, r and s are the same as described above).

4.一種由1~3中任一項之聚合性液晶組成物所得的聚合物。 4. A polymer obtained from the polymerizable liquid crystal composition according to any one of 1 to 3.

5.一種由1~3中任一項之聚合性液晶組成物所得的被膜。 A film obtained from the polymerizable liquid crystal composition according to any one of 1 to 3.

6.一種由1~3中任一項之聚合性液晶組成物所得的混合型配向薄膜。 A mixed alignment film obtained from the polymerizable liquid crystal composition according to any one of 1 to 3.

7.一種具備6之配向薄膜的光學構件。 7. An optical member comprising an alignment film of 6.

本發明之聚合性液晶組成物，不僅具有優異的光學向異性，且可提供即使於高溫環境中向異性及透明性安定的聚合物。而且，本發明之聚合性液晶組成物藉由含有少量的多價丙烯酸酯化合物(C)，具有可簡單地控制由此所得的薄膜之配向型式(水平、混合型)的優點。 The polymerizable liquid crystal composition of the present invention not only has excellent optical anisotropy, but also provides a polymer which is stable to anisotropy and transparency even in a high-temperature environment. Further, the polymerizable liquid crystal composition of the present invention has an advantage of being able to easily control the alignment type (horizontal, mixed type) of the film thus obtained by containing a small amount of the polyvalent acrylate compound (C).

此外，由本發明之組成物所得的聚合物，可適合利用作為偏光板或相位差板等之光學向異性薄膜。 Further, the polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film which is a polarizing plate or a phase difference plate.

[為實施發明之形態] [In order to implement the invention]

本說明書中使用的用語如下所述。 The terms used in this specification are as follows.

[聚合性液晶化合物]係指在分子中具有丙烯基、α-亞甲基-γ-丁內酯環等之可聚合部位與液晶構造部位，且呈現液晶相之化合物。一般而言，該「液晶構造」係指表示液晶分子時所使用的具有間隔部與液晶質(mesogen)部之構造。「液晶組成物」係指具有呈現液晶相之特性的組成物。「液晶性」係指呈現液晶相。 [Polymerizable liquid crystal compound] A compound having a polymerizable portion such as an acryl group or an α-methylene-γ-butyrolactone ring in a molecule and a liquid crystal structure portion, and exhibiting a liquid crystal phase. In general, the term "liquid crystal structure" means a structure having a spacer portion and a mesogen portion used when liquid crystal molecules are used. The "liquid crystal composition" means a composition having characteristics exhibiting a liquid crystal phase. "Liquid crystallinity" means a liquid crystal phase.

本發明所使用的聚合性液晶化合物(A)及(B)，係具有液晶構造部位，以及具有丙烯基及α-亞甲基-γ-丁內酯環構造中之任一種或兩種。 The polymerizable liquid crystal compounds (A) and (B) used in the present invention have a liquid crystal structure site and have either or both of an acryl group and an α-methylene-γ-butyrolactone ring structure.

α-亞甲基-γ-丁內酯可發揮即使於具有聚合性基之α-伸烷基-γ-丁內酯中，受到立體阻礙之影響少，具有高聚 合性之極為優異的效果。因此，為賦予使用該化合物所得的聚合物具有高Tg或耐熱性時極為有效。 Α-methylene-γ-butyrolactone exhibits little influence on steric hindrance even in α-alkyl-γ-butyrolactone having a polymerizable group, and has high aggregation. Extremely excellent results. Therefore, it is extremely effective in imparting high Tg or heat resistance to the polymer obtained by using the compound.

[聚合性液晶化合物(A)] [Polymerizable liquid crystal compound (A)]

本發明所使用的聚合性液晶化合物(A)，係以下述式[1]表示。 The polymerizable liquid crystal compound (A) used in the present invention is represented by the following formula [1].

式[1]中，R1係以下述式[3]或[4]所表示之有機基。 In the formula [1], R 1 is an organic group represented by the following formula [3] or [4].

(式中，X係表示氫原子或甲基。虛線為鍵結鍵。) (wherein X represents a hydrogen atom or a methyl group. The dotted line is a bonding bond.)

式[1]中，R2係表示氫原子、鹵素原子、氰基或甲氧基。上述鹵素原子特別是以氟原子較佳。R2以氫原子、甲氧基或氰基較佳，以氫原子或氰基更佳。 In the formula [1], R 2 represents a hydrogen atom, a halogen atom, a cyano group or a methoxy group. The above halogen atom is particularly preferably a fluorine atom. R 2 is preferably a hydrogen atom, a methoxy group or a cyano group, and more preferably a hydrogen atom or a cyano group.

亞甲基之重複部位，即稱為間隔部之部位。n1係表示亞甲基之重複數，各為獨立的2~10之整數，以3~6之整數較佳。 The repeating part of the methylene group is called the part of the spacer. The n1 system represents a repeating number of methylene groups, each of which is an independent integer of 2 to 10, and preferably an integer of 3 to 6.

q為0或1。p於q為0時為1，q為1時為0或1。 q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1.

聚合性液晶化合物(A)，係表示碟狀相或向列相之液晶相。該特性於利用偏光板或相位差板等之光學向異性之用途領域中有用。 The polymerizable liquid crystal compound (A) is a liquid crystal phase which represents a dish phase or a nematic phase. This characteristic is useful in the field of use of optical anisotropy such as a polarizing plate or a phase difference plate.

聚合性液晶化合物(A)之具體例，例如可以下述式(1)~(25)表示之化合物，惟不受此等所限制。而且，式中Me係表示甲基。 Specific examples of the polymerizable liquid crystal compound (A) include, for example, the compounds represented by the following formulas (1) to (25), but are not limited thereto. Further, in the formula, Me represents a methyl group.

[聚合性液晶化合物(B)] [Polymerizable liquid crystal compound (B)]

本發明所使用的聚合性液晶化合物(B)，係以下述式[2]表示。 The polymerizable liquid crystal compound (B) used in the present invention is represented by the following formula [2].

於式[2]中，R3及R4係與上述R1同義，可互相相同或不同。n2及n3係表示亞甲基之重複數，各獨立為2~10之整數，較佳者為3~6之整數。r為1或2。s於r為 1時為1，r為2時為0。 In the formula [2], R 3 and R 4 are synonymous with the above R 1 and may be the same or different from each other. N2 and n3 represent the number of repetitions of methylene groups, each independently being an integer of 2 to 10, preferably an integer of 3 to 6. r is 1 or 2. s is 1 when r is 1, and 0 when r is 2.

於式[2]中，R3及R4中至少一個以式[3]表示之有機基較佳。聚合性液晶化合物(B)以下述式[9]所示者更佳。 In the formula [2], at least one of R 3 and R 4 is preferably an organic group represented by the formula [3]. The polymerizable liquid crystal compound (B) is more preferably those represented by the following formula [9].

(式中，n2、n3、r及s係與上述相同) (where n2, n3, r, and s are the same as above)

聚合性液晶化合物(B)之具體例，如以下述式(26)~(116)所示之化合物，惟不受此等所限制。 Specific examples of the polymerizable liquid crystal compound (B) are compounds represented by the following formulas (26) to (116), but are not limited thereto.

[多價丙烯酸酯化合物(C)] [Multivalent acrylate compound (C)]

本發明所使用的多價丙烯酸酯化合物(C)，係由具有選自三羥甲基丙烷構造、季戊四醇構造及乙二醇構造中至少1種之構造或選自此等之至少1種經縮合的構造、全體具有3以上50以下之氧原子的多價醇與丙烯酸或其衍生物所得的多價丙烯酸酯化合物。 The polyvalent acrylate compound (C) used in the present invention is condensed by having at least one structure selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or at least one selected from the group consisting of The structure is a polyvalent acrylate compound obtained by a polyvalent alcohol having an oxygen atom of 3 or more and 50 or less, and acrylic acid or a derivative thereof.

其具體例如以下述式[5]或[6]所示者等。 Specifically, for example, it is represented by the following formula [5] or [6].

(式中，R5係甲基或以下述式[7]或[8]所示之有機基。 (wherein R 5 is a methyl group or an organic group represented by the following formula [7] or [8].

n4~n10係各獨立為0~10之整數。n11係4~10之整數。虛線為鍵結鍵。) The n4~n10 series are each an integer of 0~10. N11 is an integer from 4 to 10. The dotted line is the bond key. )

多價丙烯酸酯化合物(C)之具體例，如以下述式(117)~(127)所示之化合物，惟不受此等所限制。 Specific examples of the polyvalent acrylate compound (C) are, for example, compounds represented by the following formulas (117) to (127), but are not limited thereto.

多價丙烯酸酯化合物(C)可使用市售品，例如日本化藥(股)製KAYARAD DPHA、PET30、新中村化學工業(股)製ATM-35E、ADPH等。 As the polyvalent acrylate compound (C), a commercially available product such as KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., PET30, ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., ADPH, or the like can be used.

[聚合性液晶組成物] [Polymerized liquid crystal composition]

本發明之聚合性液晶組成物，係含有至少1種聚合性液晶化合物(A)、至少1種聚合性液晶化合物(B)、及至少1種多價丙烯酸酯化合物(C)。而且，多價丙烯酸酯化合物(C)以上述式[5]或[6]所示之化合物較佳。 The polymerizable liquid crystal composition of the present invention contains at least one polymerizable liquid crystal compound (A), at least one polymerizable liquid crystal compound (B), and at least one polyvalent acrylate compound (C). Further, the polyvalent acrylate compound (C) is preferably a compound represented by the above formula [5] or [6].

聚合性液晶化合物(A)之含量，相對於聚合性液晶化合物(B)100質量分而言為100~1,900質量分，較佳者為400~900質量分。多價丙烯酸酯化合物(C)之含量，相對於聚合性液晶化合物(A)及(B)質量分之合計量(以下兩者合併，稱為合計液晶性化合物)100質量分而言以0.5~5質量分較佳，以1~3質量分更佳。 The content of the polymerizable liquid crystal compound (A) is from 100 to 1,900 parts by mass, preferably from 400 to 900 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound (B). The content of the polyvalent acrylate compound (C) is 0.5 to 100 parts by mass based on the total mass of the polymerizable liquid crystal compounds (A) and (B) (the combination of the two is referred to as a total of the liquid crystal compound). 5 mass points are better, preferably 1 to 3 mass points.

