TW201247846A - Polymeric liquid crystal compound, polymeric liquid crystal composition, and oriented film - Google Patents

Abstract

Provided are: the polymeric liquid crystal compound represented by formula [1]; a polymeric liquid crystal composition containing same; a polymer, coating film, and oriented film obtained using same; and an optical member provided with the oriented film. (In the formula: X1, X2, X3, and X4 each independently represent a hydrogen atom or a fluorine atom; R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group; G represents a -C(=O)O- or -OC(=O)- group; and n represents an integer from 4 to 10.)

Description

201247846 VI. [Technical Field] The present invention relates to a polymerizable liquid crystal compound having polymerizability and liquid crystallinity, a composition containing the same, and a polymer and alignment film obtained by using the same, for example It can be suitably used for a material having optical characteristics such as a display device or a recording material, in particular, a polymerizable liquid crystal compound of an optical compensation film such as a polarizing plate for a liquid crystal display or a phase difference plate, a composition containing the same, and the like. The obtained polymer and alignment film. [Prior Art] The requirements for the improvement of the display quality of the liquid crystal display device, such as the improvement of the display quality of the liquid crystal display device, and the optical compensation film such as a polarizing plate or a retardation plate are required to control the polymer film having an internal molecular alignment structure. In order to meet this requirement, a film which utilizes optical anisotropy of a polymerizable liquid crystal compound has been developed. The polymerizable liquid crystal compound used herein generally has a polymerizable group and a liquid crystal structure portion (having a spacer portion and a mesogen). As the liquid crystal compound of the structural portion of the portion, an acrylic group can be widely used as the polymerizable group. Such a polymerizable liquid crystal compound is generally formed by polymerizing a film by irradiation with ultraviolet rays or the like to form a polymer (film). For example, a method in which a polymerizable liquid crystal compound having a specific acryl group is supported between a support, and the compound is held in a liquid crystal state while irradiating radiation to obtain a polymer is known (see Patent Document 1) or - 201247846 A mixture of two types of polymerizable liquid crystal compounds having an acrylic group, or a method in which a photopolymerization initiator is added to a composition of a palm liquid crystal to irradiate ultraviolet rays to obtain a polymer (refer to the patent document) 2) The polymer (film) obtained by the above-mentioned methods is a film for a polarizing plate or a phase difference plate, and the like, not only a display device such as a monitor or a television is mounted in, for example, a car. A display device used in a high temperature environment or the like. Therefore, it is very important to maintain transparency as a material for display devices in a high temperature environment. However, when the film obtained from the polymerizable liquid crystal compound has a glass transition temperature (hereinafter referred to as Tg) which is equal to or lower than the temperature of the use environment, particularly in a high-temperature environment, molecular microscopic oscillation occurs, so that the alignment is disordered, and sometimes the optical The anisotropy is significantly reduced. Further, in the field of displays, in recent years, research into the simplification of the process of using such materials as In Cell retardation films has been actively conducted. The materials used in this In Cell technology can further require high thermal stability and chemical resistance. Further, depending on the orientation pattern of the polymerizable liquid crystal compound, various alignment films such as horizontal, vertical, and mixed alignment can be obtained, and a mixed alignment film exhibiting various average tilt angles has also been reported (see Patent Document 3). Among them, the additive of the liquid crystal composition can be widely used in the field of liquid crystal displays by controlling the average tilt angle of the obtained film with a low addition amount. [Prior Art Document] -6-201247846 [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei 9-208957 (Patent Document 3) International Publication No. 08/052376 OBJECTS OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in view of such circumstances, and an object thereof is to provide an optical anisotropy excellent in stability and stable retardation and transparency even at a high temperature. Further, a polymerizable liquid crystal compound having a high degree of chemical resistance and heat resistance can be obtained, and an average angle of the mixed alignment film can be controlled at a low level, a polymerizable liquid crystal composition containing the same, and a polymerizable liquid crystal. The polymer obtained from the composition and the alignment film. [Means for Solving the Problem] The inventors of the present invention have found that a specific polymerizable liquid crystal compound having an α-methylene-γ-butyrolactone moiety has liquid crystallinity and is itself in order to solve the above problems. It is excellent in polymerizability, and at the same time, it can control the average angle of the mixed alignment film at a low addition amount, and at the same time, obtain a stable liquid crystal composition, and a polymer or film obtained from the liquid crystal composition, in optical anisotropy and transparency. The invention has excellent heat resistance and has finally completed the present invention. That is, the present invention is a polymerizable liquid crystal composition characterized by the following formula [丨] 201247846

(wherein, X1, X2, X3 and X4 each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxy group, and the G system represents -C( = 0)0- or -0C(= 0)-base, η represents an integer from 4 to 10). A polymerizable liquid crystal composition containing the polymerizable liquid crystal compound according to item 1. 3. The polymerizable liquid crystal composition according to the second aspect, which further comprises a liquid crystalline compound having one or more polymerizable groups in the molecule. 4. The polymerizable liquid crystal composition according to the third aspect, wherein the liquid crystal compound is a compound having one or more polymerizable groups represented by the following formula [2] or [3] in one molecule;

(In the formula, the dotted line indicates the bonding hand). 5. The polymerizable liquid crystal composition according to Item 3 or 4, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formula [4] or [5]; 201247846; 】

(wherein X represents a fluorine atom, a cyano group or a carbon number 4 to 8 one-valent hydrocarbon group ' Π and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9 'Μ1, M2 and M3 Respectively, the bases represented by the following formula [2] or [3] are respectively shown;

(In the formula, the dotted line indicates the bonding hand). A polymer obtained by the polymerizable liquid crystal composition according to any one of items 2 to 5. A film obtained by a polymerizable liquid crystal composition according to any one of Items 2 to 5. 8_- an alignment film obtained by the poly-Δ liquid crystal composition according to any one of items 2 to 5. 9' an optical member comprising a heart ring sigma as in item 6 or an alignment film as in item 8. 201247846 ι〇·- a compound characterized by the following formula [6];

[6] (wherein Υ represents -ΟΗ or -COOH, and k represents an integer of 4 to 10). [Effect of the Invention] The polymerizable liquid crystal compound of the present invention and the composition containing the same have excellent optical anisotropy and a polymer which is stable in a high-temperature environment and has transparency. Further, the polymerizable liquid crystal compound of the present invention has an advantage that the amount of optical anisotropy of the composition containing the composition can be controlled with a small amount of addition. Therefore, the polymer obtained from the composition containing the polymerizable liquid crystal compound can be suitably used as an optical anisotropic film such as a polarizing plate or a retardation film. [Formation for Carrying Out the Invention] The method of using the terms in this specification is as follows. The term "polymerizable liquid crystal compound" means a compound having a polymerizable site such as an acrylic group or an α-methylene lactone ring and a liquid crystal structure in the molecule and exhibiting a liquid crystal phase. This "liquid crystal structure" means a structure which can be used for a liquid crystal molecule and has a spacer portion and a crystal former portion. The "liquid crystal composition" means a composition having characteristics exhibiting a liquid crystal phase. "Crystallinity -10- 201247846" means a liquid crystal phase. Hereinafter, the present invention will be described in more detail. [Polymerizable liquid crystal compound] The polymerizable liquid crystal compound of the present invention is characterized by the following formula [1].

(wherein X1, X2, X3 and X4 each independently represent a hydrogen atom or a fluorine atom, 'R represents a halogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an oxycarbonyl group, and the G system represents - C( = 0)0- or - 〇c( = 〇)-base, η is an integer from 4 to 10). The compound represented by the formula [1] is a compound having a lactone ring and a liquid crystal structure, and has a polymerizable liquid crystal compound having an α-methylene-γ-butyrolactone moiety. Among the α-alkylidene-γ-butyrolactone-based α-alkylene-γ-butyrolactone, it has little effect on steric hindrance, and exhibits excellent effects of high polymerizability. . Further, the polymer obtained by using this compound is effective because it imparts high Tg or heat resistance. The repeating portion of the 'methylene group in the formula [1] is referred to as a portion of the so-called spacer portion. Here, η represents a repeating number of methylene groups, and is an integer of 4 to 10, and -11 - 201247846 is preferably an integer of 4 to 6. R in the formula [1] represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group. Here, the halogen atom may, for example, be fluorine, chlorine, bromine or an iodine atom, but in the present invention, it is preferably a fluorine atom. The alkyl group may be any of a straight chain, a branch, and a ring, and The carbon number is not particularly limited, but in the present invention, it is preferably a linear alkyl group having 1 to 10 carbon atoms. Specific examples of the above alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, t-butyl, t-butyl, cyclobutyl, and Pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like. The alkyl group constituting the alkoxy group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited, but in the present invention, it is preferably a linear carbon number of 1 to 1. An alkoxy group of an alkyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. N-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy and the like. The alkyl group constituting the alkoxycarbonyl group may be any of a straight chain, a branch, and a ring, and the carbon number thereof is not particularly limited, but in the present invention, it is preferably a linear carbon number 1~ 1 〇 alkyl alkoxycarbonyl. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, and a -12-201247846 isobutoxycarbonyl group. Dibutoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-decyloxycarbonyl, n-decyloxycarbonyl and the like. At least one of the hydrogen atoms of the alkyl group, the alkoxy group and the alkoxycarbonyl group may be further substituted with another substituent such as a halogen atom. Among the above R-based substituents, a hydrogen atom, a halogen atom and an azoxy group are more preferably an alkoxycarbonyl group which is preferably an ammonia atom, a gas atom or a linear alkyl group having 1 to 5 carbon atoms. . The polymerizable liquid crystal compound represented by the above formula [1] represents a liquid crystal phase of a so-called smectic phase or a nematic phase. This characteristic can be used in the field of use for utilizing optical anisotropy such as a polarizing plate or a phase difference plate. Specific examples of the polymerizable liquid crystal compound include compounds represented by the following formulas (1) to (3), and the like, and are not limited thereto. -13- 201247846

[Chemistry 7 Q

α

(CH2)5-〇

(CH2)6 ο.

