TW201124510A - Polymerizable naphthalene compound. - Google Patents

Abstract

The issue to be overcome by the invention is to provide a polymerizable compound having excellent solubility with other polymerizable compound and liquid crystal compounds while the polymerizable liquid crystal composition is formed, and excellent heat resistance and mechanical strength while the foregoing polymerizable liquid crystal composition cures. The invention provides a polymerizable compound represented by the following formula, a liquid crystal composition taking the compound as a constituent and further provides an optical anisotropic body or a liquid crystal device using the liquid crystal composition. Since the polymerizable compound of the invention has excellent solubility with other liquid crystal compound, it is in favor of being taken as the constituent of the polymerizable composition. In addition, the polymerizable composition containing the polymerizable compound according to the invention has wide liquid crystal phase temperature range. The optical anisotropic body using the polymerizable composition has high heat resistance, which is in favor of purposes such as deflection plates and phase difference plates.

Description

[Technical Field] The present invention relates to a polymerizable naphthalene compound, a liquid crystal composition containing the compound, and an optically anisotropic body or liquid crystal device which is a cured product of the liquid crystal composition. [Prior Art] In recent years, along with the progress of the information society, the importance of optical compensation films such as deflection plates and phase difference plates that are necessary for liquid crystal displays has increased, and high durability and high functionality have been required. For the optical compensation film, there has been a report of an example of a polymer using a polymerizable liquid crystal composition. Optical anisotropic bodies for optical compensation films, etc., not only optical properties but also the polymerization rate, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength, surface hardness and heat resistance of the compound are also important factors. . A compound having a structure in which a 1,4 -phenylene group is bonded by an ester bond (see Patent Document 1) and a compound having a group (see Patent Document 2) have been proposed. However, the polymerizable compound described in the cited document has problems such as low solubility. On the other hand, a polymerizable compound which forms a cinnamic acid structure in order to improve solubility is disclosed (refer to Patent Document 3). However, as a polymerizable compound which can be photoisomerized, heat resistance and mechanical strength are not obtained. improve. Further, the development of a PSA (P〇lymer Sustained Alignment) type liquid crystal display device and a PSVA (P〇lymer stabilised Vertical Alignment) type liquid crystal display device is continuing. These devices have a cured product obtained by polymerizing a polymerizable compound in a liquid crystai cell in order to control the tilt of the liquid crystal portion 201124510, and are expected to be a new generation of liquid crystal display due to their high responsiveness and high contrast. element. The cured product is formed at a certain angle with respect to the liquid crystal cell to control the alignment of the liquid crystal molecules. In a state in which a polymerizable liquid crystal composition composed of a liquid crystal compound and a polymerizable compound is disposed between substrates, a liquid crystal molecule is aligned between the substrates, and the liquid crystal molecules are aligned to each other. Irradiation of ultraviolet rays or the like in the aligned state causes the polymerizable compound to be polymerized, thereby memorizing the alignment state of the liquid crystal as a cured product. There is a problem of reliability such as @"afterimage" generated when the liquid crystal display element continues to be displayed for a long period of time, and productivity problems due to the manufacturing process. Reliability is not a single problem, but is caused by several compound factors. (1) It is caused by residual polymerizable compounds, (2) It is caused by liquid b, The change in the tilt of the daily molecule (pretilt angle of the servant, » gate, + change), and (3) the deterioration of the liquid crystal due to ultraviolet irradiation. On the other hand, in the case of productivity, in the case of the polymerizable compound used in the 隹U彺, since the absorption of the J-side and the outer-line region of 300 nm or more is small, the polymerization is not completely performed, and in order to reduce the amount of the drink Amount, discard the ultraviolet light. As a result, there is a use of a photopolymerization initiator to promote the concentration of the product due to the decrease in the density of the product and the consumption of electricity, which leads to the manufacturing cost. The method, however, due to the presence of a large amount of σ in the liquid crystal display element, & good τ, wave day, poly. The initiator and its decomposition and afterimage 4 became the cause of the voltage retention of the liquid day display element falling 4 5 201124510. In the liquid crystal composition of the conventional polymerizable compound, it is difficult to simultaneously solve the reduction of the remaining unpolymerized polymerizable compound and the improvement of productivity, and therefore it is required to use no photopolymerization initiator and to be low. A liquid crystal composition containing a polymerizable compound which is polymerized in an amount of ultraviolet rays. Further, the production of the afterimage is known as the change in the pretilt angle of the liquid crystal molecules in the liquid crystal composition containing the polymerizable compound. That is, if the polymer which is a cured product of the polymerizable compound is relatively soft, when the display element is formed, if the same pattern is continuously displayed for a long period of time, the structural change of the polymer results in a change in the pretilt angle. Since the change in the pretilt angle has a large influence on the response speed, it is a cause of the afterimage. Thus, it is effective to solve the problem that (2) is a polymerizable compound having a polymer having a rigid structure whose polymer structure does not change. An acrylate of a biphenyl skeleton is known as a polymerized ruthenium compound for a PSA type liquid crystal display device (see Patent Document 4 and Patent Document 5). However, due to the biphenyl skeleton, it hardly absorbs in the ultraviolet region of 300 nm, and it is necessary to irradiate ultraviolet rays for a long time. In addition, a polymerizable compound having a molecular structure asymmetry in order to improve solubility is disclosed (see Patent Document 6). Although the compound is improved in solubility, since a spacer is interposed between the ring structure and the polymerizable functional group, the rigidity of the molecule is lowered, and the ability to control the tilt of the liquid crystal molecules is lowered. As described above, the liquid crystal display element using the conventional polymerizable liquid crystal composition is difficult to completely have the afterimage characteristics, solubility, and stability of the pretilt angle. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. 5, No. 5, No. 5, No. 5, No. 5, pp. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-307720 (Patent Document 6). The problem to be solved is to provide a polymerizable compound which has excellent solubility with other polymerizable compounds and liquid crystal compounds when constituting a polymerizable liquid crystal composition, and exhibits excellent heat resistance when the polymerizable liquid crystal composition is cured. The mechanical strength and the polymerizable compound for PSA can improve the stability of the pretilt angle. The inventors of the present invention have studied various substituents in the polymerizable compound. As a result, it has been found that a polymerizable compound having a specific structure can solve the above problems, and the present invention has been completed. The present invention provides a polymerizable compound represented by the formula (1)

(R1 represents the following formula 丨) to any of the formula (R-15), 201124510

Ο Ο (R-2) (R-3) Ο (R-1)

CH3 (R-7) (R-8) (R-4) (R-5) ^ν, ο (R-6)

(R-ll)

K H3C H3C^V" ,. 0 H3C^^ H3C^^〇 0 '0 (R-12) (R-13) (R-9) (R-10)

(R14) (R-15), X1 'X2, X3 'X4, X5 and X6 independently of each other represent a hydrogen atom, an alkyl group, a functional alkyl group, an alkoxy group, a functional alkoxy group, a halogen group, a cyano group or Nitro, S 1 represents that the oxygen atom is not directly bonded to each other, and the methylene group thereof may be substituted by the oxygen atom '-COO-, one OCO-, or one OCOO-, one CEC-, and the carbon number is from 1 to 12. An alkyl ene group, or a single bond, L1 and L3 independently of each other represent a single bond, a 0-, an S-, a 0CH2-, a CH20-, a CO-, a c2h4-, a coo- , an oco-, an ocooch2 -' -CH2OCOO- ' -CO-NR11- ' -NR"-C0- ' - SCH2 _, a CH2S —, a CH = CH — COO —, an OCO — CH = CH — , - COO - CH = CH - ' - CH = CH - OCO -, one