於本發明之聚合性液晶組成物中，以提高其聚合反應性為目的時，亦可添加光聚合引發劑、熱聚合引發劑、光增感劑。 In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator, and a photosensitizer may be added for the purpose of improving the polymerization reactivity.

上述光聚合引發劑例如苯偶因甲醚等之苯偶因醚類、二乙氧基苯乙酮等之苯乙酮類、苯甲基二甲基縮酮等之苯甲基縮酮等。該光聚合引發劑可使用單獨1種或複數種組合使用。上述光聚合引發劑之添加量，相對於合計液晶化合物100質量分而言以5質量分以下較佳，更佳者為0.5~2.0質量分。 The photopolymerization initiator is, for example, a benzoin ether such as benzoin methyl ether, an acetophenone such as diethoxyacetophenone, or a benzyl ketal such as benzyldimethylketal. The photopolymerization initiator may be used singly or in combination of two or more. The amount of the photopolymerization initiator to be added is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass, based on 100 parts by mass of the total of the liquid crystal compound.

上述光聚合引發劑例如2,2’-偶氮雙異丁腈等。熱聚合引發劑可單獨1種使用或複數種組合使用。其添加量相對於合計液晶化合物100質量分而言以5質量分以下較佳，更佳者為0.5~2.0質量分。 The photopolymerization initiator is, for example, 2,2'-azobisisobutyronitrile or the like. The thermal polymerization initiator may be used singly or in combination of plural kinds. The amount of addition is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass, based on 100 parts by mass of the total of the liquid crystal compound.

光增感劑例如蒽等之蒽系光增感劑。光增感劑可單獨1種使用或複數種組合使用。其添加量相對於合計液晶化合物100質量分而言以5質量分以下較佳。 A photosensitizer such as a ruthenium-based photo sensitizer. The photosensitizer may be used alone or in combination of plural kinds. The amount of addition is preferably 5 parts by mass or less based on 100 parts by mass of the total of the liquid crystal compound.

而且，上述之光聚合引發劑可組合熱聚合引發劑及光增感劑中之至少1種使用。 Further, the photopolymerization initiator described above may be used in combination of at least one of a thermal polymerization initiator and a photosensitizer.

於本發明之聚合性液晶組成物中，以提高其保存安定性為目的時，亦可添加安定劑。上述安定劑例如氫醌、氫醌單甲醚等之氫醌單烷醚類、4-t-丁基兒茶酚等。安定劑可單獨1種使用或複數種組合使用。其添加量相對於合計液晶化合物100質量分而言以0.1質量分以下較佳。 In the polymerizable liquid crystal composition of the present invention, a stabilizer may be added for the purpose of improving the storage stability. The stabilizer is, for example, hydroquinone monoalkyl ether such as hydroquinone or hydroquinone monomethyl ether, or 4-t-butylcatechol. The stabilizer can be used alone or in combination of plural kinds. The amount of addition is preferably 0.1 parts by mass or less based on 100 parts by mass of the total of the liquid crystal compound.

此外，於本發明之聚合性液晶組成物中，以提高與基板之密接性為目的時，亦可添加密接促進劑。密接促進劑例如三甲基氯矽烷、二甲基乙烯基氯矽烷、甲基二苯基氯矽烷、氯甲基二甲基氯矽烷、乙烯基三氯矽烷等之氯矽烷類；三甲基甲氧基矽烷、二甲基二乙氧基矽烷、甲基二甲氧基矽烷、二甲基乙烯基乙氧基矽烷、二苯基二甲氧基矽烷、苯基三乙氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-甲基丙烯氧基丙基三甲氧基矽烷、γ-甘胺醯氧基丙基三甲氧基矽烷、γ-(N-哌啶基)丙基三甲氧基矽烷等之烷氧基矽烷類；六甲基二矽胺烷、N,N’-雙 (三甲基甲矽烷基)尿素、二甲基三甲基甲矽烷胺、N-三甲基甲矽烷基咪唑等之矽胺烷類；苯并***、苯并咪唑、吲唑、咪唑、2-巰基苯并咪唑、2-巰基苯并噻唑、2-巰基噁唑、脲唑、硫脲嘧啶、巰基咪唑、巰基嘧啶等之雜環狀化合物；1,1-二甲基尿素、1,3-二甲基尿素等之尿素化合物；硫尿素化合物等。 Further, in the polymerizable liquid crystal composition of the present invention, in order to improve the adhesion to the substrate, an adhesion promoter may be added. a adhesion promoter such as trimethylchloromethane, dimethylvinylchlorodecane, methyldiphenylchlorodecane, chloromethyldimethylchlorodecane, vinyltrichloromethane or the like; chlorodecane; Oxy decane, dimethyl diethoxy decane, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, diphenyl dimethoxy decane, phenyl triethoxy decane, γ- Chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropoxypropyltrimethoxydecane, γ-glycine methoxypropyltrimethoxydecane, γ- Alkoxydecanes such as (N-piperidinyl)propyltrimethoxydecane; hexamethyldioxane, N,N'-double Amidoxime such as (trimethylmethylalkyl) urea, dimethyltrimethylformamidine, N-trimethylformamimidazole, benzotriazole, benzimidazole, carbazole, imidazole, a heterocyclic compound such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptooxazole, ureazazole, thiouracil, mercapthylimid, pyridylpyrimidine, etc.; 1,1-dimethylurea, 1, a urea compound such as 3-dimethylurea; a sulfur urea compound or the like.

密接促進劑可單獨1種使用或複數組合種使用。其添加量相對於合計液晶性化合物100質量分而言以1質量分以下較佳。 The adhesion promoter may be used alone or in combination of plural kinds. The amount of addition is preferably 1 part by mass or less based on 100 parts by mass of the total liquid crystal compound.

此外，於本發明之聚合性液晶組成物中，以調整黏度等為目的時亦可添加有機溶劑。此時，含有有機溶劑之狀態亦可沒有呈現液晶性。 Further, in the polymerizable liquid crystal composition of the present invention, an organic solvent may be added for the purpose of adjusting the viscosity and the like. At this time, the state containing an organic solvent may not exhibit liquid crystallinity.

有機溶劑例如四氫呋喃、二噁烷等之醚類、苯、甲苯、二甲苯等之芳香族烴類；N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮等之極性溶劑；醋酸乙酯、醋酸丁酯、乳酸乙酯等之酯類；3-甲氧基丙酸甲酯、2-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、2-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、2-乙氧基丙酸乙酯等之烷氧酯類；乙二醇二甲醚、丙二醇二甲醚等之二醇二烷醚類；二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二丙二醇二甲醚等之二烷二醇二烷醚類；乙二醇單甲醚、乙二醇單***、丙二醇單甲醚、丙二醇單***等之乙二醇單烷醚類；二乙二醇單甲醚、二乙二醇單***、二丙二醇單甲醚、二丙二醇單***等之二乙二醇單烷醚類；丙二醇單甲醚乙酸酯、卡 必醇乙酸酯、乙基溶纖劑乙酸酯等之乙二醇單烷醚酯類；環己酮、甲基乙酮、甲基異丁酮、2-庚酮等之酮類等。於此等之中，就地球環境、作業環境之安全性而言，以丙二醇單甲醚、丙二醇單甲醚乙酸酯、乳酸乙酯等較佳。 An organic solvent such as an ether such as tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene or xylene; or a polar solvent such as N,N-dimethylformamide or N-methyl-2-pyrrolidone; Esters of ethyl acetate, butyl acetate, ethyl lactate, etc.; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, 2-methoxy Alkoxylates such as ethyl propyl propionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene Ethylene glycol monoalkyl ethers such as alcohol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. Ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether acetate, card Ethylene glycol monoalkyl ether esters such as alcohol alcohol acetate and ethyl cellosolve acetate; ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, etc. are preferable in terms of the safety of the earth environment and the working environment.

此等之有機溶劑，可單獨1種使用或複數種組合使用。有機溶劑之使用量，於聚合性液晶組成物中以約60~95質量%為宜。 These organic solvents may be used alone or in combination of plural kinds. The amount of the organic solvent to be used is preferably from about 60 to 95% by mass in the polymerizable liquid crystal composition.

此外，於本發明之聚合性液晶組成物中，以提高與基板之親和性為目的時，亦可添加界面活性劑。界面活性劑沒有特別的限制，例如氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等，惟以改善與基板之親和性的效果高的氟系界面活性劑較佳。 Further, in the polymerizable liquid crystal composition of the present invention, a surfactant may be added for the purpose of improving the affinity with the substrate. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. However, a fluorine-based surfactant having a high effect of improving affinity with a substrate is preferred. .

氟系界面活性劑之具體例，如(以下為商品名)、EFTOP EF301、EF303、EF352((股)Shin-Akita Kasei製)、Megafac F171、F173、R-30(DIC(股製))、Fluorad FC430、FC431(Sumitomo 3M(股)製)、ASAHI GUARD AG710、SAFLONS-382、SC101、SC102，SC103、SC104、SC105、SC106(旭硝子(股)製)等，惟不受此等所限制。而且，界面活性劑可單獨1種使用或複數種組合使用。 Specific examples of the fluorine-based surfactant are, for example, the following (trade name), EFTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F173, R-30 (DIC (shareholding)), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), ASAHI GUARD AG710, SAFLONS-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc., are not limited by these. Further, the surfactant may be used singly or in combination of plural kinds.

本發明之聚合性液晶組成物之適合例，如由聚合性液晶化合物(A)相對於聚合性液晶化合物(B)100質量分而言為400質量分~900質量分，多價丙烯酸酯化合物(C)相對於聚合性液晶化合物(A)及(B)之合計量100質量分而言 為1~3質量分，以及光引發劑相對於聚合性液晶化合物(A)及(B)之合計量100質量分而言為5質量分以下所形成者等，惟不受此等所限制。 A suitable example of the polymerizable liquid crystal composition of the present invention is a polyvalent acrylate compound (400 parts by mass to 900 parts by mass) based on 100 parts by mass of the polymerizable liquid crystal compound (A) with respect to the polymerizable liquid crystal compound (B). C) in terms of 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) The amount of the photoinitiator to be formed in an amount of 5 parts by mass or less based on 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) is not limited thereto.

本發明之聚合性液晶組成物的調製方法，沒有特別的限制，可一次性混合構成聚合性液晶組成物之各成分，亦可順序混合。於順序混合時，各成分之添加順序可為任意。 The method for preparing the polymerizable liquid crystal composition of the present invention is not particularly limited, and the components constituting the polymerizable liquid crystal composition may be mixed at once, or may be sequentially mixed. When sequentially mixed, the order of addition of each component may be arbitrary.