(CH2)7-〇

(ch2)8-o

Q

(012), 0-0

(CHA-O (CH^-O

(l) (2) (3) (4) (5) (6) (7) 14 201247846 [Chem. 8]

(CH2)10-〇 (15) 201247846

(16) (17) (18)

(19) (20) (21)

(CH2)10-〇

(22) 16 201247846 (CH^aCHj

(23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) [Synthesis of Polymeric Liquid Crystal Compounds] -17- 201247846 The polymerizable liquid crystal compound of the present invention can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited. The compound having an α-methylene-γ-butyrolactone structure can be synthesized by a method such as that proposed by Talaga et al. (Ρ. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1 990)). . This method is a method of reacting 2-(bromomethyl)propenoic acid with aldehyde and a ketone using SnCl2 as shown by the following synthesis mechanism (A1). Further, 2-(bromomethyl)acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, D. J. 0' Donnell and K. D. Berlin, Organic Synthesis, Vol. 61, 56-59 (1983)).

HO HO

Formaldehyde solution NaHC03 [Chemical 1 1 COOEt COOEt COOH -Br

R, a CHO

SnCl2/Amberlyst 15 THF^20

R· (Al) (wherein R' represents a monovalent organic group, Amberlyst (registered trademark) 15 is a Rohm & Hass company ion exchange resin. Et represents an ethyl group. Further, SnCl2 is used as a 2-bromo group. In the reaction of acrylic acid, an aldehyde or a ketone is substituted by a reaction with a corresponding acetal or ketal, and an α-methylene-γ-butyrolactone structure can also be obtained. The acetal or ketal may, for example, be a compound having dimethyl acetal, diethyl acetal -18-201247846, 1,3-dioxyl group, 1,3-dioxolane or the like. The synthesis method and protecting group in the case of showing an acetal or a ketal in the following synthesis mechanism (A2). [1 2]

(wherein R' represents the same meaning as described above. The broken line indicates the bonding hand). The intermediate compound for synthesizing the compound represented by the formula [1] can be synthesized by the method of the following synthesis mechanism (B) or (C) using the above-described synthesis mechanism (A1) or (A2). [Chemical 1 3 H〇-(CH2)n+1-Br HO—^~^~COOMe -► H〇-(CH2)n+"〇- K2C〇3/Acetone-COOMe H〇-(CH2)n+r 〇-i> PCC -COOMe CH2a2 OHC-(CH2)m Λ- -COOMe

(B) (wherein, n represents the same meaning as above. Me means methyl. PCC means pyridyl chlorochromate) -19- 201247846 [Chem. 1 4]

K2C〇3 Λ -·〇·〇·-1[>

(CH2)n-〇

-OH

(C) (wherein n represents the same meaning as described above). Then, the intermediate medium and the phenolic compound are reacted and esterified as shown in the following synthesis means (D) or (E) to obtain a polymerizable liquid crystal compound represented by the formula [1].

(wherein η, X1 to X4 and R are the same meanings as described above. DCC represents dicyclohexylcarbonyldiimide, DM ΑΡ represents Ν, Ν-dimethyl-4-aminopyridinium ratio D set)

-20- 201247846 (wherein η, X1 to X4 and R represent the same meaning as described above). [Polymerizable liquid crystal composition] The polymerizable liquid crystal composition of the present invention may be a polymerizable liquid crystal compound containing at least one kind of the polymerizable liquid crystal compound of the above formula [1], but the polymerizable liquid crystal composition of the present invention. By mixing the polymerizable liquid crystal compound of the formula [1] and the compound having a liquid crystal structure (hereinafter referred to as a specific compound), a mixed alignment film can be obtained. Therefore, it is preferable to contain at least one kind of polymerization represented by the formula [1]. A liquid crystal compound and the above specific compound. Further, the specific compounds to be mixed may be used singly or in combination of plural kinds. In this case, the specific compound may have a polymerizable group such as an acrylic group or a lactone ring, or may not. The specific compound having a polymerizable group may be monofunctional or polyfunctional. The specific compound is a compound which does not have a polymerizable group and exhibits a liquid crystal property, a compound having a polymerizable group and exhibiting liquid crystallinity, and a compound other than the polymerizable liquid crystal compound of the present invention. The polymerizable group which the above specific compound has may be, for example, a group represented by the following formula [2] or [3]. [化1 7]

(wherein the dotted line indicates a bonding hand) -21 - 201247846 The specific compound having the above polymerizable group is preferably a group represented by the following formula [4] or [5].

M'-(CH2)n-

[4] (In the formula, Μ1, Μ2 and Μ3 are each independently a group represented by the following formula [2] or [3]. X represents a hydrogen atom, a cyano group or a hydrocarbon group having a carbon number of 4 to 8 and fluorene. And f2 each independently represent an integer of 2 to 9, and g is an integer of 2 to 9) The blending ratio of the specific compound is not particularly limited, but is 100 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound of the formula [1]. 200 to 1 900 parts by mass, preferably 100 to 900 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound of the formula [1]. Specific examples of the specific compound described above include compounds represented by the following formulas (36) to (126) described in the handbook of International Publication No. 06/1 1 5 03 3 and International Publication No. 06/115112. Or a nematic liquid crystal, a ferroelectric liquid crystal, a commercially available liquid crystal composition, or the like, but is not limited thereto. -22- 201247846

(ch2)3-o

(ch2)6-o

(ch2)9-o

(36) (37) (38) (39) (40) (41) (42) (43) -23 (44)201247846 [Chemical 2 0]

(45) (46) (47) (48) -24- 201247846 [Chem. 2 1]

(ch2)4-o

Jhch2) 4-o

(49) (50)(51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62)201247846 [Chemistry 2 2

α

(CH2)5-o (CH2)5-〇 (CH2)5-o

OMe

(ch2) 5-o (CH2) wide. ο ^

(ch2)5-o

(CH2)5'〇

Ο—(CH2)3-a 〇-(Ch2)4-

Q

(CH2)5-〇

Q

Q

(CH2)5-〇

(CH2)5-〇 (CH2)5-〇

〇-(ch2)6-(T 〇-(CH2)7~〇 J—〇—(ch2)z-o

Q

(CH2)5-〇 a

(CH2)3-〇

〇-(CH2), 〇-(63) (64) (65)(66) (67)(68) (69) (70) (71) (72) (73) (74) 26-201247846 3]

(75) (76) (77) (78) (79) (80) (81) (82) (83) (84) (85) (86) (87) 27- (88) 201247846 [Chem. 2 4

ο

O-(ch2)7—〇·α

(CH2)7-〇

(89)(90) (91) (92) (93) (94) (95) (96) (97) (98) (99) (100) 28- (101)201247846 [Chem. 2 5]

(102) (103) (104) (105) (106) (107) (108) (109) (110) 〇Π) (112) (113) 29-201247846

[chemical 2 6 (ciy9-o

o (ch2)9-o

(CH2)9-〇

〇-(CH2)4*

(CH2)9-〇 ^_^°~0~〇·0'