COOC2H4- ' -OCOC2H4- ' -C2H4OCO- ' - C2H4COO -' -OCOCH2- ' - CH2COO- ' - COOCH2- ' - CH2OCO -, one CH=CH-, one CF=CF-, one CF=CH-, one CH=CF -' -cf2- ' - cf2o- > - ocf2- ' - cf2ch2- ' - ch2cf2 —, a CF2CF2 — or a CeC—(wherein R1丨 represents the 201124510 alkyl group of carbon atoms 1 to 4. ) L2 represents a ch = CH - COO - or a C2H4CO 〇 -, Μ 1 and M 2 represent l, 4 - stupid, fluorene, 4-cyclohexylene, pyridine - 2,5 - diyl, pyrimidine - 2, 5 —diyl, naphthalene_2,6-diyl, tetrahydronaphthalene-2,6-diyl or 1,3-one crocodile-2,5-diyl; \13 represents 1,4-phenylene 1,3,5-Benzenediyl, 1,4,5-benzenetriyl, i,3,4,5-phenyltetrayl, 1,4-cyclohexylene, 1,3,5-cyclohexene Base, ι, 3, 4 a ring of triazole '1,3,4,5~cyclohexenetetrayl, ° pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2 , 6-diyl, tetrahydronaphthalene-2,6-diyl or L3-dicrosin-2,5-diyl, oxime 1, M2 and M3 are independently unsubstituted or may be alkyl, or alkane Base, alkoxy, halogen, cyano or nitro Instead, m represents 0, 1, 2, and 3, and η represents 0, 1, 2, and 3. When m and η represent 2 or 3, two or three L1, L3, Μ1 and Μ2 may be the same or different ' Ζ denotes a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanate group, a trifluoromethoxy group having 1 to 12 carbon atoms which is not directly bonded to each other as an oxygen atom, and the methylene group thereof may be an oxygen atom, a sulfur atom, a C0-, a COO-, a 0C0 —, a 0C00—, a CH=CH—, a CeC—substitution, or a Ζ denotes an L4—S2—R2 (wherein R2, S2, and L4 represent the same meaning as R1, s1, and L1, respectively), k represents 1, 2 or 3, and when k represents 2 or 3, Z may be the same or different. Further, a polymerizable liquid crystal composition containing the compound as a constituent component, an optical anisotropic body using the polymerizable liquid crystal composition, a liquid crystal composition for PSA containing the compound, or a liquid crystal device is provided. The polymerizable compound ' of the present invention is useful as a constituent component of the polymerizable liquid crystal composition because it has a large birefringence anisotropy and excellent solubility with other liquid crystal compounds. Further, the polymerizable liquid crystal composition g containing the polymerizable compound of the present invention 201124510 has a high curing rate and a wide liquid crystal phase temperature range. The use of the polymerizable polymer of the polymer of the polymer of the polymer is high in heat resistance, which is advantageous for the use of a transfer plate, a phase difference plate, etc., and is also advantageous for the polymer stabilization liquid. [Embodiment] In the general formula (1), 'R1 and V' each independently represent a polymerizable group, and a specific example f of the polymerizable group is exemplified by the following. , J:,. '° (R-1)

Ο (R-2)

0 (R-3) (R-4) (R-5) ο-

V ο a (R-7) ch3 (R-8) m) 0 (R-6)

H3c.

H3C"^V o 0 0 CT (R-10) HS- ) -12) (R-13) (R14) (R-15) These polymerizable groups are polymerized by radical polymerization, free radical addition polymerization. Polymerization and anionic polymerization to harden. (4) When the ultraviolet polymerization is carried out as a polymerization method, the formula (R-1), the formula (R-2), the formula (R-4), the formula (R-), the formula (R 7), and the formula (R-11) , (R— 13.) or (R—15) is preferred, and 3 (R ′′ (R—2), (R-7), and (r—i 〇 or (R—13) are preferred. , (R— υ, formula (R—2) is particularly preferred. Those which are not directly bonded to each other, whose carbon atoms may be replaced by oxygen atoms—OCO—, OCOO—substituting sl and S2 independently of each other represent a spacer or a single bond. As the spacer, it is preferably a stretching group having a carbon number of 2 to 6 or a single bond 'the extended alkyl group as an oxygen atom? lL Millennium..

COO 201124510

Ll, L3 and L4 are independent of each other, preferably a single bond, - 〇ch2 -, - Γ u , a CH2 〇 -, - COO- ' - OCO-, - 〇c〇〇ch2 -, - CH2oco〇 -, _CH =CH—C00一一一一〇c〇ch==ch~ -cooc2H4---ococ2h4---c2h4oco——C2H4C〇〇CF2〇~, from the viewpoint of inexpensive manufacturing and liquid crystal alignment, more preferably Key, —coo—OCO-, or —0CH2___c^2〇. L2 represents ~CH=CH-c〇〇- or -c2H4C〇〇_, but in the case of obtaining a material having a large birefringence anisotropy, it is preferred to obtain a compound having a high solubility, preferably -C(tetra)Η. :Γ or —C2H4C00 ~. - M1 and M2 are preferably 'phenylene, M-cyclohexylene" "...'_pyridine-2,5-diyl and naphthalene-2,6-diyl, M3 is preferably phenyl, ... Base, stupid three base, (10) - benzene four-extension ring hexyl group, ring hexaxy three base, ... - ring house: two to 5-ring ancestral four base, ... 2,5 - two base... bite - 2,5 Tuding '2'6-one base, tetrahydronaphthalene-2,6-diyl or 1,3-diof:-yl group is more preferably M-phenylene, 1,4-cyclohexylene, naphthalene 2 , 6 ~ a group, 135 - ^ -, - phenyl, extraction, 26 _ : base, 1,3,4-benzene triyl, especially preferably μ .. κ,, - base, I3, 4 - Benzene triyl. More preferably, it is a fluorogenic sz_rV, a fluorenyl group, an alkyl group having 1 to 12 carbon atoms or a L4 - K (in the formula, 1) 2 Q2 u τ 4 and L respectively represent the same as R丨, S1 and L1, respectively. 2 meanings: 4 shows. , i + . Better. In particular, 1 or 2, (4) or Buk or 2 is preferred, n = 11 201124510. In addition, as a polymerizable compound for PSA, especially when ultraviolet light t cooperation is used as a polymerization method, it is more than (4) (r-~ (r-2)

Formula (R-"), formula (R-13) or formula (R' is more preferably (R-1), formula W) A(R-2), formula (R-7)' R—11} or (R-13), especially the formula ^—丨), and the formula (R_2). L1 and L3 are independent of each other, preferably a single bond, - 〇cH2 -, - -, -CH2〇-, _coo-, - 〇c〇_, - 〇c〇〇cH2 - 2-4 CH20C00- > _CH= CH-C00- ' -〇CO-CH=CH-. -C〇〇C2h4—, -OCOC2H4_, _C2H4〇c〇—, a c2_CF2〇—is better from the viewpoint of inexpensive manufacturing and liquid crystal alignment It is a single bond, a COO-, an OCO-, -OCh2- or -CH2〇-. L2 represents -CH=CH-CO〇- or -C2h4CO〇-, and in order to form a more rigid polymer, and to expand the conjugated system of r electrons, the polymerization rate is accelerated, preferably a CH=CH-COO-.乂^^^^^ and preferably independently of each other are a halogen such as a gas atom, an alkyl group, an alkoxy group, a fluorine or a gas, more preferably a hydrogen atom and fluorine. Preferably, ruthenium, osmium and iridium are 1,4 phenyl, 1,4, stilbene, guanidin-2,5-diyl, pyrimidine-2,5-diyl and naphthalene-2,6-di More preferably, the group is a 1,4-phenylene group and a 1,4-cyclohexylene group. 〇1 represents 〇, 1 and 2, and 11 represents 〇, 1 and 2', particularly m is 〇 or 1, η is 0 or 1 is preferable, and ❻ and η are preferably 〇. More specifically, the compound represented by the formula (I) is preferably a compound represented by the following formula (I-1) to the formula (I-46). 12 201124510

(1-1) (1-2) (1-3) >)ρ—

C) F

(Μ) (1-5)

(1-6) (1-7) (1-8)

(1-9) >_2)ρ-〇

〇-(CH2)q

(1-10) 13 201124510 > R F (CH2)p-0

(Ml) (1-12)

〇-(CH2)q-〇^~ 1~o(ch2)p-〇, (M3) ~^〇(ch2)p ~^-〇(ch2)p

O-CCH^-O-^- (1-14) -〇(ch2)—〇

〇-(CH2)q-〇-^~ (CH2)q-〇^^~ 〇-(CH2)qO-^~ (1-15) (1-16) (1-17) > (CH2)q -〇-^~ ~^-〇(ch2)p, (CH2)-o

0_(CH2V0~^~ (1-18) (1-19) 14 201124510

(1-20) (1-21) (1-22) > (CH2)-〇

(1-23) -0(CH2)p-0 〇(CH2) -o 0(CH2)p-0 〇(CH2) -o -〇(CH,)-〇

C5h"c〇-o, q ~^-0(ch2)p-0 〇-(CH2),

(1-29) (1-24) (1-25) (1-26) (1-27) (1-28) 0 Λ N- 1 (CH2)q, 0^~ -〇(CH2)p- 〇

0-(CH2)-0 (1-30) 15 201124510 OCH, -0(CH2)p-0 -〇(CH2) -ο ~^-0((:η2)ρ-0 -0(CH2)p- 0

(CH2)qCH3 (1-31) (1-32) (1-33) (1-34)

~^〇(ch2)p (1-35) (1-36)

-(CH2)qCH3 (1-37) 16 201124510

(1-38) (1-39) (1-40)

(1-41) (1-42)

(M3) (1-44) h3c oo 0 ch3 (1-45) (1-46) (wherein p and q represent integers from 0 to 12, but when 0, the bond to the aromatic ring is removed. Oxygen atom.) The compound of the present invention can be synthesized by a synthesis method described below. (Production Process 1) Production of a compound represented by the formula (1 -1) 17 201124510 by M-roxyl-Heck reaction by 6-bromo-2-naphthol and butyl acrylate and using a palladium catalyst 'A naphthalene derivative (S-1) is obtained, and an esterification reaction using propylene oxime is carried out to obtain a naphthalene derivative (S-2) having an acryloyl group. Further, a triazine derivative (S-3) obtained by detaching the tertiary butyl group and converting it into a carboxylic acid group is obtained by trifluoroacetic acid.