而且，1種成分中使用複數種化合物時，可預先混合此等混合物與其他的成分，亦可個別與其他成分混合。 Further, when a plurality of compounds are used in one component, the components and other components may be mixed in advance, or may be separately mixed with other components.

本發明之聚合性液晶組成物，係於製造光學向異體時，在液晶狀態之光聚合時，為避免誘發不受企求的熱聚合，且容易固定分子之均勻配向狀態時，以於室溫(20~40℃，以下皆相同)下呈現對映的液晶相較佳。而且，聚合性液晶組成物含有有機溶劑時，以於除去溶劑時，在室溫下呈現對映的液晶相較佳。 The polymerizable liquid crystal composition of the present invention is used at the time of photopolymerization in the case of photopolymerization in a liquid crystal state, in order to avoid inducing undesired thermal polymerization and to easily fix a uniform alignment state of molecules. Preferably, the liquid crystal phase exhibiting an enantiomer at 20 to 40 ° C, the same below. Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferred to exhibit an enantiomeric liquid crystal phase at room temperature when the solvent is removed.

本發明之聚合性液晶組成物，可適當地利用作為配向性被膜形成用組成物或塗覆液。 The polymerizable liquid crystal composition of the present invention can be suitably used as a composition for forming an alignment film or a coating liquid.

[聚合物及薄膜] [Polymer and film]

對上述說明的本發明之聚合性液晶組成物而言，藉由光照射或加熱處理，製得聚合物。而且，藉由旋轉塗覆或鑄造法將聚合性液晶組成物塗覆於基板上，且藉由光照射處理，製得薄膜。 The polymerizable liquid crystal composition of the present invention described above is obtained by light irradiation or heat treatment to obtain a polymer. Further, a polymerizable liquid crystal composition is applied onto a substrate by spin coating or casting, and a film is obtained by light irradiation treatment.

此時，基板可使用玻璃、石英、濾色片、三乙醯基纖 維素(TAC)等之塑膠薄片或薄膜等。 At this time, the substrate can use glass, quartz, color filter, triethylene fluorene fiber Plastic sheets or films such as TAC.

使用的基板，以提高所得的薄膜之混合型配向性為目的時，以可得傾斜角的方式實施配向處理較佳。配向處理的方法，可適當選擇塗覆含有聚醯亞胺前驅體、聚醯亞胺、聚乙烯基肉桂酸酯等之配向材料，且進行摩擦或自斜方照射偏光紫外線予以配向處理的方法，形成二氧化矽之斜法蒸鍍膜之方法，形成蘭米爾膜的方法等習知方法使用，為製作混合型配向薄膜時，其中以使用可得傾斜角之配向方法較佳。 When the substrate to be used is used for the purpose of improving the mixed alignment of the obtained film, it is preferred to carry out the alignment treatment so as to obtain an inclination angle. For the method of the alignment treatment, a method of applying an alignment material containing a polyimide precursor, a polyimide, a polyvinyl cinnamate, or the like, and performing an alignment treatment by rubbing or obliquely irradiating a polarized ultraviolet ray may be appropriately selected. A method of forming a smectite vapor-deposited film of cerium oxide, a method of forming a Langeir film, and the like are preferably used. In order to produce a mixed alignment film, an alignment method using a tilt angle is preferable.

於製作薄膜之方法中，亦可在塗覆聚合性液晶組成物之步驟與藉由光或熱予以聚合的步驟途中，視其所需亦可施予以熱板等進行加熱的步驟。該步驟、特別是使用含有有機溶劑之聚合性液晶組成物(塗覆液)時，作為自該組成物除去有機溶劑之手段時為有效。 In the method of producing a film, a step of heating a hot plate or the like may be applied as needed in the step of applying the polymerizable liquid crystal composition and the step of polymerizing by light or heat. This step, in particular, when a polymerizable liquid crystal composition (coating liquid) containing an organic solvent is used, it is effective as a means for removing the organic solvent from the composition.

於上述任一方法中，藉由在聚合性液晶組成物呈現液晶相的狀態進行聚合，可製得具有經配向的光學向異性之薄膜。 In any of the above methods, by performing polymerization in a state in which the polymerizable liquid crystal composition exhibits a liquid crystal phase, a film having an aligned optical anisotropy can be obtained.

藉由使用本發明之聚合性液晶組成物，可製得具有光學向異性之薄膜，該薄膜可適合使用於偏光板或相位差板等。而且，該薄膜由於在高溫下之透明性良好，故可適合利用於汽車用顯示裝置等之於高溫環境中所使用的電子機器。 By using the polymerizable liquid crystal composition of the present invention, a film having optical anisotropy can be obtained, and the film can be suitably used for a polarizing plate, a phase difference plate or the like. Further, since the film is excellent in transparency at a high temperature, it can be suitably used in an electronic device used in a high-temperature environment such as an automobile display device.

[實施例] [Examples]

於下述中，以合成例、實施例及比較例更具體地說明本發明，惟本發明不受實施例所限制。而且，實施例之各物性的測定方法及測定條件，如下所述。 In the following, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the examples. Further, the measurement methods and measurement conditions of the respective physical properties of the examples are as follows.

[1]NMR [1] NMR

將化合物溶解於氘化氫(CDCl3)或氘化二甲基亞碸(DMSO-d6)中，且使用核磁共振裝置(300MHz、吉歐魯(譯音)公司製)測定1H-NMR。 The compound was dissolved in hydrogen halide (CDCl 3 ) or deuterated dimethyl hydrazine (DMSO-d6), and 1 H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Geeol Corporation).

[2]液晶相之觀察 [2] Observation of liquid crystal phase

液晶相之同定，係將試料在高溫載台(MATS-2002S、(股)Tokai hit製)上加熱，且使用偏光顯微鏡((股)Ricon)進行觀察。相轉移溫度係使用Bruker AXS(股)製示差掃描熱分析裝置(DSC3100SR)，以掃描速度(Scan Rate)10℃/分鐘之條件進行測定。 The liquid crystal phase was fixed, and the sample was heated on a high temperature stage (MATS-2002S, manufactured by Tokai), and observed using a polarizing microscope (Ricon). The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) manufactured by Bruker AXS Co., Ltd. at a scanning rate of 10 ° C/min.

[3]霧度值 [3] Haze value

使用(有)東京電色製Spectral Haze Meter(TC-1800H)測定薄膜之霧度值。 The haze value of the film was measured using a Spectral Haze Meter (TC-1800H) manufactured by Tokyo Electric Co., Ltd.

[4]薄膜之阻滯值 [4] film retardation value

使用阻滯測定裝置(RETS-100、大塚電子(股)製)測定波長590nm之阻滯值。 The retardation value at a wavelength of 590 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).

[5]薄膜之平均傾斜角度 [5] Average tilt angle of the film

使用AxoScanTM Mueller Matrix Polarimeter(AXOMETRIX公司製)測定平均傾斜角度。 The average tilt angle was measured using AxoScan TM Mueller Matrix Polarimeter (AXOMETRIX Corporation).

[合成例1]聚合性液晶化合物(A1)之合成 [Synthesis Example 1] Synthesis of Polymerizable Liquid Crystal Compound (A1) [1]中間體化合物(I1)之合成 [1] Synthesis of intermediate compound (I1)

在附有冷卻管之500mL茄型燒瓶中加入4-氰基-4’-羥基聯苯9.8g(50.0mmol)、3-溴-1-丙醇7.0g(50.0mmol)、碳酸鉀13.8g(100mmol)及丙酮15mL，形成混合物，在64℃下攪拌48小時且進行反應。於反應完成後，在減壓下餾去溶劑，製得黃色濕潤固體。然後，混合該固體與水140mL，於其中加入二***100mL進行萃取。萃取進行3次。經分液的有機層加入無水硫酸鎂進行乾燥，且於過濾後，在減壓下餾去溶劑，製得黃色固體。使該固體藉由使用己烷/醋酸乙酯=2/1(v/v)之混合溶劑的再結晶予以精製，製得白色固體8.7g。該固體之NMR測定結果如下述所示。由該結果可知，確認該白色固體為中間體化合物(I1)(收率70%)。 To a 500 mL eggplant type flask equipped with a cooling tube, 9.8 g (50.0 mmol) of 4-cyano-4'-hydroxybiphenyl, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, and 13.8 g of potassium carbonate were added ( 100 mmol) and acetone 15 mL were formed to form a mixture, and the mixture was stirred at 64 ° C for 48 hours to carry out a reaction. After completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow-yellow solid. Then, the solid and 140 mL of water were mixed, and 100 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. The organic layer was separated and dried over anhydrous magnesium sulfate, and after filtration, the solvent was evaporated under reduced pressure to give a yellow solid. This solid was purified by recrystallization using a mixed solvent of hexane / ethyl acetate = 2 / 1 (v / v) to obtain 8.7 g of a white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was the intermediate compound (I1) (yield: 70%).

1H-NMR(CDCl3)δ：2.09(m,2H),3.90(t,2H),4.20(t,2H),6.99(d,2H),7.52(d,2H)，7.66(m,4H) 1 H-NMR (CDCl 3 ) δ: 2.09 (m, 2H), 3.90 (t, 2H), 4.20 (t, 2H), 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H) )

[2]聚合性液晶化合物(A1)之合成 [2] Synthesis of polymerizable liquid crystal compound (A1)

將上述所得的中間體化合物(I1)12.0g、與三乙胺7.7mL與少量的2,6-二-t-丁基-p-甲酚(BHT)同時溶解於四氫呋喃(THF)40mL中，在室溫下進行攪拌，藉由水浴予以冷卻，以15分鐘滴入在THF 40mL中溶解有氯化丙烯醯基4.6mL之溶液。滴完後，進行攪拌30分鐘，且除去水浴，回復至室溫、持續終夜攪拌，過濾被析出的三乙胺鹽酸鹽。自所得的液體餾去約3/4之THF，添加二氯甲烷50mL，使該有機層順序以飽和碳酸氫鈉水溶液50mL、0.5mol/L鹽酸50mL、飽和食鹽水50mL進行洗淨，且以硫酸鎂予以乾燥後，餾去溶劑，製得生成物。藉由乙醇予以再結晶後，製得聚合性液晶化合物(A1)6.0g。 12.0 g of the intermediate compound (I1) obtained above, and 7.7 mL of triethylamine and a small amount of 2,6-di-t-butyl-p-cresol (BHT) were simultaneously dissolved in 40 mL of tetrahydrofuran (THF). The mixture was stirred at room temperature, cooled by a water bath, and a solution of 4.6 mL of a chlorinated propenyl group dissolved in 40 mL of THF was added dropwise thereto over 15 minutes. After the completion of the dropwise addition, stirring was carried out for 30 minutes, and the water bath was removed, and the mixture was returned to room temperature, and stirred overnight, and the precipitated triethylamine hydrochloride was filtered. Distilled about 3/4 of THF from the obtained liquid, and added 50 mL of dichloromethane, and the organic layer was washed with 50 mL of a saturated aqueous sodium hydrogencarbonate solution, 50 mL of 0.5 mol/L hydrochloric acid, and 50 mL of saturated brine, and sulfuric acid was used. After the magnesium is dried, the solvent is distilled off to obtain a product. After recrystallization by ethanol, 6.0 g of a polymerizable liquid crystal compound (A1) was obtained.