-(CH2)5—I 0

〇-(CH2)6- .X- (CH2)9-〇-ii

(114) (115) (116) (117) (118) (119) (120) (121) (122) 023) (124) (125) (126) In the polymerizable liquid crystal compound of the present invention, it is improved For the purpose of polymerization reactivity -30-201247846, a photopolymerization initiator, a thermal polymerization initiator, a photosensitizer, or the like may be added. Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, acetophenones such as diethoxyacetamethylene, and benzoyl benzyl ketal. Ketal ketones and the like. The above photopolymerization initiators may be used singly or in combination of plural kinds. The amount of the photopolymerization initiator added is a total amount of the polymerizable liquid crystal compound represented by the formula [1] and the specific compound exhibiting liquid crystallinity (hereinafter, referred to as a total of the liquid crystal compound) 00 parts by mass is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass. The above thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile or the like. The thermal polymerization initiator may be used alone or in combination of a plurality of them, and the amount thereof is preferably 5 parts by mass or less, more preferably 0-5 to 2.0 parts by mass, per 100 parts by mass of the total liquid crystalline compound. The photosensitizing agent may, for example, be a quinone-based photosensitizer such as hydrazine. The light sensitizer may be used singly or in combination of a plurality of kinds, and the amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the total liquid crystal compound. Further, the photopolymerization initiator may be used in combination with at least one of a thermal polymerization initiator and a photosensitizer. In the polymerizable liquid crystal composition of the present invention, a stabilizer may be added for the purpose of improving the preservation stability. The stabilizer may, for example, be a hydroquinone monoalkyl ether such as hydroquinone or hydroquinone monomethyl ether or 4-tert-butylcatechol. The stabilizer may be used singly or in combination of plural kinds, and the amount thereof is preferably 0.1 part by mass or less based on 100 parts by mass of the total liquid crystal compound of -31 - 201247846. In the polymerizable liquid crystal composition of the present invention, the adhesion promoter may be added for the purpose of improving the properties with the substrate. The adhesion promoter may, for example, be trimethylchlorodecane, dimethoxyl chlorodecane, methyl diphenyl chlorodecane or chloromethyl dimethyl chlorohydrazine; trimethyl methoxy decane; Alkoxy decane such as dimethyldiethoxy fluorenylmethyldimethoxydecane, dimethylvinylethoxy decane, diphenylmethoxydecane, phenyltriethoxydecane; a nonazepine such as diazane, N,N'-bis(trimethyldecyloxy)urea, dimethyl methoxyoxyl, trimethyldecyloxyimidazole; ethylene chlorodecane, γ- Chloropropyltrimethoxydecane, γ-aminopropyltriethoxysilane, γ-methylpropenyloxypropyltrimethoxydecane, γ-glycidylpropyltrimethoxydecane, γ-(Ν a decane such as hexahydropyridyl)propyltrimethoxane; benzotriazole, benzimidazole, anthracene, imidazolium thiobenzimidazole, 2-hydrothiobenzothiazole, 2-hydrothiobenzene Further, a hetero compound such as urazolium, thiouracil, hydrothioimidazole or thiopyrimidine; a urea thiourea compound such as 1,1-dimethylurea or 1,3-diurea; and the like. The adhesion promoter may be used alone or in combination of plural kinds, and the amount of addition is preferably 10,000 parts by mass or less, based on the total amount of the liquid crystalline compound. Further, the polymerizable liquid crystal composition of the present invention may be added with an organic solvent for the purpose of scheduling or the like. In this case, liquid crystallinity may not be exhibited in the organic solvent-containing state. Alkane ethane and the like 'alkyl di-* - m /, methyltrimethyltriyl methoxyoxy, 2-D oxime sitting ring;, its quality and viscosity -32-201247846 Examples of the organic solvent include ether benzene such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; polar solvents such as N,N-dimethylformamidine N-methyl-2-pyrrolidone; and acetic acid; Esters of ethyl ester, acetic acid, ethyl lactate, etc.; 3. methyl methoxypropionate, 2-methoxymethyl ester, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate , alkoxy esters such as ethyl 3-ethionate and ethyl 2-ethoxypropionate; glycol dialkyl ethers such as ethylene dimethyl ether and propylene glycol dimethyl ether; Diethylene glycol dialkyl ethers such as ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, glycol dimethyl ether; ethylene glycol monomethyl ether glycol monoethyl Alcohol monoalkyl ethers such as ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Diethylene glycol monoethers; propylene glycol Glycol monoalkyl ether esters such as methyl ether acetate, carbitol acetate, ethyl acetate, etc.; ketones such as cyclohexanone, methyl ethyl ketone, isobutyl ketone, and 2-heptanone Wait. These organic solvents are! It is also possible to use two or more types in combination. Among these, 'safety from the global environment and the working environment is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, lactic acid, and the like. Further, the amount of the organic solvent used is about 60 to 95% by mass in the polymerizable liquid crystal compound. Further, in the polymerizable liquid crystal compound of the present invention, a surfactant may be added for the purpose of improving the affinity thereto. The above-mentioned interface activity is not particularly limited, and examples thereof include a fluorine-based surfactant and a polyoxane-based compound: an amine, a butyrate-propionic acid oxy alcohol diol di-dipropylene, a glycolate, and a hospital-based solute methyl group. Single-point, ethyl ester-suitable substrate-based agent interface-33-201247846 Active agent, non-ionic surfactant, etc., but preferably a fluorine-based surfactant having a high affinity improving effect on a substrate. Specific examples of the fluorine-based surfactant include, for example, (hereinafter, trade names), EFTOP EF 301, EF 3 03, EF 3 52 (manufactured by Tochem Products), Megfac F171, F173, R-30 (DIC ( Stock system), Fluorad FC 43 0, FC 43 1 (Sumitomo 3M (share) system), Asahiguard AG 710, Surf1 1 ο n S-3 82, SC101, SC102, SC 103, SC 104, SC 105, SC 106 (Asahi Glass Co., Ltd.), etc., but is not limited to this. In addition, the surfactant may be used alone or in combination of a plurality of them, and the amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the total liquid crystal compound. A suitable example of the polymerizable liquid crystal composition of the present invention is, for example, a polymerizable liquid crystal compound represented by the formula [1], 1 part by mass, 400-900 parts by mass of a specific compound exhibiting liquid crystallinity, and a photoinitiator. 5 parts by mass or less of the liquid crystal composition or the like, but is not limited thereto. The polymerizable liquid crystal composition described above can be suitably used as a composition or a coating liquid for forming an alignment film. The preparation method of 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 sequentially. The order of addition of each component in the case of sequential mixing is arbitrary. Further, when a plurality of compounds are used for one component, the mixture in which the mixture is mixed may be mixed with other components in advance, or may be separately mixed with other components. When the optically active liquid crystal composition of the present invention is used to produce an optical isomer, it is -34-201247846 to avoid the initiation of thermal polymerization which is not intended for photopolymerization in a liquid crystal state, and to make the molecular uniform alignment state easy to fix, preferably at room temperature. (20 to 40. (: 'The same applies hereinafter) shows a liquid crystal phase which is mutually denatured. Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferable to use a liquid crystal phase which is mutually denatured at room temperature when the solvent is removed. And a film] The polymerizable liquid crystal composition of the present invention described above can be obtained by light irradiation or heat treatment to obtain a polymer. Further, the polymerizable liquid crystal composition is held between two substrates, or spin-coated on a substrate or When a polymerizable liquid crystal composition is applied by a casting method or the like, a light irradiation treatment is performed to obtain a film. In this case, a plastic such as glass, quartz, color filter or triethylenesulfonate (TAC) can be used for the substrate. A sheet or a film, etc. Further, in one of the two substrates, a glass, a plastic sheet, a plastic film or stainless steel or an electric ore which is formed with a functional film such as tantalum may be used. The steaming shovel has a metal strip or a drum body such as chrome or aluminum. The substrate to be used is used for the purpose of improving the blending and aligning properties of the obtained film, and it is preferable to carry out an oblique alignment treatment. A method of forming a polyimide, a polyimide, a polyvinyl cinnamate, or the like, rubbing or irradiating a polarized ultraviolet ray obliquely, and forming a cerium oxide oblique vapor deposition film. A known method such as a method of LB film is appropriately selected and used, but it is preferable to use an available oblique alignment method in any of them. -35- 201247846 A method of holding a polymerizable liquid crystal composition between two substrates is A cell in which a space is formed between two substrates by a spacer or the like, and a polymerizable liquid crystal composition is injected into a unit cell by a method such as a capillary image or a space of a reduced-pressure unit cell, and then irradiated with light to be polymerized. Further, in a simpler method, a polymerizable liquid crystal composition is placed on a substrate provided with a spacer or the like, and the other substrate is stacked thereon to form a unit cell, and the light is irradiated. In this case, the polymerizable liquid crystal composition may be fluidized, or may be placed on a substrate and then fluidized by heating or the like, but must be polymerized before being overlapped with the other substrate. Further, the method of holding the polymerizable liquid crystal composition between the two substrates is to obtain the mixed alignment, so that the substrate of the single sheet is not subjected to the alignment treatment, or the vertical alignment treatment can be performed. The method of coating a polymerizable liquid crystal composition may be a step of applying a polymerizable liquid crystal composition, and a step of heating with a hot plate or the like as needed in the middle of the step of polymerizing by light or heat. In particular, when a polymerizable liquid crystal composition (coating liquid) containing an organic solvent is used, a means for removing an organic solvent from the composition is effective. Even in the method of any of the above, the polymerizable liquid crystal composition is rendered. The state of the liquid crystal phase is polymerized to obtain a film having an optical anisotropy which has been aligned. In order to obtain a polymer having a plurality of regions in different orientations in each adjacent region, a method of performing multi-regionization in the step of polymerization or a method of multi-regionizing the substrate can be used. -36- 201247846 The method of multi-regionalization by a polymerization method is a liquid crystalline liquid crystal composition in which a liquid crystal state is exposed, and ultraviolet rays are exposed through a mask to form a polymerized region, and the remaining regions are, for example, in an equal manner. A method of polymerization in a liquid state. Further, a method of multi-regionizing the substrate may be, for example, a method of rubbing the alignment material formed on the substrate via a mask, or a method of irradiating ultraviolet rays through a mask. By this method, it is possible to obtain a multi-regionized substrate in which the rubbed region and the region irradiated with ultraviolet rays are subjected to the alignment treatment and the other untreated portions. The polymerizable liquid crystal composition formed on the substrate which is multi-regionized is affected by the alignment layer and is multi-regionized. Further, in addition to the above alignment processing method, a method using an electric field or a magnetic field may be used. 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 or a phase difference plate. 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 a vehicle display device. [Embodiment] [Examples] Hereinafter, the present invention will be more specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the examples described below. Further, the measurement methods and measurement conditions of the respective physical properties in the examples are as follows. -37- 201247846