Br Pd(OAc)2 Et3N/NMP

Next, the target compound (I-1) can be obtained by an esterification reaction with a tetrahydrohexylcarbodiimide such as dicyclohexylcarbodiimide with 4-(2-propenyloxy)ethylphenol.

(Production Process 2) The production of the compound represented by the formula (II-4) is carried out by the naphthalene derivative (S_丨) and 4-(6-propenyloxyhexyloxy)benzoic acid synthesized in Process 1. An esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide is carried out to obtain a naphthalene derivative (s-4) having an acrylonitrile group. 18 201124510

HO

tBu O DCC /DMAP CH2C12

a tBu (S-4) followed by 'trifluoroacetic acid, to obtain a derivative (s~5) which decouples the tertiary butyl group and converts it into an acid group, further by using 4_(2-propenyloxy) Ethylphenol is subjected to an esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide to obtain a target compound (I _ 4).

〇(1-4) (Process 3) The compound represented by the formula (I-丨3) is produced by using dicyclohexyl dicarboxylic acid and hydroxybutyl acrylate. The esterification reaction of a dehydrating condensing agent such as carbodiimide gives a cyclohexanol monoester compound (S-6) having an acrylonitrile group. Further, an esterification reaction using a dehydration condensing agent such as dicyclohexylcarbodiimide with a naphthalene derivative (S-1) synthesized in the first step to obtain a naphthalene derivative having an acrylonitrile group (s _ 7) . 19 201124510

HOOC

COOH

, ch2ci2 (S-6) DCC/DMAP ch2ci2

Next, a naphthalene derivative (S-8) which is liberated from the tertiary butyl group and converted into a tickic acid group is obtained by trifluoroacetic acid, and further carried out by reacting with 4_(2-isopropyloxy)ethylbenzene The target compound (I _ 1 3) can be obtained by esterification using a dehydrating condensing agent such as dicyclohexylcarbodiimide.

DCC/DMAP CH2C12 A naphthalene derivative (g -9) was obtained from the neat derivative (s-1) synthesized by Process i by catalytic hydrogen reduction using palladium on carbon as a catalyst. Then, a naphthalene derivative (S-1) having a methacryl group is obtained by performing an etherification reaction with a base such as potassium carbonate with 3-chloropropyl methacrylate. 20 201124510

Next, a naphthalene derivative (S-n) which is obtained by detaching the tertiary butyl group and converting it into a carboxylic acid group is obtained by trifluoroacetic acid, and further by using a 4-(6-fluorenyl propylene methoxy hexyloxy group). The phenol is subjected to a hydration reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide to obtain the target compound (I-22).

(Production Process 5) The compound represented by the formula (1-25) is produced by 3-ethyl-3-hydroxymethyl oxetane (trade name: EOXA, manufactured by Toagosei Co., Ltd.) and 1-bromo-3-. The gas propane is subjected to an etherification reaction in the presence of a base such as sodium hydroxide to obtain an oxetane derivative (s-1 2). Then, an etherification reaction using a carbonic acid clock is carried out by a naphthalene derivative (s-sodium) synthesized in Process 1, to obtain a hetero-oxocyclobutane-based naphthalene derivative (S-13). Further, the tertiary butyl group is desorbed by trifluoroacetic acid to obtain a carboxylic acid derivative (S-14) having an oxetanyl group. 21 201124510 (S-l)

Then 'to make hydroquinone monotetrahydropyranyl ether (ie the reaction product of p-benzoic acid and 3,4-dihydro~2H-pyran) and the oxetane derivative (s-12) In the presence of an ε-reverse acid clock and the like, the progress of the reaction is carried out, and the protective group of the present is removed from the salt to obtain a derivative (g-1). Further, the target compound (I-22) can be obtained by an esterification reaction with a carboxylic acid derivative (S 14 14) having an oxetanyl group using a dehydrating condensing agent such as dicyclohexylcarbodiimide.

(Production Process 6) Production of a compound represented by the formula (1-5): A trifluoroanthracene acid needle is reacted with a naphthalene derivative (S-1) synthesized in Process 1 to obtain a trifluoroantimony-based acid ester. a naphthalene derivative (S-16). Next, the cleavage of the protecting group by dilute hydrochloric acid is further carried out by reacting the phenol group of 4-hydroxyphenylboronic acid with a compound protected by tetrahydropyranyl ether and using a catalyst of eucalyptus-miyap. A naphthalene derivative (s-17) is obtained. 22 201124510

(S-17) Next, a naphthalene derivative (s _ 18) having a mercaptopropenyl group is obtained by an etherification reaction with a 6-glycolyl hexyl acrylate using a carbonic acid detachment base. Further, the tannic acid derivative (S-19) obtained by derivatizing the tertiary butyl group with trifluoroacetic acid and the 4-(3-mercaptopropenylpropenyloxy)phenol are dehydrated using monocyclohexylcarbodiimide or the like. The esterification reaction of a condensing agent, whereby the target compound (I-5) can be obtained.

(Production Process 7) Production of a compound represented by the formula (1-39) Using p-toluenesulfonic acid, deuteration reaction of 4-benzyloxyphenol and protocatechuic acid is carried out to obtain protocatechuic acid-derived (s 2 〇). Then, the 6-hexanol and (S-20) are subjected to an etherification reaction in the presence of a carbonic acid unrecovery test, and further the benzyl group is removed by hydrogenation using palladium carbon to obtain a phenyl group having a base and a test group. Tea acid derivative (s-21). Next, a compound having two acrylic groups (S-22) was obtained by esterification reaction using 23 201124510 benzenesulfonic acid and acrylic acid.

Reflux (S-20)

(S-21)

OH ^γ0Η TsOH Toluene

(S-22) Next, the target compound can be obtained by subjecting the naphthalene derivatives (S-5) and (S-22) synthesized in Process 2 to an esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide. (I-29). (S-5) (S-22) -► DCC/DMAP CH2CI2

0-(CH2V〇^C (I, , (ch2)6-o^~ (Process 8)) The compound represented by the formula (I-34) is a 4-hydroxybenzaldehyde and a 6-gas hexyl acrylate. The etherification reaction is carried out in the presence of a base such as potassium carbonate, and the obtained compound is further reduced with sodium borohydride to obtain a benzyl alcohol derivative (S 23 ). Next, it is derived from naphthalene synthesized by Process 1. The product (S _ 1) was subjected to etherification using a Mitsunobu reaction of triphenylphosphine and azodicarboxylate diisopropyl vinegar (DIAD) to obtain a naphthalene derivative (S-24). 24 201124510 h0-O -1

CHO k2co3/dmf

-CHO -Λ· (S-l)

DIAD/TPP THF

NaBH4 THF

(S-24) (S-23) Next, a naphthalene derivative in which a tertiary butyl group is detached and converted into an acid group is obtained by trifluoroacetic acid' is further carried out by reacting with 4-cyano-3-fluorophenol The object compound (I - 34) can be obtained by an esterification reaction using a dehydrating condensing agent such as cyclohexane carbodiimide.