1H-NMR(CDCl3)δ：2.20(m,2H),4.10(t,2H),4.40(t,2H),5.81(d,1H),6.15(m,1H),6.41(d,1H),6.99(d,2H),7.55(d,2H),7.66(m,4H) 1 H-NMR (CDCl 3 ) δ: 2.20 (m, 2H), 4.10 (t, 2H), 4.40 (t, 2H), 5.81 (d, 1H), 6.15 (m, 1H), 6.41 (d, 1H) ), 6.99 (d, 2H), 7.55 (d, 2H), 7.66 (m, 4H)

[合成例2]聚合性液晶化合物(A2)之合成 [Synthesis Example 2] Synthesis of polymerizable liquid crystal compound (A2) [1]中間體化合物(I2)之合成 [1] Synthesis of intermediate compound (I2)

在附有冷卻管之100mL茄型燒瓶中加入4-氰基-4’-羥基聯苯5.0g(25.6mmol)、6-溴-1-己醇4.6g(25.6mmol)、碳酸鉀7.0g(50mmol)、及丙酮50mL，形成混合物，在64℃下攪拌24小時且進行反應。於反應完成後，在減壓下餾去溶劑，製得黃色濕潤固體。然後，混合該固體與水70mL，於其中加入二***50mL進行萃取。萃取進行3次。經分液的有機層加入無水硫酸鎂予以乾燥，且於過濾後，在減壓下餾去溶劑，製得黃色固體。將該固體溶解於醋酸乙酯3mL中，且藉由二氧化矽凝膠柱色層分析法(柱：二氧化矽凝膠60,0.063-0.200mm,Merck公司製、溶出液：己烷/醋酸乙酯=1/1(v/v)予以精製。自所得的溶液餾去溶劑，製得白色固體6.9g。該固體之NMR測定結果如下述所示。由該結果可確認該白色固體為中間體化合物(I2)(收率91%)。 To a 100 mL eggplant type flask equipped with a cooling tube, 5.0 g (25.6 mmol) of 4-cyano-4'-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, and 7.0 g of potassium carbonate were added ( 50 mmol) and acetone 50 mL were combined to form a mixture, and the mixture was stirred at 64 ° C for 24 hours to carry out a reaction. After completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow-yellow solid. Then, 70 mL of the solid and water were mixed, and 50 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. The organic layer was separated and dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was dissolved in 3 mL of ethyl acetate and analyzed by a ceria gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/acetic acid) Ethyl ester = 1/1 (v/v) was purified, and the solvent was evaporated to give 6.9 g of a white solid. The NMR measurement results of the solid were as follows. From the results, it was confirmed that the white solid was in the middle. Compound (I2) (yield 91%).

1H-NMR(DMSO-d6)δ：1.26(m,6H),1.69(m,2H),3.37(t,2H),4.03(t,2H),7.06(d,2H),7.69(d,2H)，7.85(m,4H) 1 H-NMR (DMSO-d 6 ) δ: 1.26 (m, 6H), 1.69 (m, 2H), 3.37 (t, 2H), 4.03 (t, 2H), 7.06 (d, 2H), 7.69 (d) , 2H), 7.85 (m, 4H)

[2]中間體化合物(F2)之合成 [2] Synthesis of intermediate compound (F2)

然後，在附有冷卻管之200mL三口燒瓶中加入氯鉻酸吡錠鹽(PCC)2.2g(10.0mmol)及二氯甲烷30.0mL，於攪拌混合的狀態下滴入於二氯甲烷50.0mL中溶解有上述所得的中間體化合物(I2)2.95g(10.0mmol)之溶液，再於40℃下攪拌0.5小時。然後，在除去附著於燒瓶壁之油狀物的溶液中加入二***90mL進行減壓過濾後，在減壓下餾去溶劑，製得深綠色濕潤的固體。將該固體溶解於醋酸乙酯3mL中，以二氧化矽凝膠柱色層分析法(柱：二氧化矽凝膠60,0.063-0.200mm,Merck公司製、溶出液：己烷/醋酸乙酯=1/1(v/v)予以精製。自所得的溶液餾去溶劑，製得無色固體2.8g。該固體之NMR測定結果如下述所示。由該結果可確認該無色固體為中間體化合物(F2)(收率93%)。 Then, 2.2 g (10.0 mmol) of chlorochromate pyridinium salt (PCC) and 30.0 mL of dichloromethane were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was added dropwise to 50.0 mL of dichloromethane while stirring and mixing. A solution of 2.95 g (10.0 mmol) of the intermediate compound (I2) obtained above was dissolved, and the mixture was stirred at 40 ° C for 0.5 hour. Then, 90 mL of diethyl ether was added to the solution of the oily substance adhering to the wall of the flask, and the mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a dark green solid. The solid was dissolved in 3 mL of ethyl acetate, and analyzed by ruthenium dioxide gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) The solvent was distilled off from the obtained solution to obtain 2.8 g of a colorless solid. The NMR measurement results of the solid were as follows. From the results, it was confirmed that the colorless solid was an intermediate compound. (F2) (yield 93%).

1H-NMR(CDCl3)δ：1.84(m,6H),2.50(m,2H),4.02(m,2H),6.99(d,2H),7.53(d,2H),7.91(m,4H)，9.80(s,1H) 1 H-NMR (CDCl 3 ) δ: 1.84 (m, 6H), 2.50 (m, 2H), 4.02 (m, 2H), 6.99 (d, 2H), 7.53 (d, 2H), 7.91 (m, 4H) ), 9.80 (s, 1H)

[3]聚合性液晶化合物(A2)之合成 [3] Synthesis of polymerizable liquid crystal compound (A2)

最後，在附有冷卻管之50mL茄型燒瓶中加入上述所得的中間體化合物(F2)2.9g(10.0mmol)、2-(溴化甲基)丙烯酸1.65g(10.0mmol)、Amberlyst(註冊商標)15(Rome & Haas公司商品名)1.6g、THF 16.0mL、氯化錫(II)1.9g(10.0mmol)及純水4.0mL，形成混合物，在70℃下攪拌7小時且進行反應。於反應完成後，在減壓下過濾反應液，與純水30mL混合，且於其中加入二***50mL進行萃取。萃取進行3次。在經萃取的有機層中加入無水硫酸鎂予以乾燥，且自減壓過濾後之溶液餾去溶劑，製得黃色固體。將該固體溶解於醋酸乙酯2mL中，且藉由二氧化矽凝膠柱色層分析法(柱：二氧化矽凝膠60,0.063-0.200mm,Merck公司製、溶出液：己烷/醋酸乙酯=2/1(v/v)予以精製。自所得的溶液餾去溶劑，製得白色固體1.5g。該固體之NMR測定結果如下述所示。由該結果可確認該白色固體為目的之聚合性液晶化合物(A2)(收率41%)。 Finally, 2.9 g (10.0 mmol) of the intermediate compound (F2) obtained above, 1.65 g (10.0 mmol) of 2-(brominated methyl)acrylic acid, and Amberlyst (registered trademark) were added to a 50 mL eggplant type flask equipped with a cooling tube. 15 (Rome & Haas brand name) 1.6 g, THF 16.0 mL, tin (II) chloride 1.9 g (10.0 mmol), and pure water 4.0 mL were formed to form a mixture, and the mixture was stirred at 70 ° C for 7 hours to carry out a reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure, and mixed with 30 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the extracted organic layer to dryness, and the solvent was filtered off from the filtrate under reduced pressure to give a yellow solid. The solid was dissolved in 2 mL of ethyl acetate and analyzed by a ceria gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/acetic acid) Ethyl acetate = 2/1 (v/v) was purified, and the solvent was distilled off from the obtained solution to obtain 1.5 g of a white solid. The NMR measurement results of the solid were as follows. From this result, the white solid was confirmed. Polymerizable liquid crystal compound (A2) (yield 41%).

1H-NMR(CDCl3)δ：1.57(m,6H),1.85(m,2H),2.60(m,1H),3.05(m,1H),4.01(t,2H),4.54(m,1H),5.63(m,1H),6.23(m,1H) ,7.00(d,2H),7.52(d,2H),7.68(m,4H) 1 H-NMR (CDCl 3 ) δ: 1.57 (m, 6H), 1.85 (m, 2H), 2.60 (m, 1H), 3.05 (m, 1H), 4.01 (t, 2H), 4.54 (m, 1H) ), 5.63 (m, 1H), 6.23 (m, 1H), 7.00 (d, 2H), 7.52 (d, 2H), 7.68 (m, 4H)

而且，觀察該聚合性液晶化合物(A2)之液晶性的結果，在84℃下形成等方性液體狀態，降溫時，於61℃下相轉移成液晶相(向列相)。 Further, as a result of observing the liquid crystallinity of the polymerizable liquid crystal compound (A2), an isotropic liquid state was formed at 84 ° C, and when the temperature was lowered, the phase was transferred to a liquid crystal phase (nematic phase) at 61 ° C.