[1] NMR The compound was dissolved in dihydrochloroform (CDC13) or hydrogenated dimethyl hydrazide (DMSO-d6), and the W-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Diol). [2] Observation of the liquid crystal phase The liquid crystal phase was evaluated by heating the sample on the heating stage (MATS-2002S 's) and using a polarizing microscope (manufactured by Nikon Co., Ltd.). The phase transition temperature is a Bruker AXS (share) differential scanning thermal analysis device (DSC 3100 SR, hereinafter referred to as DSC), which is measured at a scan rate of 1 (TC/min. [3] Yes) The film was measured by Spectral Haze Meter (TC-1 800H) manufactured by Tokyo Electro-Color Co., Ltd. [4] Delay of film 测定 Measurement of wavelength 590 nm using a delay measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.) Delay 値 [5] Average tilt angle of film The average tilt angle of wavelength 5 90 nm was measured using AxoScanTM Mueller Matrix Polarimeter (manufactured by AXOMETRIX Co., Ltd.) -38 - 201247846 [Synthesis Example 1] Synthesis of polymerizable liquid crystal compound (El) [1] Synthesis of Intermediate Compound (A 1 ) [Chemical 2 7]

Br-(CH2)rOH K: 2C03/ acetone

In a 500 ml eggplant type flask equipped with a cooling tube, 4-cyano-4'-hydroxybiphenyl 9.8 g (50.0 mmol), 3-bromo-1-propanol 7.0 g (50.0 mmol), and potassium carbonate 13.8 g (100 mmol) were added. And 150 ml of acetone to form a mixture' while stirring at 64 ° C for 48 hours. After the end of the reaction, the solvent was evaporated under reduced pressure to give a yellow wet solid. Thereafter, the solid was mixed with water for 140 m and then diethyl ether (1 ml) was added thereto for extraction. The extraction system was performed 3 times. The organic layer was separated and dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. This solid was purified by recrystallization using a mixed solution of hexane / ethyl acetate = 2 / 1 (v / v) to afford 8.7 g of a white solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was the intermediate compound (A1) (yield 70%). 'H-NMR(CDC13)5: 2.09(m, 2H), 3.90(t, 2H), 4.20(t, 2H)s 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H) [2] Synthesis of polymerizable liquid crystal compound (El) -39- 201247846

12.0 g of the above-obtained intermediate compound (A1) and 7.7 ml of triethylamine and a small amount of ruthenium (2,6·di-t-butyl-p-cresol) were dissolved in tetrahydrofuran (THF) 40 ml in the room. The mixture was stirred under a cooling water and cooled in a water bath, and a solution of 4.6 ml of acrylonitrile chloride dissolved in 40 ml of THF was added dropwise over 15 minutes. After the dropwise addition, the mixture was stirred for 30 minutes, and the water bath was removed to return to room temperature while stirring was continued overnight to filter the precipitated triethylamine hydrochloride. The THF was distilled off from the obtained filtrate to about 3/4, and 50 ml of dichloromethane was added thereto, and the organic layer was washed successively with 50 ml of a saturated aqueous solution of sodium hydrogencarbonate, 50 ml of 0.5 mol/liter hydrochloric acid, and 50 ml of saturated brine. After drying, the solvent was distilled off to obtain a product. After recrystallization from ethanol, 6.0 g of a polymerizable liquid crystal compound (El) was obtained. 1H-NMR(CDC13)6: 2.20(m, 2H), 4.1〇(t, 2H), 4.4〇(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) [Synthesis Example 2] Synthesis of polymerizable liquid crystal compound (E2)] Synthesis of intermediate compound (A2) 9】

Br-(CH2)6-OH K2C03/Acetone

〇-(CH2)6-〇H (A2) -40- 201247846 In a cooling tube l〇〇ml eggplant type flask, add 4-cyano-4'-hydroxybiphenyl 5.0g (25.6mmol), 6 - 4.6 g (25.6 mmol) of bromo-1-hexanol, 7 g of potassium carbonate (50 mmol) and 50 ml of acetone were mixed to form a mixture, and the mixture was stirred while stirring at 64 t for 24 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow solid. Thereafter, the solid and 70 ml of water were mixed and 50 ml of diethyl ether was added thereto for extraction. The extraction system was carried out 3 times. The organic layer of the separated liquid was dried over anhydrous magnesium sulfate, 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 chromatography on a column of cerium oxide gel column (column: silica gel 60, 0_063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) =1 / 1 (v / v)) refined. The solvent was distilled off from the obtained solution to give a white solid (6 g). The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was the intermediate compound (A2) (yield: 91%). 1H-NMR(DMSO-d6)5: 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) U] Synthesis of intermediate compound (B2) [Chemical 3 Ο]

0—(CH2)6_0H (Α2) PCC, CH, C17

O-(CH2)5-CHO (B2) Then, in a 200 ml three-necked flask equipped with a cooling tube, PCC 2.2g -41 - 201247846 (10.Ommol) and CH2C12 3 0.0ml were added and stirred and mixed, and the above was added dropwise. The obtained intermediate compound (A2) 2.95 g (10 mmol) was dissolved in a solution of 50.0 ml of CH2C12, and further stirred at 40 ° C for 0.5 hour. Thereafter, the solution of the oil adhering to the wall of the flask was removed, and 90 ml of diethyl ether was added thereto, followed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure to give a thick green solid. Ethyl acetate in 3 ml, analyzed by chrome dioxide 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 give 2.8 g of colorless solid. The results of NMR measurement of this solid are shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (?2) (yield: 93%). 'H-NMR (CDC13) 5 : 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, 1 H) [3] Synthesis of polymerizable liquid crystal compound (E2) [Chemical 3 1]

Finally, in the 50 ml eggplant flask with a cooling tube, the intermediate compound (B 2 ) obtained above was added 3.0 g (1 0.0 mm 〇丨), 2-(bromomethyl-42-201247846), and the acid was 1.65 g. (1 0_Ommol), A mber 1 yst (registered trademark) ι 5 1.6g, THF 16.0ml, tin (II) chloride 1.9g (10.Ommol), and pure water 4 · 0 m 1 to form a mixture The reaction was carried out by stirring at 70 ° C for 7 hours. After the completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with purified water (30 ml), and then 50 ml of diethyl ether. The extraction system was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was evaporated from vacuo. The solid was dissolved in 2 ml of ethyl acetate and analyzed by chromatography on a column of cerium oxide gel column (column: oxidized chopped gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) =2/1 (v/v)) Refined. The solvent was distilled off from the obtained solution to obtain 1.5 g of a white solid. The results of NMR measurement of this solid are shown below. From the result, the polymerizable liquid crystal compound (E 2 ) for the purpose of the white solid was confirmed (yield 41%). Ή-ΝΜΚ(〇0€ΐ3)δ : 1.57(111, 6Η), 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) and 'observing the liquid crystal of the polymerizable liquid crystal compound (E2) The result of the phase is an isocratic liquid state at 84 ° C, and it is transferred toward the liquid crystal phase (nematic phase) at 6 ι when the temperature is lowered. [Synthesis Example 3] Synthesis of polymerizable liquid crystal compound (e 3 ) [1] Synthesis of intermediate compound (A3) -43- 201247846

[化3 2] HO

COOCH3

H〇-(CH2)6-Br /^XW-propyl H0-(CH2)6-0-^_||C00CH3 (A3) In a 200 ml eggplant flask with cooling tube, add 7.61 g of 4-hydroxybenzoic acid methyl vinegar (50.0 mmol), 9.2 g (50.0 mmol) of 6-bromo-1-hexanol, 3.8 g (100 mmol) of potassium carbonate, and 70 ml of acetone were mixed to form a mixture, and the mixture was stirred at 64 ° C for 24 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a yellow wet solid. The solid was analyzed by a color column of a ceria gel column (column: silica sand gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 1 / 1 (v/) v)) Refined. The solvent was evaporated from the obtained solution to give a white solid (11.3 g). The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid was the intermediate compound (A3) (yield: 90%). 'H-NMR (CDC13) 5 : 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] Synthesis of intermediate compound (B3) [Chemical 3 3] HO-(CH2)6-〇-^ ^-CO〇CH3 —PCC,CH2Cl2 , 0HC-(CH2)5-0—^~~ ^-cooch3 (A3) (B3) Then, add PCC 2.2g (10.Ommol) and CH2C12 15_0ml in a three-necked flask with a cooling tube and mix and mix, and add -44 - 201247846 2.5 g (10 mmol) of the obtained intermediate compound (A3) was dissolved in 15.0 ml of CH2C12, and further stirred at room temperature for 6 hours. Then, the solution of the oily substance adhering to the wall of the flask was removed, and 90 ml of diethyl ether was added thereto, followed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid. The solid was analyzed by a color column of cerium oxide gel column (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1 (v/v) ))refined. The solvent was distilled off from the obtained solution to obtain 1.3 g of a colorless solid. The results of NMR measurement of this solid are shown below. From this result, it was confirmed that this colorless solid was the intermediate compound (B3) (yield 50%). 1 H-NMR (CDC13) 6 : 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] Synthesis of intermediate compound (C3) [Chemical 3 4]

Then, in the cooling flask 5 Oml eggplant type flask, 1.25 g (5.0 mmol) of the intermediate compound (B3) obtained above, 〇.83 g (5.0 mmol) of 2-(bromomethyl)acrylate, and Amberlyst (registered) were added. Trademark) 15-45-201247846 0.8 g, THF 8.0 ml, tin chloride (II) 0.95 g (5.0 mmol), and pure water 2.0 ml to form a mixture, and the mixture was stirred at 7 ° C for 5 hours while reacting. After the completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 40 ml of purified water, and then 50 ml of diethyl ether was added to extract. The extraction system was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction and dried, and the solvent was evaporated to give a colorless solid (1,5 g). The NMR measurement results of this solid are shown below. From this result, it was confirmed that the colorless solid was the intermediate compound (C3) (yield: 94%). 1 H-NMR (DMSO-d6) 5 : 1.3-1.8 (m, 8H), 2.62 (m, 1 Η), 3.04 (s, 1 Η), 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] Synthesis of intermediate compound (D3) [Chemical 3 5