(1-34)

CF,COOH (S-24) HO_^~CN __ DCC /DMAP CH2CI2 ~^-〇(CH2)6-〇- The compound of the present invention can be used for nematic liquid crystal, smectic liquid crystal, chiral nematic Liquid crystal, chiral smectic liquid crystal and cholesteric liquid crystal composition. In the liquid crystal composition of the present invention, a polymerizable liquid crystal compound to be contained in the polymerizable liquid crystal composition of the present invention may be added to the polymerizable liquid crystal composition of the present invention in any range, in addition to the use of the compound of the present invention. A decyloxy group or a methyl propyl decyloxy group is a chemical substance of a polymerizable functional group. Further, the polymerizable liquid crystal compound is preferably a compound having two or more polymerizable functional groups in the molecule. Further, when the liquid helium composition of the present invention is a cholesteric liquid crystal, it is preferred to add a chiral compound. It is also possible to add a liquid crystal composition having no polymerizable group, and it is excellent in compatibility. 1 This is a useful material of a polymer stabilized liquid crystal device: a specific example of a polymerizable compound other than ruthenium, except for a compound having a pass-through type There is no limitation other than the 25 k 201124510 oxy group used as a combination (R - 2 or more polymerizable liquid crystal compounds 'preferably the compound τ is enriched with propylene 1) or methacryloxy (R - 2) Further, it is preferably a polymerizable functional group contained in the molecule. Specifically, a polymerizable liquid crystal compound which is preferably used in combination is represented by the formula (II) R21-S21.L21-M21-fL22-M22·^-A21 (II) (wherein the polymerizable group 'β indicates a single The bond or has: ^~12 carbon atoms of the alkyl group 'here, more than one, as the oxygen atoms are not directly bonded to each other' carbon atoms can be gas atoms, _coo ', OCO-, OCOO - Substituted, L21 and L22 are independent of each other.

Key, -〇-, _S-,_0CH2_, ~CH2〇_-C〇, - COO-, - OCO-, - 〇COOCH2-, -CH2〇c〇〇- c〇-NR23---NR23-CO- --CH= N——SCH2——CH2S -, -CH= CH-COO-, - OOC- CH= CH-, - c〇〇C2H4 -, one OCOC2H4 -, one C2H4OCO -, - c 〇COCH2-, -CH2COO-, -CH=CH-, -C2H4-, -CF=CH-, -CH=CF-, -CF2-, -CF20-, -OCF2 -, -CF2CH2-, one CH2CF2-, one CF2CF2 - or (wherein R23 represents an alkyl group having 1 to 4 carbon atoms), and M21 and M22 independently of each other represent 1,4 -phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, and mouth Biting a 2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or 1,3-diofan-2,5-diyl, Μ21 and Μ22 independently of each other Unsubstituted or substituted by alkyl, halogenated alkyl, alkoxy, dentated alkoxy, cyclin, cyano or nitro, 121 represents 0, 1, 2 or 3, when 121 represents 2 or 26 201124510 3 o'clock 2 or 3 L22 and m22 may be the same or different. A2 is not H, F, C1, CN, SCN, OCF3, an alkyl group having 1 to 12 carbon atoms, and the oxygen atom is not directly bonded to each other, and the methylene group may be an oxygen atom or a sulfur atom. CO—, a COO—, an OCO—, a 〇c〇〇〆, _CH=CH~~, ^CEC_ substitution, or A21 is preferably -l23 / S22_R22 (wherein, L23, S22, and r22 are independently represented The same meaning as L2丨, s21, R21.) The compound represented, especially the compound, L21, B22 and L23 independently represent a single bond, a 〇-, -c〇〇- or an OCQ-' M21 and M22 independently represent a compound of M-phenyl, fluorene, 4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl. The compound represented by the formula (Π), specifically, is preferably a compound represented by the formula (Π - formula (II-22). 27 201124510

(II-1) α

(11-3) (Π-4) (11-6) τ. 1 (CH2)a-0 -0(CH2)a-0

〇-(CH2),,〇- O-CCH^O- (U-8) -0(CH2)a-0

〇-(CH2)b〇- (II-10)

28 201124510 Q' Ο

(II-12) > (CH2)a-〇- c -〇(CH2)a-〇-

~^0(CH2)a-0 ~^r-0(CH2)a-0 oc

o •ch3 OOC5Hn } ^ -〇-(CH2)b〇- -0-(0^0 -O-CCH^O-

〇-(CH2 > (CH2)a-0 -0(CH2)a-0

〇-(CH2)b〇- o-(ch2: 〇-(CH2)b〇 F F -0(CH2)a-0

〇-(CH2)bO^~ -0(CH2)a-0

〇~iCH2)b〇-^ o-CCH^oH 〇-(CH2)b〇-^~ (wherein, a and b represent integers of 0 to 丨2, but when they are 〇, they are not directly bonded to each other, And one of the oxygen atoms is removed. In addition, the polymerizable liquid (Π-13) (11-14) (II-15) (II-16) (H-17) (II- used for the liquid crystal composition of the present invention. 18) (U-19) (II-20) (11-21) (11-22), Oxygen) Crystal 4 29 29 201124510 物 'In order to adjust the liquid crystal temperature range and birefringence, and reduce the It is preferred to blend the formula (II-23) to the formula (II-33). ~y<)(CH2)a-〇—/=\ ° W ^ °~{_)-〇-(ΡΗ2χ€Η3^0(CH2)a-〇-〇-^^^〇'(CH2)bCH3

CH^CHj 〇-(CH2)bCH3 ~^-〇(CH2)a-〇-~^-〇(CH2)a-〇-Q-二〇K0-(CH2)bCH3 -〇(CH2)a-〇- ~^-0(CH2)a-0- cp 〇_(CH2)bCH3

O o. -〇-((:Η2ν:Η3 (11-23) (11-24) (11-25) (Π-26) (11-27) 01-28) (II-29) (II-30 (Π-31) (Π-32) (II-33) Further, as a composition for a PSA (Polymer Sustained Alignment) type liquid crystal or a PSVA (Polymer Stabilised Vertical Alignment) type liquid crystal, in addition to the polymerizable compound of the present invention It can also be blended with the general formula (II-34) to the general formula (II-43). 201124510

〇-(CH2)b〇-^~ (Π-34) ~^-〇(CH2)a-Ο

-〇-(CH2)b〇 乂~ (II-35) (11-36) (11-37) CH3 — H - (CH2)b〇

o (11-38) CH,

〇(CH2v〇 O

〇-(CH2)b〇-

o (11-39) CH,

o(CH2)a-o O

0-(CH2)b0 h3q

o (11-39) CH,

O 〇(CH2)a-o

(11-40)

o (Π-41) CH,

O

-〇(CH2)a - O

O-(ch2v>

H3C (H-42)

O

CH, HXQ ¢) (11-43) Remove (wherein, a and b represent an integer of 0 to 12', but when it is 〇, an oxygen atom bonded to the aromatic ring.) 31 201124510 The blending amount of the chiral compound is preferably from 5% to 30% by weight, more preferably from 2 to 20% by weight, based on the liquid crystal composition.

When the liquid crystal composition of the present invention is a cholesteric liquid crystal, a chiral compound is usually added, and a specific compound such as a formula (ΠΙ_ 〇~(πι-8) is O-CCH^O-^ (UU1)

(ΠΙ*2) (Π 1-3) (ΙΙΜ) (ΙΠ-5) (1) 1-6)