[合成例3]聚合性液晶化合物(B1)之合成 [Synthesis Example 3] Synthesis of Polymerizable Liquid Crystal Compound (B1) [1]中間體化合物(I3)之合成 [1] Synthesis of intermediate compound (I3)

在附有冷卻管之200mL茄型燒瓶中加入4-羥基苯甲酸甲酯7.61g(50.0mmol)、6-溴-1-己醇9.1g(50.0mmol)、碳酸鉀13.8g(100mmol)、及丙酮70mL，形成混合物，在64℃(加熱回流)下攪拌24小時且進行反應。於反應完成後，減壓過濾反應液，在減壓下餾去溶劑，製得黃色濕潤固體。使該固體藉由二氧化矽凝膠柱色層分析法(柱：二氧化矽凝膠60,0.063-0.200mm,Merck公司製、溶出液：己烷/醋酸乙酯=1/1(v/v))予以精製。自所得的溶液餾去溶劑，製得白色固體11.3g。該固體之NMR測定結果如下述所示。由該結果可確認該白色固體為目的之中間體化合物(I3)(收率90%)。 To a 200 mL eggplant type flask equipped with a cooling tube, 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and 70 mL of acetone was formed to form a mixture, which was stirred at 64 ° C (heated reflux) for 24 hours and reacted. After completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated to vacuo. The solid was subjected to ceria gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 1/1 (v/) v)) Refined. The solvent was distilled away from the obtained solution to obtain 11.3 g of a white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was the objective intermediate compound (I3) (yield: 90%).

1H-NMR(CDCl3)δ：1.3-1.7(m,8H),3.67(m,2H), 3.88(s,3H),4.03(t,2H),6.91(d,2H),7.99(d,2H) 1 H-NMR (CDCl 3 ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d) , 2H)

[2]中間體化合物(F3)之合成 [2] Synthesis of intermediate compound (F3)

然後，在附有冷卻管之100mL三口燒瓶中加入PCC 2.2g(10.0mmol)及二氯甲烷15.0mL，於攪拌混合的狀態下滴入於二氯甲烷15.0mL中溶解有上述所得的中間體化合物(I3)2.5g(10.0mmol)之溶液，再於室溫下攪拌6小時。然後，在除去附著於燒瓶壁之油狀物的溶液中加入二***90mL，於減壓過濾後，在減壓下餾去溶劑，製得深綠色濕潤的固體。將該固體以二氧化矽凝膠柱色層分析法(柱：二氧化矽凝膠60,0.063-0.200mm,Merck公司製、溶出液：己烷/醋酸乙酯=2/1(v/v)予以精製。自所得的溶液餾去溶劑，製得無色固體1.3g。該固體之NMR測定結果如下述所示。由該結果可確認該無色固體為中間體化合物(F3)(收率50%)。 Then, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane were placed in a 100 mL three-necked flask equipped with a cooling tube, and the intermediate compound obtained above was dissolved in 15.0 mL of dichloromethane while stirring and mixing. (I3) A solution of 2.5 g (10.0 mmol) was stirred at room temperature for 6 hours. Then, 90 mL of diethyl ether was added to the solution which removed the oil which adhered to the wall of the flask, and after filtration under reduced pressure, the solvent was distilled off under reduced pressure to obtain a dark green moist solid. The solid was analyzed by cerium oxide gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 2/1 (v/v) The solvent was distilled off from the obtained solution to obtain 1.3 g of a colorless solid. The NMR measurement results of the solid were as follows. From the results, it was confirmed that the colorless solid was the intermediate compound (F3) (yield 50%) ).

1H-NMR(CDCl3)δ：1.3-1.8(m,6H),2.49(t,2H),3.88(s,3H),3.99(t,2H),6.87(d,2H),7.99(d,2H)，9.78(s,1H) 1 H-NMR (CDCl 3 ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d) , 2H), 9.78 (s, 1H)

[3]中間體化合物(G3)之合成 [3] Synthesis of intermediate compound (G3)

其次，在附有冷卻管之50mL茄型燒瓶中加入上述所得的中間體化合物(F3)1.25g(5.0mmol)、2-(溴化甲基)丙烯酸0.83g(5.0mmol)、Amberlyst(註冊商標)15(Rome & Haas公司商品名)0.8g、THF 8.0mL、氯化錫(II)0.95g(5.0mmol)及純水2.0mL，形成混合物，在70℃下攪拌5小時且進行反應。於反應完成後，減壓過濾反應液，與純水40mL混合，且於其中加入二***50mL進行萃取。萃取進行3次。在萃取後的有機層中加入無水硫酸鎂予以乾燥，且自減壓過濾後之溶液餾去溶劑，製得無色固體1.5g。該固體之NMR測定結果如下述所示。由該結果可確認該無色固體為中間體化合物(G3)(收率94%)。 Next, 1.25 g (5.0 mmol) of the intermediate compound (F3) obtained above, 0.83 g (5.0 mmol) of 2-(brominated methyl)acrylic acid, and Amberlyst (registered trademark) were placed in a 50 mL eggplant type flask equipped with a cooling tube. 15 (Rome & Haas brand name) 0.8 g, THF 8.0 mL, tin (II) chloride 0.95 g (5.0 mmol), and pure water 2.0 mL, and a mixture was formed, and the mixture was stirred at 70 ° C for 5 hours to carry out a reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 40 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off from the filtrate under reduced pressure to obtain 1.5 g of a colorless solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the colorless solid was the intermediate compound (G3) (yield: 94%).

1H-NMR(DMSO-d6)δ：1.3-1.8(m,8H),2.62(m,1H),3.04(s,1H),3.81(s,3H),4.05(t,2H),4.54(m,1H),5.70(s,1H),6.01(s,1H),7.03(d,2H),7.89(d,2H) 1 H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H)

[4]中間體化合物(H3)之合成 [4] Synthesis of intermediate compound (H3)

在附有冷卻管之100mL茄型燒瓶中加入乙醇35mL，上述所得的中間體化合物(G3)1.5g(4.7mmol)、及10質量%氫氧化鈉水溶液5mL，形成混合物，在85℃下攪拌3小時且進行反應。於反應完成後，在500mL燒杯中加入水300mL與反應液，於室溫下進行攪拌30分鐘後，滴入10質量%HCl水溶液5mL後，予以過濾，製得白色固體1.3g。然後，在附有冷卻管之50mL茄型燒瓶中加入所得的白色固體1.1g、Amberlyst(註冊商標)15(Rome & Haas公司商品名)1.0g、THF 20.0mL，形成混合物，在70℃下攪拌5小時且進行反應。於反應完成後，自減壓過濾反應液後之溶液餾去溶劑，製得黃色固體。使該黃色固體藉由再結晶(己烷/醋酸乙酯=1/1(v/v))予以精製後，製得白色固體0.9g。該固體之NMR測定結果如下述所示。由該結果可確認該白色固體為目的之中間體化合物(H3)(收率71%)。 In a 100 mL eggplant type flask equipped with a cooling tube, 35 mL of ethanol, 1.5 g (4.7 mmol) of the obtained intermediate compound (G3), and 5 mL of a 10% by mass aqueous sodium hydroxide solution were added to form a mixture, and the mixture was stirred at 85 ° C. The reaction was carried out in an hour. After completion of the reaction, 300 mL of water and a reaction liquid were added to a 500 mL beaker, and the mixture was stirred at room temperature for 30 minutes, and then 5 mL of a 10% by mass aqueous HCl solution was added dropwise thereto, followed by filtration to obtain 1.3 g of a white solid. Then, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 (trade name of Rome & Haas Co., Ltd.), and 20.0 mL of THF were added to a 50 mL eggplant type flask equipped with a cooling tube to form a mixture, which was stirred at 70 ° C. The reaction was carried out for 5 hours. After completion of the reaction, the solvent was filtered off from the reaction mixture under reduced pressure to give a yellow solid. The yellow solid was purified by recrystallization (hexane/ethyl acetate = 1/1 (v/v)) to yield a white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was the objective compound (H3) (yield: 71%).

1H-NMR(DMSO-d6)δ：1.2-1.8(m,8H),2.60(m,1H),3.09(m,1H),4.04(m,2H),4.55(m,1H),5.69(s,1H),6.02(s,1H),6.99(d,2H),7.88(d,2H),12.5(s,broad,1H) 1 H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H)

[5]化合物(P3)之合成 [5] Synthesis of Compound (P3)

將3-溴-1-丙醇19.2g(138.0mmol)、與三乙胺(TEA)18.9mL與少量的BHT同時溶解於THF 100mL中，在室溫下進行攪拌，藉由水浴予以冷卻下，以15分鐘滴入在THF 50mL中溶解有氯化丙烯醯基12.2mL(150mmol)之溶液。滴完後，進行攪拌30分鐘，且除去水浴，回復至室溫且持續終夜攪拌，過濾被析出的TEA鹽酸鹽。自該濾液餾去THF，添加二***100mL，使該有機層順序以各80mL之飽和碳酸氫鈉水溶液、0.5mol/L鹽酸、飽和食鹽水進行洗淨，且以硫酸鎂予以乾燥後，餾去溶劑，製得化合物(P3)18.2g。該固體以NMR測定的結果，如下述所示。 19.2 g (138.0 mmol) of 3-bromo-1-propanol and 18.9 mL of triethylamine (TEA) and a small amount of BHT were simultaneously dissolved in 100 mL of THF, stirred at room temperature, and cooled by a water bath. A solution of 12.2 mL (150 mmol) of chlorinated propenylhydrazine was dissolved in 50 mL of THF over 15 minutes. After the completion of the dropwise addition, stirring was carried out for 30 minutes, and the water bath was removed, and the mixture was returned to room temperature and stirred overnight, and the precipitated TEA hydrochloride was filtered. The THF was distilled off from the filtrate, and 100 mL of diethyl ether was added thereto, and the organic layer was washed successively with 80 mL of a saturated aqueous sodium hydrogencarbonate solution, 0.5 mol/L hydrochloric acid, and brine, dried over magnesium sulfate, and then evaporated. Solvent, the compound (P3) was obtained in an amount of 18.2 g. The solid was measured by NMR as shown below.