(CH2)s COOCHi (C3)

1) NaOH (aq) / EtOH 2) Amberlyst 15 THF

In a cooling tube l〇〇ml eggplant type flask, 35 ml of ethanol, the intermediate compound (C 3 ) 1 · 5 g (4 · 7 mm ο 1 ) obtained above, and a 1% by mass aqueous sodium hydroxide solution were added. A mixture was formed at 5 m 1 and reacted while stirring at 85 ° C for 3 hours. After the reaction was completed, 300 ml of water and a reaction liquid were added to a beaker of 500 ml, and the mixture was stirred at room temperature for 30 minutes, and then 5 ml of a 10% by mass aqueous solution of HCl was added dropwise thereto, followed by filtration to obtain a white solid (1.3 g). Then, in a 50 ml eggplant type flask equipped with a cooling tube, the obtained -46-201247846 white solid l.lg, Amberlyst (registered trademark) 15 l.Og, and THF 20.0 ml were added to form a mixture, which was stirred at 70 ° C. After the reaction was completed for 5 hours, the solvent was evaporated under reduced pressure to give a yellow solid. The yellow solid was purified by recrystallization (hexane / ethyl acetate = l/l (v/v)) to give a white solid. The results of NMR measurement of this solid are shown below. From this result, it was confirmed that this white solid was the intermediate compound (D 3 ) (yield 71%). 1H-NMR (DMSO-d6) 8 : 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3. 〇9 (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] Synthesis of compound (P 3 ) [Chemical 3 6 I HO—(CH2)3—Br +

19.2 g (138.0 mmol) of 3-bromo-1-propanol and 18.9 ml of triethylamine were dissolved in 100 ml of THF in a small amount, stirred at room temperature, cooled in a water bath, and dissolved in 15 minutes. THF 50 ml of propylene hydrazine chloride 12.2 ml (150 mmol) was stirred for 30 minutes, and the water bath was removed and returned to room temperature while stirring was continued overnight. The precipitated TEA hydrochloride was filtered, and 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/liter of hydrochloric acid, and saturated brine. After drying over magnesium sulfate, the solvent was evaporated to give a compound -47-201247846 (P3) 18.2 g. The results of the NMR measurement are shown in the following 〇'H-NMR (CDC13) 5: 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] Synthesis of intermediate compound (G3) [Chemical 3 7]

Br—(CH2:

In a 500 ml eggplant type flask with a cooling tube, 17.6 g (94.3 mmol) of biphenol, 1 8.2 g (9 4.3 mm ο 1 ) of compound (P 3 ), 24.0 g (190 mmol) of potassium carbonate, and 250 ml of acetone were added to form a mixture. The mixture was stirred at a temperature of 54 ° C for 20 hours while reacting. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and the solvent was evaporated under reduced pressure to give 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/acetic acid ethyl acetate = 2/1 (v/v)). The solvent was distilled away from the solution obtained here to obtain 6.1 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this white solid was the intermediate compound (G3) (yield 22%). 1H-NMR(CDC13)6: 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), -48- 201247846 6.87(d,2H),6.99(d,2H),7.46(m,4H) [7] Synthesis of intermediate compound (E3) [Chemical 3 8] α

(CH2)s (D3)

COOH + HO

DCC/DMAP

CH2C12

6.1 g (20.0 mmol) of the intermediate compound (D3) obtained above, 6.0 g (20.0 mmol) of the intermediate compound (G3), 8 g of DMAP 〇.〇, and a small amount of BHT were stirred at room temperature, and suspended in two. In 10 ml of methyl chloride, 4.7 g (23.0 mmol) of DCC dissolved in 20 ml of dichloromethane was added and stirred overnight, and the precipitated DCC urea was filtered, and the filtrate was sequentially subjected to 60 ml of each of .5 mol/liter of hydrochloric acid. After washing with a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution and dried over magnesium sulfate, the solvent was evaporated, and then recrystallized from ethanol to obtain a polymerizable liquid crystal compound (E3) 8.8 g (yield 75%) ° 'H -NMRCCDChia : 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, 2H), 7.25(m, 2H), 7.54(m, 2H), 7.59(m, 2H), 8.17(d, 2H) -49- 201247846 And 'observing this polymerizable liquid crystal compound (E3) As a result of the liquid crystal phase, the phase transitions to a phase X phase at 109 ° C when heated, and the phase transitions to a nematic phase at 144 ° C, and becomes isotropic at 168 ° C. Liquid state. [Example 1] Synthesis of Compound (Z1) [1] Synthesis of Intermediate Compound (P 1 ) [Chemical 3 9] /==\ K2C〇3 Η〇~\ /—\ /~COOEt + H〇-( CH2)„—Br —^__^

In a 200 ml eggplant flask with a cooling tube, 4-(4-hydroxyphenyl)benoic acid Ethyl Ester was added. 2.1 g (50.0 mmol), 11-bromo ·Bu-f-carbonol 12.5g (5 0.0 mmo 1 ), potassium carbonate 13. 3 g (1 0 0 mm ο 1 ), and acetone 1 0 0 m 1 to form a mixture, stirring at 641 for 24 hours while And make it react. After the reaction was completed, the reaction solution was poured into 300 ml of pure water to obtain a white solid (20.3 g). From this result, it was confirmed that this white solid was the intermediate compound (P 1 ) (yield 98%) 0 'H-NMR (CDCl3) 6 :1 .3-1 .7 (m, 1 9 Η), 1 · 8 1 (m, 2 Η), 3.67 (m, 2H), 4.02 (m, 2H), 4.42 (t, 2H), 6.97 (d, 2H), 7.57 (d, 2H), 7.62 (d, 2H), 8.09 (d, 2H) -50- 201247846 [2] Synthesis of intermediate compound (Ql)

COOEt (PI) PCC CH2C12 OHC-(CH2), 〇-〇

COOEt (Ql) Then, PCC llg (51 mmol) and CH2CI2 l〇〇ml were added to a 50 〇 ml three-necked flask equipped with a cooling tube to disturb the mixed state, and the intermediate compound (PI) obtained above was added dropwise to 20 g. (49 mmol) was dissolved in a solution of 10 ml of CH2C12 and stirred at room temperature for further 5 hours. Thereafter, the solution of the oily substance attached to the wall of the flask was removed, and 100 ml of diethyl ether was added thereto, followed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid. This solid was purified by cerium oxide gel column chromatography (column: cerium dioxide gel 60, 0.063-0.200 mm 'Merck' eluent: ethyl acetate). The solvent was distilled away from the obtained solution to give a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this colorless solid was the intermediate compound (Q 1 ) (yield 62%). 1H-NMR(CDC13)5: 1.20- 1.65 (m, 19H), 1.81 (m, 2H), 2.41 (t, 2H), 4.11 (t, 2H), 4.42 (m, 2H), 6.99 (d, 2H) ), 7.57(d, 2H), 7.63(d, 2H), 8.01(d, 2H), 9.77(s, 1H) [3] Synthesis of intermediate compound (R1) -51 - 201247846 [Chem. 4 1] OHC —(CH2)10—Ο

OOEt (Q1)

-Br COOH

SnCl2/HCl(aq) THF

(CH2)i〇-〇

ΌΟΕτ (Rl) Then, in a 200 ml eggplant type flask equipped with a cooling tube, 12.4 g (30 mmol) of the intermediate compound (Ql) obtained above, 5.4 g (33 mmol) of 2-(bromomethyl)acrylic acid, 75 ml of THF, and chlorine were added. 6.3 g (33 mmol) of tin (II) and 24 ml of a 1% by mass aqueous solution of HCl were mixed to form a mixture, which was stirred while stirring at 70 ° C for 24 hours. After the completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain 15 g of a white solid. The results of this solid measurement by NMR are shown below. From this result, the intermediate compound (R1) for the purpose of the white solid was identified. 1H-NMR(CDC13)6: 1.30 (m, 12H), 1.41 (t, 3H), 1.47 (m, 12H), 1.58 (m , 2H), 1.81(m, 2H), 2.54(m, 1H), 3.06(m, 1H), 4.13(m, 2H), 4.48(m, 2H), 4.55(m, 1H)# 5.66(s, 1H), 6.23(s, 1H), 7.00(d, 2H), 7.55(d, 2H), 7.66(d, 2H), 8.11(d, 2H) [4] Synthesis of compound (Z1) [Chemical 4 2 】