(wherein ρ and q represent an integer of 0 to 12, but when it is 0, the oxygen atom bonded to the aromatic ring is removed.) Further, in the liquid crystal composition of the present invention, a polymerizable group may be added. The liquid crystal composition 'is a nematic liquid crystal composition used for a general liquid crystal device (for example, STN (Super Twisted Nematic) liquid crystal, TN (Twisted Nematic) liquid crystal, TFT (Thin Film Electrocrystal 32 201124510) liquid ss, etc. And a ferroelectric liquid crystal composition, etc. Further, a compound having a polymerizable functional group and not exhibiting liquid crystallinity may be added. Such a compound is generally formed in the technical field as a polymer forming monomer c. The oligomer can be used in a particularly limited manner, and the amount of addition needs to be adjusted to the liquid crystal property of the display. The liquid crystal composition of the invention has a naphthalene skeleton having a relatively wide π electron. Therefore, even if it is not added, a polymerization initiator can be polymerized by heat and light, but it is preferred to add a photopolymerization initiator. The concentration of the photopolymerization initiator to be added is preferably 〇 10 to 10% by mass, more preferably 〇2 to 1% by mass, particularly preferably 0.4 to 5% by mass. The photoinitiator may be exemplified by benzoin ethers, diphenyl ketones, acetophenones, benzyl ketals, and mercaptophosphine oxides. Further, in order to improve the storage stability of the liquid crystal composition of the present invention, a stabilizer may be added thereto. Stabilizers which can be used, for example, may be exemplified by p-phenols and hydroquinone monoalkyl groups. Ethers, tertiary butyl phthalate, gallic phenols, thiophenols, nitro compounds, glutathione, phyllo- naphthols, nitroso compounds, etc. When using stabilizers The amount of addition is preferably in the range of 〜. 5 to 1% by mass, more preferably 0.02 to 〇 5% by mass, and particularly preferably 0.03 to 0.1% by mass, based on the liquid crystal composition. When the liquid crystal composition is used as a raw material for a retardation film, a polarizing film, or an alignment film, or for printing inks, paints, and protective films, metal, metal complex, dye, pigment, pigment, and fluorite may be added depending on the purpose. Light materials, photosynthetic materials, surfactants, leveling agents, touch Agent, agglomerating agent, polysaccharide, ultraviolet absorber, infrared absorber, anti-33 201124510 oxidizing agent, ion exchange resin, metal oxide such as titanium dioxide, etc. Next, the optical anisotropic body of the present invention will be described. The optically-isotropic body produced by polymerizing the liquid crystal composition of the invention can be used for various purposes. For example, when the polymerizable liquid crystal composition of the present invention is polymerized in a non-aligned state, it can be used as a light-scattering plate, a depolarizing plate, In addition, the optical anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an alignment state is useful for optical anisotropy in terms of the properties of the invention. Such an optical anisotropy The body can be produced, for example, by coating the surface of the polymerizable liquid crystal composition of the present invention on a substrate subjected to a nibbing treatment with a cloth or the like, or by using a cloth or the like on the surface of the substrate on which the organic thin layer is formed. On the substrate subjected to the rubbing treatment, or on the substrate having the alignment film on which Si〇2 is obliquely deposited, or after being sandwiched between the substrates, Out of a liquid crystal polymer. Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include a spin coating method, a die coating method, an extrusion coating method, a roll coating method, a bar coating method, a gravure coating method, a spray coating method, a dip coating method, and the like. Printing method, etc. Further, the polymerizable liquid crystal composition can be used as it is, and an organic solvent can be added thereto. The organic solvent may, for example, be ethyl acetate, tetrahydrofuran, toluene, hexane, decyl alcohol, ethanol, dimethylformamide, dioxane, isopropanol, acetone 'methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone. 7~butyrolactone, acetate-2-ethoxyethane, propylene glycol monomethyl ether acetate, ν~methylpyrrolidone. These may be used singly or in combination, and the vapor pressure and the solubility of the polymerizable liquid crystal composition may be appropriately selected. Further, the amount of addition is preferably 90% by weight or less. The method of volatilizing the added organic solvent 34 201124510 can be carried out by natural drying, heat drying, drying under reduced pressure, and drying under reduced pressure. In order to further improve the coating property of the polymerizable liquid crystal material, it is effective to provide an intermediate layer such as a polyimide film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. When an intermediate layer such as a polyimide film is provided on the substrate, the adhesion between the optically anisotropic body and the substrate obtained by polymerizing the polymerizable liquid crystal material is not good, and it can be effectively used as a means for improving the adhesion. The method of sandwiching the liquid crystal composition between the substrates exemplifies an injection method using a capillary phenomenon. It is also effective to decompress the space formed by the substrate; and then inject the liquid crystal material. The alignment treatment other than the rubbing treatment or the oblique vapor deposition of Si〇2 may be performed by using a liquid crystal material in the flow direction, an electric field or a magnetic field. These alignment methods can be used singly or in combination. Further, a photo-alignment method can also be used instead of the rubbing alignment treatment method. This method is, for example, an organic film having a photodimerization functional group in a molecule such as polyethylene cinnamate, an organic film having a functional group which is optically isomerized, or an organic film such as polyimide. The polarized light, preferably irradiated with polarized ultraviolet rays, thereby forming an alignment film. Since the alignment of the alignment can be easily achieved by using the photomask in the photoalignment method, the molecular alignment in the optical anisotropic body can be precisely controlled. The shape of the substrate 'in addition to the flat plate' may also include a curved surface as a constituent portion. The material constituting the substrate can be used regardless of the organic material or the inorganic material. Examples of the organic material constituting the substrate material include polyethylene terephthalate, polycarbonate, polyimine, polyamine, polymethyl 35 201124510 basal-夂f酉曰, polystyrene , polyethylene gas, polytetraethylene, polytrimethylene, polyaryl compounds, poly-column, ethyl cellulose, cellulose polymerization, etc., in addition, inorganic materials, for example, can be listed Shi Xi, glass, calcite, etc. When it is not possible to obtain an appropriate alignment property by rubbing these substrates with a cloth or the like, an organic film such as a polyimide film or a polyvinyl alcohol film may be formed on the surface of the substrate by a known method, and then rubbed with a cloth or the like. Further, a polyimide film for providing a pretilt angle for a conventional D-N liquid crystal device or an STN liquid crystal device is particularly preferable because it can more precisely control the molecular alignment structure inside the optical anisotropic body. Further, when the alignment state is controlled by an electric field, a substrate having an electrode layer is used. The attack time is preferably such that an organic film such as the above-mentioned polyimide film is formed on the electrode. c The method of polymerizing the liquid crystal composition of the present invention is preferably a method of performing polymerization by irradiation with an active light such as ultraviolet rays or an electron beam because it is desired to rapidly polymerize. When using UV light... Use a bias to use a non-biased source. Further, when the liquid crystal composition is polymerized under (four) between the two substrates, at least the substrate on the irradiation surface side must have appropriate transparency with respect to the active energy ray. In addition, it is also possible to adopt a method in which a mask is used for light irradiation, and only after the polymerization is performed, the condition of the electric field, the magnetic field or the temperature is changed, and the unaligned state is changed & The temperature at which the active energy ejector HH is irradiated is preferably within a temperature range in which the liquid crystal state of the liquid of the present invention is maintained. In particular, when it is desired to manufacture an optical anisotropic body by photopolymerization by 36 201124510, it is avoided. From the standpoint of causing undesired thermal polymerization, it is preferred to carry out the polymerization as close as possible to the temperature at room temperature, i.e., /, and 5, preferably at a temperature of 25 ° C. The intensity of the active energy ray is higher. 〇W.cmW/cm2~2w/cm2. When the intensity is 〇lmW/cm2 or less, 'It takes a long time to complete photopolymerization, and productivity is deteriorated, and when it is 2 W/cm2 or more, polymerizable liquid crystal The compound or the polymerizable liquid crystal composition may be deteriorated. The optically anisotropic body of the present invention obtained by polymerization may be subjected to heat treatment in order to reduce initial characteristics and to exhibit stable characteristics. The temperature is in the range of 50 to 250 Å, and the heat treatment time is preferably in the range of 30 seconds to 12 hours. The optical anisotropic body of the present invention produced by this method can be peeled off from the substrate and used alone. In addition, the obtained optically anisotropic bulk layer may be used by being bonded to another substrate. The polymerizable compound represented by the general formula (1) of the present invention may be added to the non-ionic layer. A polymerizable liquid crystal composition is used for polymerizing a polymerizable compound in a liquid crystal composition containing a polymerizable compound, and can be used for a liquid crystal display device in which the alignment energy of a non-polymerizable liquid crystal composition is restricted. It is effective in a PSA (Polymer Sustained _gnment) type liquid crystal display device and a psvA (p〇lymer Stabilised Vemcal Alignment) type liquid crystal display device, and is used as a driving method for AM-LCD (active matrix type liquid crystal display element). ), TN (nematic liquid crystal display element) and STN ~ [CD (super twisted nematic liquid crystal display 37 201124510 display element), and special For AM -. LCI) Further, it may also be used

OCB (Optically Compensated Birefringence)-LCD and IPS-LCD (In-Plane Switching Liquid Crystal Display Element), and can be used for transmissive or reflective liquid crystal display elements. The liquid crystal composition of the present invention contains at least one polymerizable compound represented by the formula (I), and is preferably contained in one to five kinds, and more preferably in one to three kinds. In addition, when the content ratio of the polymerizable compound represented by the formula (1) is small, the alignment regulating force for the non-polymerizable liquid crystal compound is weak, and if the content ratio is large, the energy required for the polymerization increases. The amount of the polymerizable compound remaining without being polymerized is not preferable. Therefore, the lower limit is preferably 〇 1% by mass, more preferably 〇 〇 3 % by mass, and the upper limit is preferably 2. 〇 by mass, more preferably 丨〇 by mass %. The non-polymerizable liquid crystal composition may be a single compound or a mixture of two or more compounds. Further, when the liquid crystal composition is a mixture of two or more kinds of compounds, each compound can exhibit a liquid crystal phase alone. However, as a composition, a compound which does not exhibit a liquid crystal phase may be added as long as a liquid crystal phase is exhibited. The non-polymerizable liquid crystal composition ' can be a compound represented by the formula (m), a compound selected from the group consisting of compounds represented by the formula (IVa), the formula (IVb) and the formula (iVc), The compound selected from the group consisting of the compounds represented by the general formula (Va), the general formula (Vb) and the general formula (Vc) is appropriately selected and adjusted. Wherein, the general formula (III) is: R21—M21—L21—M22—(−L22~M23)—R22 (ιυ) (wherein R21 and R22 independently of each other represent a burning group having 1 to 1 carbon atoms or a dilute group having 2 to 10 carbon atoms, and 1 methylene group present in these groups 38 201124510 or 2 or more non-adjacent groups may be -〇~