1H-NMR(CDCl3)δ：2.20(m,2H),3.45(t,2H),4.33(t,2H),5.84(d,1H),6.13(m,1H),6.44(d,1H) 1 H-NMR (CDCl 3 ) δ: 2.20 (m, 2H), 3.45 (t, 2H), 4.33 (t, 2H), 5.84 (d, 1H), 6.13 (m, 1H), 6.44 (d, 1H) )

[6]中間體化合物(J3)之合成 [6] Synthesis of intermediate compound (J3)

在附有冷卻管之500mL茄型燒瓶中加入4-羥基-4’-雙酚17.6g(94.3mmol)、化合物(P3)18.2g(94.3mmol)、碳酸鉀24.0g(190mmol)、及丙酮250mL，形成混合物，在溫度54℃下攪拌20小時且進行反應。於反應完成後，減壓過濾反應液並在減壓下餾去溶劑，製得黃色濕潤固體。將該固體藉由柱色層分析法(柱：二氧化矽凝膠60,0.063-0.200mm,Merck公司製、溶出液：己烷/醋酸乙酯=2/1)予以精製。自此處所得的溶液餾去溶劑，製得白色固體6.1g。該固體之NMR測定結果如下述所示。由該結果可確認該白色固體為中間體化合物(J3)(收率22%)。 In a 500 mL eggplant type flask equipped with a cooling tube, 14.6 g (94.3 mmol) of 4-hydroxy-4'-bisphenol, 18.2 g (94.3 mmol) of the compound (P3), 24.0 g (190 mmol) of potassium carbonate, and 250 mL of acetone were added. The mixture was formed and stirred at a temperature of 54 ° C for 20 hours and the reaction was carried out. After completion of the reaction, the reaction solution was filtered under reduced pressure and the solvent was evaporated to vacuo to yield a yellow wet solid. This solid was purified by column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 2/1). The solvent was distilled off from the solution obtained here to give 6.1 g of white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was an intermediate compound (J3) (yield: 22%).

1H-NMR(CDCl3)δ：2.21(m,2H),4.13(t,2H),4.40(t,2H),4.99(s,1H),5.87(d,1H),6.15(m,1H),6.40(d,1H),6.87(d,2H),6.99(d,2H)，7.46(m,4H) 1 H-NMR (CDCl 3 ) δ: 2.21 (m, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 4.99 (s, 1H), 5.87 (d, 1H), 6.15 (m, 1H) ), 6.40 (d, 1H), 6.87 (d, 2H), 6.99 (d, 2H), 7.46 (m, 4H)

[7]聚合性液晶化合物(B1)之合成 [7] Synthesis of polymerizable liquid crystal compound (B1)

將上述所得的中間體化合物(H3)6.1g(20.0mmol)、中間體化合物(J3)6.0g(20.0mmol)、N,N-二甲基-4-胺基吡啶 (DMAP)0.08g及少量的2,6-二-tert-丁基-p-甲酚(BHT)在室溫、攪拌下，懸浮於二氯甲烷10mL，於其中加入溶解有二氯甲烷20mL之二氯環己基羧二醯亞胺(DCC)4.7g(23.0mmol)，進行終夜攪拌後，過濾分別被析出的DCC尿素，且使該濾液順序各以60mL之0.5mol/L鹽酸與飽和碳酸氫鈉水溶液與飽和食鹽水洗淨2次，且以硫酸鎂予以乾燥後，餾去溶劑，藉由乙醇進行再結晶操作，製得聚合性液晶化合物(B1)8.8g(收率為75%)。該固體以NMR測定的結果，如下述所示。 6.1 g (20.0 mmol) of the intermediate compound (H3) obtained above, intermediate compound (J3) 6.0 g (20.0 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.08g and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) were suspended in 10 mL of dichloromethane at room temperature with stirring, and 20 mL of dichloromethane was dissolved therein. Dichlorocyclohexylcarboxydiimide (DCC) 4.7 g (23.0 mmol), after stirring overnight, the separated DCC urea was filtered, and the filtrate was sequentially placed with 60 mL of 0.5 mol/L hydrochloric acid and saturated hydrogen carbonate. After the sodium aqueous solution and the saturated aqueous sodium chloride solution were washed twice, and dried over magnesium sulfate, the solvent was distilled off, and recrystallization was carried out by ethanol to obtain 8.8 g (yield: 75%) of the polymerizable liquid crystal compound (B1). The solid was measured by NMR as shown below.

1H-NMR(CDCl3)δ：1.53(m,6H),1.81(m,2H),2.20(m,2H),2.60(m,1H),3.07(m,1H),4.06(t,2H),4.12(t,2H),4.40(t,2H),4.54(m,1H),5.63(d,1H),5.85(d,1H),6.10(m,1H),6.24(d,1H),6.42(d,1H),6.97(d,4H),7.25(m,2H),7.54(m,2H),7.59(m,2H),8.17(d,2H) 1 H-NMR (CDCl 3 ) δ: 1.53 (m, 6H), 1.81 (m, 2H), 2.20 (m, 2H), 2.60 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H) ), 4.12 (t, 2H), 4.40 (t, 2H), 4.54 (m, 1H), 5.63 (d, 1H), 5.85 (d, 1H), 6.10 (m, 1H), 6.24 (d, 1H) , 6.42 (d, 1H), 6.97 (d, 4H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)

而且，觀察該聚合性液晶化合物(B1)之液晶性的結果，於昇溫時、109℃下相轉移成碟狀X相，且在144℃下相轉移成向列相，在168℃下形成等方性液體狀態。 Further, as a result of observing the liquid crystallinity of the polymerizable liquid crystal compound (B1), the phase was transferred to a discotic X phase at a temperature of 109 ° C at a temperature rise, and the phase was transferred to a nematic phase at 144 ° C, and formed at 168 ° C. Square liquid state.

[實施例、比較例]聚合性液晶組成物及其聚合物(薄膜) [Examples, Comparative Examples] Polymeric liquid crystal composition and polymer (film) thereof

下述實施例及比較例所使用的化合物，如下所述。而且，實施例1~8所使用的組成物之組成如表1所示，比較例1~5所使用的組成物之組成如表2所示。 The compounds used in the following examples and comparative examples are as follows. Further, the compositions of the compositions used in Examples 1 to 8 are shown in Table 1, and the compositions of the compositions used in Comparative Examples 1 to 5 are shown in Table 2.

而且，下述化合物(C1)、(C2)、(C3)、(C5)及(E1)係新中村化學工業(股)之製品，化合物(C4)係日本化藥(股) 之製品，化合物(E2)係東京化成工業(股)之製品。化合物(E3)為已知。 Further, the following compounds (C1), (C2), (C3), (C5), and (E1) are products of Shin-Nakamura Chemical Industry Co., Ltd., and the compound (C4) is a Japanese chemical (share). The product (E2) is a product of Tokyo Chemical Industry Co., Ltd. Compound (E3) is known.

[實施例1]聚合性液晶組成物及其聚合物(薄膜) [Example 1] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C1)9mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 9 mg of the polyvalent acrylate compound (C1), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

將該聚合性液晶組成物藉由旋轉塗覆器(1,000rpm、20秒)塗覆於附液晶配向膜之基板的液晶配向膜面上，在100℃之熱板上預燒成60秒後，放冷至室溫。此時，基板上之聚合性組成物為液晶狀態。此處所使用的附液晶配向膜之基板，係在附ITO之玻璃基板的ITO面上，藉由旋 轉塗覆器塗覆液晶配向劑(日產化學工業(股)製SE-1410)，且在230℃下進行燒成，形成厚度100nm之薄膜後，實施摩擦處理者。 The polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by a spin coater (1,000 rpm, 20 seconds), and calcined on a hot plate at 100 ° C for 60 seconds. Allow to cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with a liquid crystal alignment film used here is attached to the ITO surface of the ITO-attached glass substrate by spin The transfer coater was coated with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries Co., Ltd.), and fired at 230 ° C to form a film having a thickness of 100 nm, and then subjected to a rubbing treatment.

其次，使在附液晶配向膜之基板上所形成的塗膜在氮氣環境中使用鹵化甲烷燈、以2,000mJ/cm2強度之光照射，使聚合性液晶組成物予以聚合。 Next, the coating film formed on the substrate with the liquid crystal alignment film was irradiated with a methane lamp under a nitrogen atmosphere at a light intensity of 2,000 mJ/cm 2 to polymerize the polymerizable liquid crystal composition.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯值為117nm，霧度值為1.44。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 117 nm and the haze value was 1.44.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為109nm，霧度值為1.30。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 109 nm and the haze value was 1.30.

[實施例2]聚合性液晶組成物及其聚合物(薄膜) [Example 2] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C2)15mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the polyvalent acrylate compound (C2), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator. 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯 值為121nm，霧度值為0.66。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). Blocking The value was 121 nm and the haze value was 0.66.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為109nm，霧度值為0.38。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 109 nm and the haze value was 0.38.

[實施例3]聚合性液晶組成物及其聚合物(薄膜) [Example 3] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C3)15mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the polyvalent acrylate compound (C3), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯值為115nm，霧度值為0.08。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 115 nm and the haze value was 0.08.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為98nm，霧度值為0.07。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 98 nm and the haze value was 0.07.

[實施例4]聚合性液晶組成物及其聚合物(薄膜) [Example 4] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C4)9mg、光聚合引發劑之Ciba Geigy公司製 Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 9 mg of the polyvalent acrylate compound (C4), and a photopolymerization initiator manufactured by Ciba Geigy Co., Ltd. 4 mg of Irgacure 369 (trade name) and 0.6 mg of R30 (manufactured by DIC Co., Ltd.) of a surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯值為101nm，霧度值為0.05。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 101 nm and the haze value was 0.05.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為92nm，霧度值為0.07。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 92 nm and the haze value was 0.07.

[實施例5]聚合性液晶組成物及其聚合物(薄膜) [Example 5] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C4)15mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the polyvalent acrylate compound (C4), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯 值為96nm，霧度值為1.15。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). Blocking The value was 96 nm and the haze value was 1.15.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為95nm，霧度值為2.18。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 95 nm and the haze value was 2.18.

[實施例6]聚合性液晶組成物及其聚合物(薄膜) [Example 6] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C5)3mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 3 mg of the polyvalent acrylate compound (C5), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯值為106nm，霧度值為0.03。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 106 nm and the haze value was 0.03.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為99nm，霧度值為0.08。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 99 nm and the haze value was 0.08.

[比較例1]聚合性液晶組成物及其聚合物(薄膜) [Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、化合物(E1)15mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the compound (E1), and a photopolymerization initiator, Irgacure, Ciba Geigy Co., Ltd. 4 mg of 369 (trade name) and 0.6 mg of R30 (manufactured by DIC) of a surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.7μm，以偏光顯微鏡觀察時，確認薄膜在基板面上水平配向(傾斜角<10°)。其阻滯值為296nm，霧度值為0.08。 The film thickness of the obtained film was 1.7 μm, and it was confirmed by a polarizing microscope that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 296 nm and the haze value was 0.08.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為201nm，霧度值為0.08。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 201 nm and the haze value was 0.08.