(ζι) -52- 201247846 In a cooling tube 5 00 ml eggplant type flask, 200 ml of ethanol, 15 g of the intermediate compound (R1) obtained above, and 80 ml of a 10% by mass aqueous sodium hydroxide solution were added to form a mixture. The reaction was carried out while stirring at 85 ° C for 5 hours. After the completion of the reaction, 500 ml of water and a reaction liquid were poured into a beaker of 1 000 ml, stirred at room temperature for 30 minutes, and then 50 ml of a 10 mass/° HC1 aqueous solution was added dropwise thereto, followed by filtration to obtain a white solid. Then, a white solid obtained, a THF of 200 ml, and a 10% by mass aqueous solution of HCl were added to a cooling tube of a 50 ml eggplant type flask to form a mixture, and the mixture was stirred at 70 ° C for 5 hours to cause a reaction. After the completion of the reaction, 500 ml of water and the reaction liquid were placed in a beaker of 1 000 ml, and filtered to obtain 12 g of a white solid. The results of the measurement of the solid by NMR are shown below. From the result, the compound (Z 1 ) for the white solid was confirmed. (Yield 89%, yield from Q1). 1H-NMR (DMSO-d6) 5 : 1.32 (m, 14H), 1.57 (m, 2H) 5 1.71 (m, 2H), 2.54 (m, 1H), 3.09 (m, 1H), 4.01 (m, 2H) ), 4.55(m, 1 H), 5.69(s, 1H), 6.02(s, 1H), 7.05(d, 2H), 7.67(d, 2H), 7.73(d, 2H)S 7.97(d, 2H ), 12.89 (s, broad, 1H) [Example 2] Synthesis of Compound (Z2) [1] Synthesis of Intermediate Compound (P2) - 53 - 201247846 [Chem. 4 3]

Add 15.0 g (72 mmol) of 4-(4-hydroxyphenyl)benzoate ethyl ester to a 500 ml eggplant flask with a cooling tube, 4-bromobutyl-1,3-dioxolane 1 7.4 g (50.0 mmol) ), potassium carbonate 1 9 · 3 g (1 40 mm ο 1 ), and acetone 200 ml to form a mixture, which was stirred at 64 ° C for 48 hours while allowing to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to give 26.1 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this white solid was the intermediate compound (P2) (yield 98%). 'H-NMR(CDC13)5 : 1.4 1 (t, 3 Η), 1. 5 5 -2.0 0 (m, 6H), 3.86 (m, 2H), 3.99 (m, 4H), 4.39 (m, 2H) ), 4.89 (m, 1H), 6.97 (d, 2H), 7.61 (m, 4H), 8.07 (d, 2H) [2] Synthesis of intermediate compound (R2) [4 4]

-54- 201247846 Then, in the cooling tube 300 ml eggplant type flask, the intermediate compound (P2) obtained above was added to 8.5 g (50 mmol), 2-(bromomethyl)acrylic acid 9.1 g (55 mmol), and THF 114 ml. Further, a mixture of 10.4 g (55 mmol) of tin (II) chloride and 36 ml of an aqueous solution of 10% by mass of HCl was formed, and the mixture was stirred at 70 ° C for 20 hours to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain 18.7 g of a white solid. The results of this solid measurement by NMR are shown below. From the results, it was confirmed that the colorless solid was the intermediate compound (R2) (yield: 95%). 1H-NMR (CDC13) 0 : 1.42 (t, 3H), 1.60- 1.95 (m, 6H), 2.64 (m, 1 Η), 3. 1 1 (s, 1 Η), 4.0 3 ( t, 2 Η), 4.4 2 (m, 2Η), 4.58(m, 1H), 5.64(s, 1 H), 6.24(s, 1H), 6.99(d, 2H), 7.63(m, 4H), 8. 12(d, 2H) [3] Synthesis of intermediate compound (Z2) [Chemical 4 5]

COOEt (R2)

1) 10% NaOH(aq)/EtQH> 2) 10% HCl(aq)/THF

^J>-(CH2)4-〇In a 5〇〇ml eggplant type flask with a cooling tube, adding 2〇〇mi of ethanol, the intermediate compound (R 2 ) obtained above 1 8.7 g ( 4 7 mm ο 1 And 10% by mass of a 10% by mass aqueous sodium hydroxide solution was formed to form a mixture, and the mixture was stirred while stirring at 85 t for 5 hours. After the completion of the reaction, water 6 〇 0 mi and reaction liquid -55-201247846 were placed in a beaker of 1 000 ml, stirred at room temperature for 30 minutes, and filtered to give a white solid. Then, a white solid obtained, a THF of 200 ml, and a 10 mass% HCl aqueous solution of 5 〇ml were placed in a cooling tube 50 ml eggplant flask to form a mixture, which was stirred at 70 ° C for 5 hours to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain 15.9 g of a white solid. The results of the measurement of the solid by NMR are shown below. From the result, the compound (Z2) (yield: 92%) of the white solid was confirmed. 1 H-NMR (DMSO-d6) 5 : 1 · 5 0 (m, 2H), 1. 7 5 (m, 4H), 2.5 8 (m , 1H), 3 .1 2 (m, 1 Η), 4.04(m, 2H), 4.59(m, 1H), 5.72(s, 1H), 6.03 (s5 1 Η), 7.04(d, 2H), 7.7 6(m, 4H), 7.97(d, 2H), 1 2.91 (s, broad, 1H) [Example 3] Synthesis of polymerizable liquid crystal compound (Z3) [Chemical 4 6]

The compound (Z2) obtained in Example 2 1 _〇g (2.7 mmol), phenolphthalein_3 g (3.1 mmol), DMAP O.OlOg and a small amount of BHT were stirred at room temperature to suspend in dichloromethane 20 ml. Further, a solution of 0.7 g (3.5 mmol) of DCC dissolved in 5 ml of dichloromethane was added and stirred overnight. Filtration-56-201247846 The DCC urea precipitated separately, and the filtrate was washed twice with 0.5 mol/L hydrochloric acid 50 ml, saturated sodium bicarbonate 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and then evaporated. Recrystallization by ethanol to obtain 0.4 g of the desired polymerizable liquid crystal compound (Z3) (yield 36% - NMR (CDC13) 8 : 1. 6 - 1.9 (m, 6H), 2 · 6 3 (m, 1H), 3 · 0 7 (m, 1H), 4.06(t, 2H), 4 _ 5 7 (m, 1H), 5.64 (d, 1H), 6.24(d, 1H), 6.99(d, 2H) 7.24(d, 3H), 7.4 5(m, 2H), 7.59(m, 2H), 7.71(m, 2H), 8.25(d, 2H) Further, the liquid crystal phase of the polymerizable liquid crystal compound (Z 3 ) was observed. As a result, at the temperature rise, the phase was transferred to a smectic phase at 10 ° C, and the phase was transferred to a nematic phase at 1 14 ° C, and thermally polymerized at 12 ° C. [Example 4] Polymerizable liquid crystal compound Synthesis of (Z4) [Chem. 4 7]

The compound (Z2) obtained in Example 2 (2.0 g (5.5 mmol)), the compound (Q4) (methyl 4-hydroxybenzoate, manufactured by Tokyo Chemical Industry Co., Ltd.), 9 g (6.0 mmol), DMAP 0.005 g A small amount of BHT was stirred at -57-201247846 at room temperature, suspended in 25 ml of dichloromethane, and a solution of DCC 1.4 g (7.0 mm 〇l) dissolved in 5 ml of dichloromethane was added and stirred overnight. The DCC urea precipitated was filtered, and the filtrate was washed twice with 0.5 ml/L hydrochloric acid 50 ml, saturated sodium bicarbonate aqueous solution 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and the solvent was evaporated. Recrystallization and recrystallization to obtain the objective polymerizable liquid crystal compound (Z4) 2.1 g (yield 76%) 0 1 H-NMR (CDC13) 6 : 1.60-1.95 (m, 6H), 2.61 (m, 1H), 3.07(m, 1 H), 3.98(s, 3H), 4.01(t, 2H), 4.54 (m, 1H), 5.64(d, 1 H), 6.25(d, 1 H), 6.9 9 (d, 2 H), 7.2 6 (d, 2 H), 7.62 (m, 2H), 7.71 (m, 2H), 8.15 (d, 2H), 8.24 (d, 2H) Further, the polymerizable liquid crystal compound (Z4) was observed. As a result of the liquid crystal phase, the phase was transferred to a smectic phase at 105 ° C at a temperature rise, and was thermally polymerized at 130 ° C. [Example 5] Synthesis of polymerizable liquid crystal compound (Z5) [Chem. 4 8]

The compound (Z 1 ) obtained in Example 1 was 3.0 g (6·7 mm ο 1 ), and the compound (Q5 ) (2,3-difluorophenol, manufactured by Tokyo Chemical Industry Co., Ltd.) -58- 201247846 0.9g (6.7 mmol), DMAP 0.05 g and a small amount of BHT were stirred at room temperature, suspended in 30 ml of dichloromethane, and a solution of 1.9 g (9.0 mmol) of DCC dissolved in 10 ml of dichloromethane was added and stirred overnight. The DCC urea precipitated was filtered, and the filtrate was washed twice with 0.5 mol/L hydrochloric acid 50 ml, saturated sodium bicarbonate aqueous solution 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and then evaporated to ethyl alcohol. The crystal was recrystallized to obtain 2.9 g (yield: 77%) of the desired polymerizable liquid crystal compound (Z5). j-NMRiCDClW : 1.25 to 1.95 (m, 1 8 Η), 2.5 5 (m, 1 Η), 3.08 (m, 1 Η), 4.04 (t, 2H), 4.54 (m, 1H), 5.62 (d , 1H), 6.23(d, 1H), 6.99(d, 2H), 7.13(m, 3H), 7.62(m, 2H), 7.72(m, 2H), 8.23(d, 2H) As a result of the liquid crystal phase of the liquid crystal compound (Z5), the phase was transferred to the smectic A phase at 9 1 t at the time of temperature rise, and became an isotropic liquid state at 1 〇 6 °C. [Example 6] Synthesis of polymerizable liquid crystal compound (Z6) [1] Synthesis of intermediate compound (Q6) [Chem. 4 9]