--- S generation, and i or more of the above-mentioned β 7 L present in these groups may be substituted by a fluorine atom or a gas atom, and m21, M22 and M23 are independently selected from (a) trans-1 , a 4-folded cyclohexyl group (a sub-american or

Two or more non-contiguous fluorenylene groups may be substituted by -〇_ or one s~ soil S. ), (b) l, 4—phenylene (one _ch= or non-contiguous two or more _CH= may be replaced by —N=), 3 fluoro-^4—extension Stupid and 3,5-difluoro- 1,4-phenylene, and (c) 1,4-cyclohexylene (1,4-cyclohexenylene), 1,4-bicyclic (2.2.2) arsenic Base, piperidine-2,5-diyl, naphthalene_2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-:tetrahydronaphthalene-2,6-di The group in the group consisting of 〇, 〇 represents 〇, 1 or 2, and L21 and L22 represent each other independently, a single bond, a CH2CH2—, a (ch2)4—, a _0CH2—, —CH2O—' — 〇CF2 — ' — CF2〇— ' — COO — ' — OCO — ' — CH=CH---CH=N—or —(:Ξ(:_, when there are multiple L22 and/or M23, they may be the same or different The formula (IVa), the formula (IVb) and the formula (iVc) are: 39 201124510

R32_M33 (IVa)

(IVb)

L38-m38Vy33 g (IVc) (wherein R, r32 and R33 independently of each other represent an alkyl group having from 1 to 10 carbon atoms or an alkenyl group having from 2 to 10 carbon atoms, and one subgroup present in these groups Two or more methylene groups which are non-contiguous or non-contiguous may be substituted by -哎-S- and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms or gas atoms, M3 丨, Μ32, Μ33, Μ34, Μ", M37 and M38 are independently of each other and are selected from (d) trans-l,4--cyclohexylene (one methylene group present in the group or two or more sub-adjacent The methyl group may be substituted by or with s.), (e) l, 4 a phenyl group (one one CH= or two or more non-contiguous ones in the group may be replaced by a nitrogen atom), 3—Fluoro-1,4-phenylene and 3,5-difluoro-1,4-phenylene, and (〇1,4-cyclohexylene, !, 4-bicyclo(2.2.2) a group consisting of octyl, piperidinyl-yl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl and decaquinone~2,6-diyl a group in the above group, the hydrogen contained in the group (d), the group (e) or the group (f) The atom may be replaced by a cyano group, a fluorine atom, a trifluoromethyl group, a trifluorodecyloxy group or a 201124510 gas atom, and LJI, L32, l33, τ ” τ “represents a single bond, —COO—”〇c〇: 'L37 and π are independent of each other -CH2CH2 - ' - (CH2)4, ~C Η 2 Ο —, — ο "p2 -, a CF2O - or a [Ξ 34 35 -, an och2 c —, when there are multiple Μ32, Μ34 , M35, e t36 , 38 M, M37, M38, l3I, l33 5, L and/or 1^, they may be the same, + Χ3Ι, Χ32, Χ33, Χ34, χ35, / hydrogen or fluorine atom, : independently of each other, Y3, Y32 and γ33 are independent of each other, cyanide, 氦垆1, non-hydrogen atom, fluorine atom, chloroproperyl group, aryl group: trimethoxy, trimethylethyl or difluoromethyl The oxy group, at least one of X31, X32 or γ3丨 represents a fluorine atom, a gas atom, a cyano group, a thiocyanyl group, a trifluoromethoxy group, a gas. Each of the methyl groups, 2, 2, 2—Trifluoroethyl nibble—either methoxy, or at least one of the hydrogen atoms contained in M31 or Μ” is not a chaotic group, a fluorine atom, a tris-methyl group, a Sandon methoxy group or a gas atom.

X

At least one of X χ or γ represents a fluorine atom, a gas atom, a cyano group, a thiocyanyl group, a trisyl methoxy group, a trifluoromethyl group, a 2,2,2-trisylethyl group or a difluorodecyloxy group. Or at least one of the hydrogen atoms contained in Μ33 'Μ34 or μ35 represents at least one of cyano, fluorogenic+, trifluoromethyl, trifluoromethoxy or ban i atoms, X36, X" or Y33 a fluorine atom, a chlorine atom, a cyano group, a thiocyanyl 'trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a difluorodecyloxy group, or a M36, M" or m38 At least 41 of the hydrogen-containing atoms 201124510 fluorodecyloxy or a gas atom, 1 or 2, but d + e and one represents a cyano group, a fluorine atom, a trifluoromethyl group, = c, d, e, f, and g each other Independently, 〇f + g is 2 or less. The general formula (Va), the general formula (Vb) and the general formula (Vc) are: R41—Μ41 ten L41 one Μ4 ten L·42

L43-M43j7R44

R43_M47-^.L47_M48^.L48.