[比較例2]聚合性液晶組成物及其聚合物(薄膜) [Comparative Example 2] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、化合物(E2)30mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of a polymerizable liquid crystal compound (A1), 90 mg of a polymerizable liquid crystal compound (A2), 60 mg of a polymerizable liquid crystal compound (B1), 30 mg of a compound (E2), and a photopolymerization initiator, Irgacure 369 (trade name), manufactured by Ciba Geigy Co., Ltd., 4 mg And 0.6 mg of R30 (manufactured by DIC) of the surfactant was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.9μm，以偏光顯微鏡觀察時，確認薄膜在基板面上水平配向(傾斜角<10°)。其阻滯值為261nm，霧度值為0.08。 The film thickness of the obtained film was 1.9 μm, and it was confirmed by a polarizing microscope that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 261 nm and the haze value was 0.08.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為 144nm，霧度值為0.08。 After the film was heated on a hot plate at 200 ° C for 30 minutes, the retardation value was At 144 nm, the haze value was 0.08.

[比較例3]聚合性液晶組成物及其聚合物(薄膜) [Comparative Example 3] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、化合物(E3)30mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of a polymerizable liquid crystal compound (A1), 90 mg of a polymerizable liquid crystal compound (A2), 60 mg of a polymerizable liquid crystal compound (B1), 30 mg of a compound (E3), and a photopolymerization initiator, Irgacure 369 (trade name), manufactured by Ciba Geigy Co., Ltd., 4 mg And 0.6 mg of R30 (manufactured by DIC) of the surfactant was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.9μm，以偏光顯微鏡觀察時，確認薄膜在基板面上水平配向(傾斜角<10°)。其阻滯值為328nm，霧度值為0.16。 The film thickness of the obtained film was 1.9 μm, and it was confirmed by a polarizing microscope that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 328 nm and the haze value was 0.16.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為265nm，霧度值為0.16。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 265 nm and the haze value was 0.16.

[比較例4]聚合性液晶組成物及其聚合物(薄膜) [Comparative Example 4] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., Ltd., and a surfactant of a photopolymerization initiator 0.6 mg of R30 (manufactured by DIC Co., Ltd.) was dissolved in 0.7 g of cyclohexanone to prepare a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製 作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 The same procedure as in Example 1 was carried out except that the polymerizable liquid crystal composition was used. As a film. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上水平配向(傾斜角<10°)。其阻滯值為289nm，霧度值為0.16。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 289 nm and the haze value was 0.16.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為209nm，霧度值為0.16。 After the film was heated on a hot plate at 200 ° C for 30 minutes, the retardation value was 209 nm and the haze value was 0.16.

[比較例5]聚合性液晶組成物及其聚合物(薄膜) [Comparative Example 5] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)150mg、多價丙烯酸酯化合物(C4)9mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 150 mg of the polymerizable liquid crystal compound (A2), 9 mg of the polyvalent acrylate compound (C4), and 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., Ltd. as a photopolymerization initiator, and a surfactant 0.6 mg of R30 (manufactured by DIC Co., Ltd.) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

除使用該聚合性液晶組成物外，與實施例1相同地製作薄膜。而且，預燒成後之基板上的聚合性組成物為液晶狀態。 A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上水平配向(傾斜角<10°)。其阻滯值為258nm，霧度值為1.49。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 258 nm and the haze value was 1.49.

使該薄膜在200℃之熱板上加熱30分鐘後，阻滯值為18nm，霧度值為0.24。 After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 18 nm and the haze value was 0.24.

上述實施例1~6及比較例1~5之結果如下述表3所示。而且，表3中△nd值之熱安定性(%)，係相對於燒成 前△nd值而言燒成後△nd值的比例。 The results of the above Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 3 below. Moreover, the thermal stability (%) of the Δnd value in Table 3 is relative to the firing. The ratio of the Δnd value after firing is the Δnd value.

此外，以上述實施例1~6所製作的薄膜在波長590nm的阻滯值角度相關性如第1圖所示，且以上述比較例1~5所製作的薄膜在波長590nm之阻滯值角度相關性如第2圖所示。 Further, the retardation values of the films prepared in the above Examples 1 to 6 at a wavelength of 590 nm are as shown in Fig. 1, and the films prepared in the above Comparative Examples 1 to 5 have a retardation angle at a wavelength of 590 nm. The correlation is shown in Figure 2.

其次，以實施例說明有關藉由配向薄膜製作步驟控制配向型式(水平或混合型)。 Next, the embodiment will be described with respect to controlling the alignment pattern (horizontal or hybrid type) by the alignment film forming step.

[實施例7]聚合性液晶組成物及其聚合物(薄膜) [Example 7] Polymerizable liquid crystal composition and polymer (film) thereof

將聚合性液晶化合物(A1)150mg、聚合性液晶化合物(A2)90mg、聚合性液晶化合物(B1)60mg、多價丙烯酸酯化合物(C4)4.5mg、光聚合引發劑之Ciba Geigy公司製Irgacure 369(商品名)4mg、及界面活性劑之R30(DIC(股)製)0.6mg溶解於環己酮0.7g中，製得聚合性液晶組成物。 150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 4.5 mg of the polyvalent acrylate compound (C4), and Irgacure 369 manufactured by Ciba Geigy Co., Ltd. as a photopolymerization initiator. (trade name) 4 mg and R30 (manufactured by DIC Co., Ltd.) of 0.6 mg of a surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

將該聚合性液晶組成物藉由旋轉塗覆器(1,000rpm、20秒)塗覆於附液晶配向膜之基板的液晶配向膜面上，在100℃之熱板上預燒成60秒後，放冷至室溫。此時，基板上之聚合性組成物為液晶狀態。此處所使用的附液晶配向膜之基板，係在附ITO之玻璃基板的ITO面上，藉由旋轉塗覆器塗覆液晶配向劑(日產化學工業(股)製PAOC-120)，且在130℃下進行燒成，形成厚度200nm之薄膜後，自斜方(40°)照射500mJ/cm2之偏光UV光者。 The polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by a spin coater (1,000 rpm, 20 seconds), and calcined on a hot plate at 100 ° C for 60 seconds. Allow to cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with a liquid crystal alignment film used here is coated on a ITO surface of a glass substrate with ITO, and a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries Co., Ltd.) is coated by a spin coater at 130 After firing at a temperature of ° C to form a film having a thickness of 200 nm, a polarized UV light of 500 mJ/cm 2 was irradiated from an oblique angle (40°).

其次，使在附液晶配向膜之基板上所形成的塗膜在氮氣環境中使用鹵化甲烷燈、以2,000mJ/cm2強度之光照射，使聚合性液晶組成物予以聚合。 Next, the coating film formed on the substrate with the liquid crystal alignment film was irradiated with a methane lamp under a nitrogen atmosphere at a light intensity of 2,000 mJ/cm 2 to polymerize the polymerizable liquid crystal composition.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上混合配向(平均傾斜角40°)。其阻滯值為143nm，霧度值為0.13。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 143 nm and the haze value was 0.13.

[實施例8]聚合性液晶組成物及其聚合物(薄膜) [Example 8] Polymerizable liquid crystal composition and polymer (film) thereof

除使實施例7所得的聚合性液晶組成物藉由旋轉塗覆器(1,000rpm、20秒)塗覆於附液晶配向膜之基板的液晶配向膜面上，在100℃之熱板上預燒成60秒後，放冷至室溫。此時，基板上之聚合性組成物為液晶狀態。此處所使用的附液晶配向膜之基板，係在附ITO之玻璃基板的ITO面上，藉由旋轉塗覆器塗覆液晶配向劑(日產化學工業(股)製PAOC-120)，且在130℃下進行燒成，形成厚度200nm之薄膜後，自正上方照射1000mJ/cm2之偏光UV光者。 The polymerizable liquid crystal composition obtained in Example 7 was coated on a liquid crystal alignment film surface of a substrate with a liquid crystal alignment film by a spin coater (1,000 rpm, 20 seconds), and calcined on a hot plate at 100 ° C. After 60 seconds, let cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with a liquid crystal alignment film used here is coated on a ITO surface of a glass substrate with ITO, and a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries Co., Ltd.) is coated by a spin coater at 130 After firing at a temperature of ° C to form a film having a thickness of 200 nm, a polarized UV light of 1000 mJ/cm 2 was irradiated from directly above.

其次，使在附液晶配向膜之基板上所形成的塗膜在氮氣環境中使用鹵化甲烷燈、以2,000mJ/cm2強度之光照射，使聚合性液晶組成物予以聚合。 Next, the coating film formed on the substrate with the liquid crystal alignment film was irradiated with a methane lamp under a nitrogen atmosphere at a light intensity of 2,000 mJ/cm 2 to polymerize the polymerizable liquid crystal composition.

所得的薄膜之膜厚為1.8μm，以偏光顯微鏡觀察時，確認薄膜在基板面上水平配向。其阻滯值為306nm，霧度值為0.13。 The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. The retardation value was 306 nm and the haze value was 0.13.

上述實施例7，8所製作的薄膜在波長590nm之阻滯值角度相關性如第3圖所示。 The angle dependence of the retardation values of the films prepared in the above Examples 7 and 8 at a wavelength of 590 nm is shown in Fig. 3.

[產業上之利用價值] [Industry use value]

由本發明組成物所得的聚合物，可適合利用作為偏光板或相位差板等之光學向異性薄膜。 The polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film which is a polarizing plate or a phase difference plate.

[第1圖]係表示實施例1~6所得的薄膜在波長590nm之阻滯值角度相關性的圖。 [Fig. 1] is a graph showing the angular dependence of the retardation values of the films obtained in Examples 1 to 6 at a wavelength of 590 nm.

[第2圖]係表示比較例1~5所得的薄膜在波長590nm之阻滯值角度相關性的圖。 [Fig. 2] is a graph showing the angular correlation of the retardation values of the films obtained in Comparative Examples 1 to 5 at a wavelength of 590 nm.

[第3圖]係表示實施例7~8所得的薄膜在波長590nm之阻滯值角度相關性的圖。 [Fig. 3] is a graph showing the angular dependence of the retardation values of the films obtained in Examples 7 to 8 at a wavelength of 590 nm.