(P6) (Q6) In a 100 ml eggplant type flask equipped with a cooling tube, 5.0 g (-59-201247846 32 mmol) of the compound (P6) (2-fluoro-4-hydroxybenzoic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) was added. 50 ml (55 mmol) of n-butanol and 2 ml of sulfuric acid were added to form a mixture, and the mixture was stirred at 10 ° C for 2 hours to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water and mixed, and then diethyl ether i〇0mi was added for extraction. The extracted organic layer was dried over anhydrous magnesium sulfate and dried, and the solvent was distilled off from the filtrate under reduced pressure. , 6.6 g of a white solid was obtained. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that the solid was the intermediate compound (Q 6 ) (yield: 97%) » 'H-NMR (CDC13) 5 : 0.98 (t, 3H), 1.47 (m, 2H), 1.74 (m, 2H), 4.32 (m, 2H), 6.27 (s, 1H), 6.47 (m, 2H), 7.88 (m, 1H) [2] Synthesis of polymerizable liquid crystal compound (Z6) [Chemical 5 0]

DCC, DMAP CH2CIj

The compound (z 1 ) obtained in Example 1 was 2.3 g (5.0 mm ο 1 ) ' of the intermediate compound (Q6) obtained in the above 1.lg (5.0 mmol), DMAP 0.040 g and a small amount of BHT at room temperature. After stirring, it was suspended in 20 ml of dichloromethane, and a solution of DCC 1.4 g (7.0 mmol) dissolved in 5 ml of dichloromethane was added and stirred overnight. Filtration of the precipitated DCC urea, -60- 201247846 The filtrate was washed twice with 50 ml of 5 mol/L hydrochloric acid, 50 ml of a saturated aqueous solution of sodium hydrogencarbonate, and 50 ml of saturated brine, dried over magnesium sulfate and then evaporated. The solvent was recrystallized and purified with ethanol to obtain 2.5 g (yield: 76%) of the desired polymerizable liquid crystal compound (Z6). , H-NMR (CDC13) 5 : 1.15 (t, 3H), 1.25- 1.90 (m, 22H), 2.56 (m, 1H), 3.10 (m, 1H), 4.05 (t, 2H), 4.37 (t, 2H), 4.56(m,1H), 5.63(d, 1H), 6.24(d, 1H), 7.02(d, 2H), 7.14(m, 2H)S 7.60 (d, 2H), 7.72(d, 2H ), 8.05 (m, 1H), 8.23 (d, 2H) Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z6), the phase was transferred to a layer A phase at a temperature of 58 ° C at a temperature rise, and 127 T: thermal polymerization was carried out. Reaction 〇 [Example 7] Synthesis of polymerizable liquid crystal compound (Z7) [Chemical 5 1]

The compound (Z2) obtained in Example 2, 2-5 g (7.4 mmol), 4-fluoroindole, 84 g (7.5 mmol), DMAP 0·1 g, and a small amount of hydrazine were stirred at room temperature to suspend in dichloromethane. In 30 ml, a solution of Dcc 2.lg (1〇.〇mmol) dissolved in 10 ml of monochloromethane was added and stirred for -61 - 201247846 night. The DCC urea precipitated was filtered, and the filtrate was washed twice with 50 ml of hydrochloric acid, 50 ml of a saturated aqueous sodium hydrogencarbonate solution and 50 ml of a saturated aqueous sodium chloride solution, and dried under magnesium sulfate. Ethanol was recrystallized and purified to obtain the objective polymerizable liquid crystal compound (Z7) 1.4 g (yield 4 1%) » 'H-NMR (CDCl3) 6 : 1.67 (m, 2H), 1.80 (m, 2H), 1.90 (m, 2H), 2.64 (m, 1H), 3.10 (m, 1H), 4.04 (m, 2H), 4.57 (m, 1H), 5.65 (m, 1H), 6.25 (m, 1H), 6.99 ( d, 2H), 7.10(m, 2H), 7.20(m, 2H), 7.61(d, 2H), 7.71(d, 4H), 8.24(d, 2H) Further, the polymerizable liquid crystal compound (Z 7 ) was observed. As a result of the liquid crystal phase, the phase was transferred to a smectic phase at 79 ° C at a temperature rise, and the phase was transferred to a nematic phase at 120 ° C to carry out thermal polymerization at 129 ° C. [Example 8] Synthesis of Compound (Z8) [1] Synthesis of Intermediate Compound (P8) [Chemical 5 2] /==\ /==\ ^iC〇3 )~0H + 〔 >~(CH2) 4-Br -S®~~-

In a 500 ml eggplant type flask with a cooling tube, 18.6 g (100 mmol) of biphenol, 1 0.0 g (4 8 mmo 1 ) of 4-bromobutyl-1,3-dioxapentane, and 13.8 g (100 mmol) of potassium carbonate were added. And acetone 200 ml to form a mixture -62-201247846, which was stirred at 64 ° C for 24 hours while allowing to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain a white solid. This solid was mixed with 50 ml of methanol, and the solvent was evaporated to give a white solid. Then, this solid was mixed with 70 ml of chloroform, and the solvent was evaporated to give 7.2 g of white solid. The result of this solid measurement by NMR is shown below. From this result, it was confirmed that this white solid was the intermediate compound (P8) (yield 48%). ^-NMRiCDChia : 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H), 6.87 (m, 4H), 7.42 (m, 4H) [2] Synthesis of compound (Z8) [Chemical 5 3]

(P8) (Z8) Next, the intermediate compound (P8) obtained above was added to a cooling tube 300 ml eggplant type flask, 7.2 g (23 mmol) and 2-(bromomethyl)acrylic acid 4.1 g (25 mmol). Further, THF (60 ml), tin (II) chloride (4.7 g) (25 mmol), and 10% by mass of an aqueous HC1 solution (19 ml) were mixed to form a mixture, and the mixture was stirred at 70 ° C for 5 hours while reacting. After the reaction, the reaction mixture was poured into 200 ml of pure water to give a white solid 6. lg. The results of the measurement of the solid by NMR are shown below. From the result -63-201247846, the compound (Z 8 ) for the purpose of the white solid was confirmed (yield 78%) 〇^-NMRCCDChie: 1.60- 1.95 (m, 6H), 2.64 (m, 1 Η), 3.11 (s, 1Η), 4.02(t, 2H), 4.60(m, 1H), 4.82(s, 1H), 5.64(s, 1H), 6.24(s, 1H), 6.94(d, 2H), 7.44( m, 4H) [Example 9] Synthesis of polymerizable liquid crystal compound (Z9) [Chemical 5 4]

(Z9) The compound (Z8) obtained in Example 8 was 0.9 g (2.5 mmol), 4-fluorobenzoic acid 0.458 (2.51111 «〇丨), and 〇^1? 0.03 Lu and a small amount of BHT were stirred at room temperature, suspended in 15 ml of dichloromethane, and a solution of DCC 0.7 g (3.5 mmol) dissolved in 5 ml of dichloromethane was added and stirred overnight. The DCC urea precipitated was filtered, and the filtrate was washed successively with 50 ml of α·5ιηο 1 liter of hydrochloric acid, 50 ml of a saturated aqueous sodium hydrogencarbonate solution, and 50 ml of a saturated aqueous sodium chloride solution. After drying over magnesium sulfate, the solvent was distilled off. Recrystallization was carried out to obtain a desired polymerizable liquid crystal compound (Z 9 ) Qjg (yield 82%). The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that the polymerizable liquid crystal compound (Z9) » -64- 201247846 'H-NMR (CDCl3) 6 : 1.59 (m, 2H), 1.7 0 (m, 2 H), 1. 8 6 (m, 2H) ), 2.59(m, 1H), 3.08(m, 1H), 4.00(m, 2H), 4.57(m, 1H), 5.64(m, 1H), 6.25(m, 1H), 6.96(d, 2H) 7.20 (m, 4H), 7.50 (m, 2H), 7.60 (d, 2H), 8.20 (m, 2H) Further, the liquid crystal phase of the polymerizable liquid crystal compound (Z9) was observed, and the temperature was raised at 99 °C. The lower phase was transferred to a smectic phase, and the phase was transferred to a nematic phase at 112 ° C and thermally polymerized at 123 ° C. [Examples 1 to 10, Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) The compounds used in the following examples and comparative examples are as follows. Further, Example 10 will be used. The composition of the composition prepared in ~15 and Comparative Example 1 is shown in Table 1 (in mg). [5 5]