L49-M49^R46 (Va) (Vb) (Vc) (wherein d2, R43, and mr46 independently of each other represent an alkyl group having 1 to 10 Å or a carbon number of 2 to 1 Å. Alkenyl group, one methylene group present in these groups or two or more methylene groups which are not adjacent may be substituted by one 0- or one S-, and one or two or more hydrogens present in these groups The atom may be substituted by a fluorine atom or a gas atom, and Μ, Μ42, Μ43, Μ44, Μ45, Μ46, Μ47, M48 and M49 are independently of each other and are selected from (g) trans-1,4-, 4-cyclohexyl (in this group) The presence of two subunits of the 曱 曱 戈 非 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 、 、 、 、 、 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― Non-contiguous two or more CH = can be substituted by a nitrogen atom), and (i) 1,4 - cyclohexylene, 1,4 -bicyclo(2_2 · 2) octylene, piperidine - 2, 5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl and decahydronaphthalene-2,6-diyl 42 201124510, base (h) or a group of fluorene difluoromethyl groups, trifluoromethoxy groups or groups in the group (i) The above group (g) atoms may be substituted by a cyano group, a fluorine atom or a chaotic atom, respectively, 47 L and L49 are each independently CH2CH2-, _(CH2)4, -cf2o- or -Cs L41, L42, L43, L44 , L45, L46, l stand for single bond, -COO-, one 〇c〇__, __ ~〇CH2- ' -ch2o- ^ -ocf2- c-, ϊ44, τ 46 47 iV1 ' M ' L41 > L43 . , \2 and / or π 夺, they may be the same or different, and each other independently represents a trimethyl, tri(a)oxy or a gas atom, X43, χ45, χ46 _# and X each other Independently representing hydrogen atom II, methyl, trifluoromethoxy or fluorine atom, but any of χ4, and χ42 represents a fluorine atom, X43, Χ44, and χ45, χ46, γ47 4R ( any of It means that a fluorine atom, and any one of X represents a fluorine atom, but X46 and X47 are different from each other to represent a fluorine atom, and χ46 and X48 do not simultaneously represent an atom, and 〇 represents anthracene two: 〇...h, "...,... independently of each other Indicates that ., . . . , J+r and s+t are 2 or less.) The human liquid crystal composition preferably contains at least one compound represented by the general formula (111), which is selected from the general formula (IVa) and the general formula. The compounds of the group consisting of IVb) and the compound represented by the formula (IVe) or the compound selected from the group consisting of the compound of the formula (Va), the formula of the formula and the formula of the formula are preferably contained! Two or more compounds represented by the formula (ΠΙ) and further comprising one or a group of humans u selected from the group consisting of the formula (IVa), the formula (ivb), and the formula 〇Vc) The liquid crystal composition of the compound in the group, and the compound represented by the above formula or the formula of the compound represented by the formula (Va) and the formula (Vb) A liquid crystal composition of a compound in the group consisting of the compounds represented by the general formula (Ve). The two substrates of the liquid crystal cell used for the liquid crystal display element may be made of a flexible transparent material such as glass or plastic, or may be an opaque material such as Shi Xi. The transparent substrate having a transparent electrode layer can be obtained by using indium tin oxide (ITO) on a transparent substrate such as a glass plate. The color former ' can be produced, for example, by a pigment dispersion method, a printing method, a plating method, or a dyeing method. A method of producing a color filter by a pigment dispersion method will be described by way of an example in which a curable coloring composition for a color former is applied onto the transparent substrate to perform patterning treatment, and (4) by heating or light irradiation. It hardens. # By performing this step separately for the red and blue colors, the pixel portion for the color numerator can be made. In addition to this, a pixel electrode provided with an active element such as a TFT, a thin film diode, a metal insulator, or a metal specific resistance element may be provided on the cough substrate. The substrate is opposed to each other such that the transparent electrode layer is inside. At this time, the interval between the substrates can be adjusted through the separator. At this time, the thickness of the preferred layer to be obtained is adjusted to 丨~丨(9)^. More preferably, it is i 5 to the core claw, and when a polarizing plate is used, it is preferable to adjust the refractive index anisotropy of the liquid crystal and the product of each thickness d to maximize the contrast. In addition, when there are two polarizing plates, The viewing angle and contrast can be adjusted to be good by adjusting the polarization axis of each polarizing plate. The retardation film for expanding the viewing angle can also be used. The separator, for example, can be exemplified by glass particles, plastic particles, and oxidation. Ming particles, 44 201124510 "materials, etc., and then a sealing agent such as an epoxy thermosetting composition is screen-printed on the substrate in the form of a liquid crystal injection port, and the substrates are bonded to each other and heated to form a sealant. Thermosetting: A method of sandwiching a polymer-stabilized liquid crystal composition between two substrates can be carried out by a general vacuum injection method, an ODF method, etc. As a method of polymerizing a polymerizable compound, since it is desired to rapidly carry out polymerization, It is preferably a method of performing polymerization by irradiating ultraviolet rays or an active energy source such as an electron beam. When ultraviolet rays are used, a polarized light source can be used or non-polarized light can be used. When the liquid crystal composition is polymerized in a state in which the liquid crystal composition is sandwiched between the two substrates, at least the substrate on the irradiation surface side must have appropriate transparency with respect to the active energy ray. Alternatively, such a method may be employed. When a light is irradiated, a mask is used, and only a specific portion is polymerized, and the alignment state of the unpolymerized portion is changed by changing conditions such as an electric field, a magnetic field, or a temperature, and the active energy ray is further irradiated to be polymerized. In the case of applying an alternating current to the liquid crystal composition containing the polymerizable compound, it is preferably subjected to ultraviolet light exposure. The alternating current applied is preferably an alternating current of frequency to position z, more preferably frequency _ to _ζ, and the voltage can be based on The desired liquid crystal display W pretilt angle is selected. That is to say, 'the pretilt angle of the liquid crystal display element can be applied. In the MVA mode liquid crystal display, from the viewpoint of alignment and contrast, Preferably, the tilt angle is controlled from 80 degrees to 89 degrees. The temperature at the time of: is preferably maintained in the liquid crystal composition of the present invention. In the temperature range of the state, it is preferably at a temperature close to room temperature, that is, in the case of the model 45 201124510, it is 15 to 6 (concentration at the temperature of TC. The lamp that generates ultraviolet light can use a metal toothed lamp, high pressure Mercury lamp, ultra-high pressure mercury lamp, etc. Further, 'the wavelength of the ultraviolet ray to be irradiated' is preferably required to illuminate the ultraviolet ray in the wavelength region of the absorption wavelength region of the non-liquid crystal composition, and it is preferably used to filter out the ultraviolet ray. The strength is preferably 〇imW/cm2 to 100 W/cm2, more preferably 2 mW/cm2 to 8 〇w/cm2. The energy of the irradiated ultraviolet ray can be appropriately adjusted, preferably from 1 〇 to 1 〇〇〇〇mj/ More preferably, it is 100 to 70 〇〇mJ/cm2. When the ultraviolet ray is irradiated, the intensity can be changed. The time of irradiating the ultraviolet ray can be appropriately selected depending on the intensity of the irradiated ultraviolet ray, preferably 10 to 600 seconds. Further, the liquid crystal display element of the present invention obtained by polymerization can exhibit stable characteristics in order to reduce the initial characteristic change, and can also be subjected to heat treatment. The heat treatment temperature is in the range of 50 to 25 (TC range, and the heat treatment time is preferably in the range of 30 seconds to 12 hours. The polymerizable compound used in the present invention must control the alignment of the liquid crystal material after polymerization, and maintain it for a long time. Therefore, the alignment restriction force of the liquid crystal and the mechanical strength of the cured product are required. Further, if a polymerizable compound remains after curing, or a large amount of polymerization initiator remains, display defects may occur, so even if it is required The polymerization may be carried out using a small amount of a polymerization initiator or without using a polymerization initiator. A compound having a polymerizable functional group and exhibiting no liquid crystallinity may be added. Such a compound is usually recognized as a technical field in the art. The polymer-forming monomer or the polymer-forming oligomer can be used without particular limitation. However, after the polymerizable compound is cured, the liquid crystal layer must exhibit a liquid crystal phase, as shown in & In the case of a liquid crystal composition, the amount of addition must be adjusted to exhibit liquid crystallinity. It is preferable to contain one type of ～5⁄4', and it is preferable to contain one type to three types. In addition, if the content of the polymerizable compound is small, the alignment resistance of the liquid crystal molecules is weakened, and if the content ratio is too high, 'Bei, the energy required for the polymerization increases, and the amount of the polymerizable compound remaining without polymerization increases, so the lower limit is preferably 0.01% by mass, more preferably 0. 03% by mass, and the upper limit is 2% by mass. Further, the polymerizable compound represented by the formula (I) may be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added as needed. In the case of the compound represented by the formula (I), the concentration of the photopolymerization initiator is preferably 丨~(7)% by mass, more preferably 〇2 to 〇质量%, and particularly preferably 0.4 to 5% by mass. The photoinitiator may, for example, be a succinct, a dipyridyl ketone, a ketone ketone, a benzyl ketal or a mercaptophosphine oxide. The thermal polymerization initiator may be azodi Nitrile, albino peroxide, etc. In addition, 'in order to improve the liquid of the present invention Stabilizers may also be added to the storage stability of the composition. Stabilizers which can be used, for example, may be exemplified by the class of dioxin, the succinyl ether, and the tertiary butyl succinyl phenol. , gallic phenols, thiophenols, nitro compounds, valenic amines, stone naphthols, nitroso compounds, etc. The addition amount 'with respect to the liquid crystal composition' when using a stabilizer is preferably 〇. 〇〇 5 to 1% by mass, more preferably 0.02 to 0.5 mass 0/〇, particularly preferably 〇.〇3 to 0J% by mass. Example 47 201124510 The following 'is explained in more detail by way of examples. The present invention is not limited to the examples. The % in the compositions of the following examples and comparative examples indicates "% by mass". (Example 1) A stirring device, a cooler, and a thermometer are provided. The reaction vessel was charged with 20 g (90 mmol) of 6-bromo-naphthol, 17 g (n4 mmol) of butyl acrylate, 13.5 g (134 mmol) of triethylamine, 1; g of palladium acetate, 3〇〇ml dimethylformamide, heat the reactor under nitrogen to i &£>c, Reaction. After completion of the reaction, ethyl acetate and THF were added, and then the organic layer was washed with 1% aqueous hydrochloric acid, purified water, and brine. After distilling off the solvent, it was purified by a 2-fold (weight ratio) gel column to obtain 13 5 g of the compound represented by the formula (1). (1) Next, in a reaction vessel equipped with a stirring device, a cooler, and a thermometer, 1 g (37 mmol) of the compound represented by the above formula (1), and 9.2 g (37 mmol) 4 were charged. One (3-propenyloxypropoxy)benzoic acid, 5 mg of dinonylaminopyridine '150 ml of dioxane, and the reaction vessel was kept below $ °C with an ice bath. Under a nitrogen atmosphere, 5. 5 g (44 g mole) of diisopropylcarbodiimide was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction mixture was filtered, 2 ml of methane methane was added to the filtrate, and the mixture was washed with a 10% aqueous hydrochloric acid solution, and then washed with saturated brine and dried over anhydrous sodium sulfate. The (weight ratio) Shishi gum column was made into (4), and recrystallized from the red MW nail material to obtain 12 g of the target compound represented by the formula (2). 48 (2) 201124510

Further, 12 g of the compound represented by the formula (2) was dissolved in a reaction vessel equipped with a stirring device, a cooler and a thermometer. After the second gas methane, the commercial solution 5 plus monofluoroacetic acid was mixed for 30 minutes at the temperature. Then, pure water was added to precipitate a solid. The solid was dissolved in 15 ml of ethyl acetate, 15 ml of hydrogen, and the organic layer was washed with brine. The solvent was evaporated to give 9 g of the compound of formula (3).