Claims (8)

一種聚合性液晶組成物，其特徵為含有(A)選自以下述式[1]表示之聚合性液晶化合物中之至少1種、(B)選自以下述式[2]表示的聚合性液晶化合物中之至少1種，及(C)選自多元丙烯酸酯化合物之至少1種，該多元丙烯酸酯化合物為具有選自三羥甲基丙烷構造、季戊四醇構造及乙二醇構造中之至少一種的構造或將選自此等中之至少1種予以縮合的構造且為全體具有3個以上50個以下之氧原子的由多元醇與丙烯酸或其衍生物所得者， [式中，R1、R3及R4係各獨立地為以下述式[3]或[4]表示的有機基， (式中，X係表示氫原子或甲基；虛線係表示鍵結鍵)R2係表示氫原子、鹵素原子、氰基或甲氧基；n1、n2及n3係各獨立地表示2~10之整數；q係表示0或1；p係當q為0時為1，當q為1時為0或1；r係表示1或2；s係當r為1時為1，當r為2時為0]。 A polymerizable liquid crystal composition comprising (A) at least one selected from the group consisting of polymerizable liquid crystal compounds represented by the following formula [1], and (B) selected from the group consisting of polymerizable liquid crystals represented by the following formula [2] At least one of the compounds, and (C) is at least one selected from the group consisting of a polyvalent acrylate compound having at least one selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure. a structure obtained by condensing at least one selected from the group consisting of a polyol, an acrylic acid or a derivative thereof, having a structure in which at least one of these is condensed, and having three or more oxygen atoms in total [wherein R 1 , R 3 and R 4 are each independently an organic group represented by the following formula [3] or [4], (wherein X represents a hydrogen atom or a methyl group; the broken line represents a bond; R 2 represents a hydrogen atom, a halogen atom, a cyano group or a methoxy group; and n1, n2 and n3 each independently represent 2 to 10; An integer; q is 0 or 1; p is 1 when q is 0, 0 or 1 when q is 1, r is 1 or 2; s is 1 when r is 1, when r is 2 o'clock is 0]. 如申請專利範圍第1項之聚合性液晶組成物，其中上述多元丙烯酸酯化合物(C)係以下述式[5]或[6]表示， (式中，R5係表示甲基、或以下述式[7]或[8]表示的有機基， n4~n10係各獨立地為0~10之整數；n11係4~10之整數；虛線係表示鍵結鍵)。 The polymerizable liquid crystal composition according to claim 1, wherein the polybasic acrylate compound (C) is represented by the following formula [5] or [6]. (wherein R 5 represents a methyl group or an organic group represented by the following formula [7] or [8], N4~n10 are each independently an integer from 0 to 10; n11 is an integer from 4 to 10; the dotted line indicates a bonding key). 如申請專利範圍第1或2項之聚合性液晶組成物，其中前述聚合性液晶化合物(B)係以下述式[9]表示， (式中，n2、n3、r及s係與上述相同)。 The polymerizable liquid crystal composition according to claim 1 or 2, wherein the polymerizable liquid crystal compound (B) is represented by the following formula [9]. (wherein n2, n3, r and s are the same as described above). 如申請專利範圍第1項之聚合性液晶組成物，其中聚合性液晶化合物(A)之含量在相對於聚合性液晶化合物(B)100質量分而言為100~1,900質量分，多價丙烯酸酯化合物(C)之含量在相對於聚合性液晶化合物(A)及(B)之合計100質量分而言為0.5~5質量分。 The polymerizable liquid crystal composition of the first aspect of the invention, wherein the content of the polymerizable liquid crystal compound (A) is from 100 to 1,900 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound (B), and the polyvalent acrylate The content of the compound (C) is 0.5 to 5 parts by mass based on 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B). 一種聚合物，其特徵為由如申請專利範圍第1~4 項中任一項之聚合性液晶組成物所得。 a polymer characterized by the first to fourth aspects of the patent application The polymerizable liquid crystal composition of any one of the items. 一種被膜，其特徵為由如申請專利範圍第1~4項中任一項之聚合性液晶組成物所得。 A film obtained by the polymerizable liquid crystal composition according to any one of claims 1 to 4 of the patent application. 一種混合型配向薄膜，其特徵為由如申請專利範圍第1~4項中任一項之聚合性液晶組成物所得。 A hybrid alignment film obtained by the polymerizable liquid crystal composition according to any one of claims 1 to 4. 一種光學構件，其特徵為具備如申請專利範圍第7項之配向薄膜。 An optical member characterized by comprising an alignment film according to item 7 of the patent application.
TW101133777A 2011-09-15 2012-09-14 Polymerizable liquid crystal composition and alignment film TWI555826B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011201793 2011-09-15

Publications (2)

Publication Number Publication Date
TW201326372A TW201326372A (en) 2013-07-01
TWI555826B true TWI555826B (en) 2016-11-01

Family

ID=47883283

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101133777A TWI555826B (en) 2011-09-15 2012-09-14 Polymerizable liquid crystal composition and alignment film

Country Status (5)

Country Link
JP (1) JP5958471B2 (en)
KR (1) KR102045532B1 (en)
CN (1) CN103827155B (en)
TW (1) TWI555826B (en)
WO (1) WO2013039053A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6536403B2 (en) * 2013-08-23 2019-07-03 日産化学株式会社 Composition for film formation and single layer coating type horizontal alignment film
WO2015098702A1 (en) * 2013-12-25 2015-07-02 Dic株式会社 Compound containing mesogenic group, and mixture, composition, and optically anisotropic body using said compound
KR20170105012A (en) * 2015-01-16 2017-09-18 디아이씨 가부시끼가이샤 Polymerizable composition and optically anisotropic body using same
WO2017138509A1 (en) * 2016-02-10 2017-08-17 日産化学工業株式会社 Liquid-crystal composition and horizontal-alignment single-layer film formed by coating fluid application
KR102538719B1 (en) * 2016-12-08 2023-06-01 메르크 파텐트 게엠베하 Polymerisable compounds and the use thereof in liquid-crystal displays

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200804569A (en) * 2006-06-29 2008-01-16 Chisso Corp Polymerizable liquid crystal composition
TW200838856A (en) * 2006-12-15 2008-10-01 Nissan Chemical Ind Ltd Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and alignment film

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270407A (en) 1985-09-25 1987-03-31 Fuji Photo Film Co Ltd Preparation of orientated film
JP3134525B2 (en) * 1992-08-07 2001-02-13 三菱化学株式会社 Dimming material and dimming element comprising the same
JPH09208957A (en) 1996-01-31 1997-08-12 Teijin Ltd Production of optical isomer
TW373123B (en) 1996-07-26 1999-11-01 Merck Patent Gmbh Combination of optical elements, means to produce substantially linear polarized light, optical retardation film and liquid crystal display device
JP4099955B2 (en) * 2000-10-02 2008-06-11 オムロン株式会社 (Polymer / liquid crystal) composite film display device and method for manufacturing the same
JP4066318B2 (en) * 2001-02-23 2008-03-26 日本化薬株式会社 Retardation film comprising UV-curable resin composition for alignment film and polymer film having liquid crystal compound
JP4507490B2 (en) * 2002-12-26 2010-07-21 チッソ株式会社 Photopolymerizable liquid crystal composition and liquid crystal film
JP4721721B2 (en) * 2004-02-18 2011-07-13 株式会社Ａｄｅｋａ Polymerizable compound and polymerizable liquid crystal composition containing the compound
US7862867B2 (en) * 2006-10-05 2011-01-04 Nissan Chemical Industries, Ltd. Bifunctional polymerizable compound, polymerizable liquid crystal composition, and oriented film
WO2008052376A1 (en) 2006-11-03 2008-05-08 Rolic Ag Birefringent layer of c-plate and o-plate type
WO2008123235A1 (en) * 2007-03-30 2008-10-16 Dic Corporation Polymer-stabilized liquid crystal composition, liquid crystal display, and process for production of liquid crystal display
JP2009069813A (en) * 2007-08-20 2009-04-02 Fujifilm Corp Phase difference film, polarizer, and liquid crystal display device using the same
JP2009086257A (en) * 2007-09-28 2009-04-23 Dainippon Printing Co Ltd Retardation film
JP5578079B2 (en) * 2008-10-14 2014-08-27 日産化学工業株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition and alignment film
EP2479170B1 (en) * 2009-09-16 2018-01-03 Nissan Chemical Industries, Ltd. Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and oriented film
JPWO2012011435A1 (en) * 2010-07-20 2013-09-09 日本ゼオン株式会社 Retardation film laminate used for stereoscopic image device
JP2012256007A (en) * 2011-06-10 2012-12-27 Nippon Zeon Co Ltd Liquid crystal composition for patterned retardation film, patterned retardation film, and stereoscopic display device
TW201310140A (en) * 2011-06-22 2013-03-01 Zeon Corp Pattern phase difference plate and manufacturing method thereof, and liquid crystal display device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200804569A (en) * 2006-06-29 2008-01-16 Chisso Corp Polymerizable liquid crystal composition
TW200838856A (en) * 2006-12-15 2008-10-01 Nissan Chemical Ind Ltd Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and alignment film

Also Published As

Publication number Publication date
JPWO2013039053A1 (en) 2015-03-26
TW201326372A (en) 2013-07-01
CN103827155B (en) 2016-03-16
WO2013039053A1 (en) 2013-03-21
KR102045532B1 (en) 2019-11-15
JP5958471B2 (en) 2016-08-02
KR20140062483A (en) 2014-05-23
CN103827155A (en) 2014-05-28

Similar Documents

Publication Publication Date Title
TWI421244B (en) A polymerizable liquid crystal compound and a polymerizable liquid crystal composition and an alignment film
TWI405759B (en) A difunctional polymerizable compound, a polymerizable liquid crystal composition and an alignment film
TWI488846B (en) Polymerizable liquid crystal compounds and polymerizable liquid crystal compositions and alignment films
TWI394822B (en) Polymerizable liquid crystal compounds and polymerizable liquid crystal compositions containing the same, and polymers obtainable therefrom
TWI519527B (en) A polymerizable liquid crystal compound, a polymerizable liquid crystal composition, and a alignment film
TWI500743B (en) Polymerizable compounds, polymerizable liquid crystal compositions, polymers and alignment films
TWI555826B (en) Polymerizable liquid crystal composition and alignment film
TWI703388B (en) Composition for manufacturing liquid crystal alignment film for horizontal electric field drive type liquid crystal display element, liquid crystal alignment film using the composition and manufacturing method thereof, and liquid crystal display element having liquid crystal alignment film and manufacturing method thereof
TWI521048B (en) A polymerizable liquid crystal compound, a polymerizable liquid crystal composition, and a alignment film
TW201527393A (en) Film forming composition and monolayer coating type horizontal alignment film