-65 201247846

Compound (mg) E1 E2 E3 Z3 Z4 Z5 Z7 Example 10 120 90 60 30 - - - Example 11 120 90 60 - 30 - - Example 12 90 90 60 - 60 - - Example 13 90 90 60 - - 60 - Example 14 120 90 60 - - 30 Example 15 90 90 60 - - 60 Comparative Example 1 120 120 60 - • - - [Example ί] Polymerizable liquid crystal composition and polymer (film) Polymerization property 20 mg of the liquid crystal compound (E 1 ), 90 mg of the polymerizable liquid crystal compound (E2 ), 60 mg of the polymerizable liquid crystal compound (E3 ), 30 mg of the polymerizable liquid crystal compound (Z3 ), and Irgacure 3 69 by Ciba Geigy Co., Ltd. As a commercial product, 4 mg of R30 (manufactured by DIC Co., Ltd.) of 4 mg and a surfactant was dissolved in 7 g of cyclohexanone oxime to obtain a polymerizable liquid crystal composition. The polymerizable liquid crystal composition was applied by spin coating (100 rpm, 20 seconds) to a liquid crystal alignment film attached to a liquid crystal alignment film substrate, prebaked on a hot plate at 100 ° C for 60 seconds, and then allowed to cool to Room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The liquid crystal alignment film substrate-66-201247846 used here is coated with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries Co., Ltd.) on an ITO glass substrate with an ITO glass substrate, and fired at 23 ° C. After forming a film having a thickness of 100 nm, a rubbing treatment was performed. Then, the coating film formed on the liquid crystal alignment film substrate was irradiated with a strong light of 2000 mJ/cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. The film thickness of the obtained film was 1.9 μm, and it was observed by a polarizing microscope, and it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay 値 is 3 02 nm and 霾値 is 0.32. After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1·7 μm, the retardation 値 was 238 nm, and the enthalpy was 0.17. Further, the film was heated at 160 ° C for 30 minutes. After heating on a hot plate at 200 ° C for 1 hour, the film thickness was 1 · 6 μm, the retardation 値 was 213 nm, and the enthalpy was 0.08. [Example 1 1] Polymerizable liquid crystal composition and polymer (film) The polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z4), and the polymerizability was obtained in the same manner as in Example 1 Liquid crystal composition. Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10 . Further, the composition on the substrate after prebaking is in a liquid crystal state. The film thickness of the obtained film was 1.8 μm, and it was observed by a polarizing microscope, and it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay 値 is 29 nm and 霾値 is 0.24. After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was -67 - 201247846 1.7 μηι, the retardation 値 was 30 nm, and the enthalpy was 0.24. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation 値 was 33 nm, and the enthalpy was 0.16» [Example 12] Polymerizable liquid crystal composition and polymer (film) 90 mg of polymerizable liquid crystal compound (E 1 ), 90 mg of polymerizable liquid crystal compound (E2 ), 60 mg of polymerizable liquid crystal compound (E3 ), and polymerizable liquid crystal compound (Z4 ) 60 mg 4 mg of Irgacure 3 69 (trade name) manufactured by Ciba Geigy Co., Ltd. and R30 (manufactured by DIC Co., Ltd.) of a photopolymerization initiator were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition. . Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 1 . Further, the composition on the substrate after prebaking is in a liquid crystal state. The film thickness of the obtained film was 1.8 μm, and it was observed by a polarizing microscope, and it was confirmed that the film was horizontally aligned on the substrate surface. Then, its delay is lnm, and it is 〇.〇〇. After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1 · 7 μηι ' retardation 値 was 1 nm, and 霾値 was 0.09. Further, the film after heating at 1 60 t: for 30 minutes was heated to 20 (on a hot plate of TC for 1 hour), and the film thickness was 1·6 μm, and the retardation was 1 nm, and the enthalpy was 0.01. [Example 1 3] Polymerizable liquid crystal composition and polymer (film) The polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z5), and the polymerizable property was obtained in the same manner as in Example 12 - 68-201247846 Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. Further, the composition on the substrate after prebaking was liquid crystal ί, and the film thickness of the film was 1 · 9 μm, after the polarizing microscope. It was confirmed that the film was horizontally aligned to the substrate surface. Then, it was extended by 2 nm and the enthalpy was 0.21. After heating the film on a hot plate at 160 ° C for 30 minutes, 1·7 μηι, the retardation 値 was 2 nm, and the 霾値 was 0.14. » Further, the film after heating for 30 minutes was heated on a hot plate at 200 ° C for a film thickness of 1.6 μm, a retardation of 2 nm, and a enthalpy of 0.08. [Example 14] Polymerizable liquid crystal composition and The polymer (film) combines polymerizable liquid crystal A liquid crystal composition was obtained in the same manner as in Example 10 except that the material (Z3) was changed to the polymerizable liquid crystal (Z7). Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. Further, prebaking was carried out. The composition on the substrate after baking was a film thickness of 1·8 μm in a liquid crystal film. After a polarizing microscope, it was confirmed that the film was horizontally aligned to the substrate surface. Then, the film was extended at 305 nm and the enthalpy was 0.29. After heating the film on a hot plate at 160 ° C for 30 minutes, 1.7 μm, the retardation 値 was 260 nm, and the enthalpy was 0.24. Further, the film heated at ° C for 30 minutes was heated on a heating plate of 20 (TC). The film thickness was 1.6 μm, the retardation 値 was 232 nm, and the enthalpy was 0.16. The voltaic state was observed. The latent film was observed to have a film thickness of 1 60 ° C after the compound polymerization method and the canine state. 160 1 hour -69 - 201247846 [Example 15] Polymerizable liquid crystal composition and polymer (film) The polymerizable liquid crystal compound (Z4) was changed to a polymerizable liquid crystal compound (Z7), and other examples and examples 1 2 the same way The polymerizable liquid crystal composition was used. A film was obtained in the same manner as in Example 10 using this polymerizable liquid crystal composition. Further, the composition on the substrate after prebaking was in a liquid crystal state. 1. 8 μm, after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned to the substrate surface. Then, the retardation 値 was 86 nm > 缰値 was 0.09. The film was heated on a hot plate at 1 60 ° C for 30 minutes. Thereafter, the film thickness was 1.7 μm, the retardation enthalpy was 86 nm, and the enthalpy was 0.08. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 20 ° C for 1 hour, the film thickness was 1.6 μm, the retardation 値 was 85 nm, and the enthalpy was 0.08» [Comparative Example 1] Polymerizability Liquid crystal composition and polymer (film) The polymerizable liquid crystal compound (E 1 ) 1 20 mg, the polymerizable liquid crystal compound (E2) 120 mg, the polymerizable liquid crystal compound (E3) 60 mg, and a photopolymerization initiator 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 cyclohexanone oxime. 7 g to obtain a polymerizable liquid crystal composition. Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 1 . Further, the composition on the substrate after prebaking is in a liquid crystal state. The film thickness of the obtained film was 1.9 μm, and after observing -70 to 201247846 by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay 値 is 299 nm, and 霾値 is 〇·〇9. After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, and the retardation 2 was 2 34 nm 霾値 0.0 0.08. Further, the film heated at 160 ° C for 30 minutes was heated on a hot plate at 200 ° C for 1 hour, and then the film thickness was 1.7 μm, and the retardation 値 was 205 nm' 霾値 0.08. The above Examples 10 to 15 and Comparative Example 1 are summarized in Table 2, and the retardation angle dependence of the wavelength of 590 nm of the film produced in the above Examples 1 to 15 and Comparative Example 1 is expressed in figure 1. Further, the results of measuring the average tilt angles of the wavelengths of 5 90 nm of the films produced in the above Examples 1 to 15 and Comparative Example 1 are shown in Table 2. [Table 2]

And(nm) 霾値 average tilt angle exposure post-bake 1 bake 2 (%) (°) Example 10 302 238 213 0.17 14 Example 11 29 30 33 0.24 61 Example 12 1 1 1 0.09 88 Example 13 2 2 2 0.14 85 Example 14 305 260 232 0.24 10 Example 15 86 86 85 0.08 50 Comparative Example 1 299 234 205 0.08 5 Baking 1: 160 ° C, heating for 30 minutes, baking 2: 160 ° C, heating 30 minutes - 20 ° C, heating for 1 hour As shown in Table 2, it can be seen that the film made in Examples 10 to 15 is guaranteed to be very low after baking (i.e., The thermal stability is high. Further, by adding the polymerizable liquid crystal compound of the present invention, the average angle can be controlled. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the retardation angle dependence of the wavelengths of 590 nm of each of the films obtained in Examples 1 to 15 and Comparative Example 1. -72-

Claims (1)

201247846 VII. Patent application scope: 1. A polymerizable liquid crystal composition characterized by the following formula [Chemical 1] [1] (wherein, X1, X2, X3 and X4 each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a _ atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group 'G Represents - C( = 0)0 - or - 〇C( = 0)-base, η represents an integer from 4 to 10). 2. A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1 of the patent application. 3. The polymerizable liquid crystal composition according to the second aspect of the invention, which further comprises a liquid crystalline compound having one or more polymerizable groups in one molecule. 4. The polymerizable liquid crystal composition according to the third aspect of the invention, wherein the liquid crystal compound is a compound having one or more polymerizable groups represented by the following formula [2] or [3] in one molecule; 2] -73- 201247846 (In the formula, the dotted line indicates the keying hand). 5. The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formula [4] or [5]; [化3] M1—(CH2)n— (wherein X represents a fluorine atom, an aryl group or a valent hydrocarbon group having a carbon number of 4-8, Π and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9, Mi, M2 and M3 Respectively, the bases represented by the following formula [2] or [3] are respectively shown; (In the formula, the dotted line indicates the bonding hand). 6. A polymer which is obtained by the polymerizable liquid crystal composition according to any one of claims 2 to 5 of the patent application, wherein the film is as described in claims 2 to 5 of the patent application. The polymerizable liquid crystal composition of any one of them is obtained. A contiguous film of 2 to 5, which is obtained by a polymerizable liquid crystal composition according to any one of claims 74-201247846. An optical member comprising a polymer as claimed in claim 6 or an alignment film according to item 8 of the patent application. 10. A compound characterized by the following formula [6]; [Chemical 5] Τ>-(€Η^-〇-/~Λ-ηΓΊκ-Υ [6] (wherein Υ represents -ΟΗ Or - COOH,k represents an integer from 4 to 10.) -75-