(3) Next, in a reaction vessel equipped with a stirring apparatus, a cooler, and a thermometer, 9 g (20 mmol) of the compound represented by the above formula, and 39 g (2 Torr of millimolar) acrylic acid = 2 - ( 4-Hydroxyphenyl)ethyl ester, 24 mg of dinonylaminopyridine, 100 ml of dioxane, and the reaction vessel was kept below 5 ° C with an ice bath. Under a nitrogen atmosphere, 3 g (24 mmol) of diisopropylcarbodiimide was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction mixture was filtered, 2 ml of methane methane was added to the filtrate, and washed with a 10% aqueous hydrochloric acid solution, and washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, it was purified by using a double-stranded (by weight) silica gel column and recrystallized from dichloromethane/nonanol to obtain 7 g of the target compound represented by the formula (4). The compound exhibits a smectic liquid crystal phase at 13 8 ° C to 17 5 ° C and is at 175. (: The nematic liquid crystal phase is displayed in a wide range of up to 220 ° C. ~^-〇(ch2)3-o 49 (4) 201124510 (physical value) !Η_ NMR (solvent: deuterated gas imitation): ( 5 : 2.21(t,2H), 3.00(t, 2H) ' 4.16(t,2H),4.3 7- 4_41(m,4H),5_82- 5.87(m,2H), 6.09- 6_18(m,2H) , 6.38 - 6.45 (m, 2H), 6.72 (d, 1H), 7.00 (dd, 2H), 7.14 (dd, 2H), 7.26 - 7.29 (m, 2H), 7.39 (dd, 1H), 7.70 - 7.76 (m, 2H), 7.84 (d, 1H), 7.92 (d, 1H), 8.00 (m, 2H), 8.18- 8.20 (m, 2H) l3C-NMR (solvent: deuterated gas): (5: 28.4, 34·4, 61.1, 64'6, 64.8, 114.3, 117.4, 118.8, 121.6, 122.4, 128.2, 128.5, 129.8, 130", 131.5, 131.2, 131.5, 132.4, 134.9, 135.3, 146.3, 149.9, 163.2 , 164.8, 165.4, 166.0, 166.1 Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652 - 1622, 809 cm.i Melting point: 138 ° C (Example 2) with stirring device, cooler and thermometer Into the reaction vessel, 7 g (26 mmol) of the compound of the formula 〇) described in Example 1 and 4.6 g (31 mmol) of 3-propylpropyl propylene were charged. Ester, 4.3 g (31 mmol) of carbonic acid unloading, iOOmi trimethylamine, and the reactor was heated to 9 Torr in a solvent atmosphere, and then the organic layer was washed with 10% saturated brine. After the solvent, the silica gel column is purified to obtain a °C of the formula (5), and the reaction is carried out for 6 hours. After the reaction is completed, the aqueous solution of hydrochloric acid, pure water, and saturated saline is added to the mixture for 2 times (weight). The target is compounded by a silica gel column.

(5) 50 0 201124510 Further, in a reaction vessel equipped with a stirring device, a cooler and a thermometer, '8 g of the compound of the formula (5) is dissolved in 15 ml of dioxane, and 10 ml of trifluoroacetic acid is added dropwise. Stir at room temperature for 3 minutes. Then, pure water was added to precipitate a solid. The solid was dissolved in 150 ml of ethyl acetate, 150 ml of hexanes, and the organic layer was washed with brine. The solvent was distilled off to obtain 6 g of a compound of the formula (6).

Then, 'in a reaction vessel equipped with a stirring device, a cooler and a thermometer,' was charged 6 g (1 8.4 mmol) of the compound represented by the above formula (6), and 3.5 g (18.4 mmol) of acrylic acid = 2 - (4) -Hydroxyphenyl)ethyl ester, 240 mg of dimethylamino group, 100 ml of dioxane' and the reaction vessel was kept below with an ice bath. Under a nitrogen atmosphere, 2.8 g (22 mmol) of diisopropylcarbodiimide was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction mixture was filtered, 200 ml of dioxane was added to the filtrate, and the mixture was washed with a 1% aqueous solution of hydrochloric acid, and the mixture was washed with saturated brine and dried over anhydrous sodium sulfate. After distilling off the solvent, it was purified by a two-fold (by weight) silica gel column and recrystallized from dichloromethane/nonanol to obtain 5 g of the target compound of the formula (7). This compound exhibited a smectic liquid crystal phase at 94 ° C to 102 ° C, from i 〇 2t to 128. (: The nematic liquid crystal phase is shown.

(physical value) Η — Ν Μ R (> gluten. Long-term gas imitation)·(5 . 2_23(t, 2Η), 3 00(t 51 201124510 2H), 4.22(t, 2H), 4.3 7— 4.43 (m,4H),5.82—5.88(m,2H), 6.09- 6.1 8(m,2H),6.3 8 - 6.45(m,2H),6.66(d,1H),7.08 -7_15(m,3H) , 7.17- (dd, 1H), 7.23 - 7.28 (m, 2H), 7.68 - 7.79 (m, 3H), 7.91 (s, 1H), 7.79 (d, 1H) 13C-NMR (solvent: deuterated gas imitation ): δ : 28.5, 34.5, 61.3, 64.4, 64_8, 106.7, 116.1, 119.7, 121.6, 124.1, 127.6, 128.3, 128.6, 129.6, 129.9, 130.3, 130.8, 130.9, 135.2, 135.8, 146.8, 158.1 Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652 - 1622 > 809 cm'1 Melting point: 94 ° C (Example 3) In a reaction vessel equipped with a stirring device, a cooler and a thermometer, 6 g (18.4) The compound represented by the formula (6) described in Example 2, 3.6 g (18.4 mmol) of 4, monocyano-4-hydroxyl stupid, 24 mg of dinonylaminopyridine, 100 ml of two gas曱 ,, and keep the reaction vessel below 5 °c with an ice bath. Under nitrogen, slowly instill 2 8g (22 Mohr) diisopropylcarbodiimide. After the completion of the dropwise addition, the reaction vessel was returned to room temperature for 5 hours. After filtering the reaction solution, 2 ml of dioxane was added to the filtrate, and 10 The organic layer was washed with a saturated aqueous solution of hydrochloric acid, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was evaporated, the residue was purified by using a two-fold weight ratio of the Shiqi gum column. Recrystallization, thereby obtaining 5.3 g of the target compound represented by the formula (8), which exhibits a nematic liquid crystal phase in a wide range from 15 to 220 ° C. 52 201124510

H-NMR (solvent: deuterated gas): 5: 2.23 (t, 2H), 4.21 (t, 2H), 4.41 (t, 2H), 5, 83 (dd, 1H), 6.11 - 6.15 (m) ,1H),6.41 -6_45(m,lH)'6.68(d,lH),7.14-7.17(m,2H),7.25-7.33(m,2H) ' 7.57- 7.77(m,8H),7.88(s , 1H), 8.00 (d, 1H) 13C_ NMR (solvent: deuterated gas imitation): 5: 28·5, 61.2, 64.4, 106.7, 110.9, 115.7, 118.8, 119.7, 122.3, 124", 127.6, 128.2, 128,6,129.4,130.3,130.9,132.6,135.9,136.6, 144.8,147.2,151.3,158.2,165.4,166.1 -V·.' Infrared Absorption Spectrum (IR) (KBr) : 2925,2855,1760,1652 — 1622,809cm-1

Melting point: 159 ° C (Example 4) In a reaction vessel equipped with a stirring device, a cooler, and a thermometer, 4 g (14 mmol) of the compound represented by the formula (1) described in Example 1 and 4.2 g ( 14.4 millimoles) 4 mono(6-propenyloxyhexyloxy)benzoic acid, 200 mg dinonylaminopyridinium, 2.2 g ( 17.2 mmol) of diisopropylcarbodiimide, 150 ml Dichlorosilane 'reacted under nitrogen for 6 hours. After completion of the reaction, 100 ml of dioxane was added, and then the organic layer was washed with a hydrazine aqueous solution of hydrochloric acid, purified water, and brine. After distilling off the solvent, it was purified by using a two-fold (by weight) ruthenium column to give 7 g of the compound of the formula (9). 53 (9) 201124510 )-〇(ch2)6,〇

In a reaction vessel equipped with a mixing device, a cooler and a thermometer, 7 g of the compound of the formula (9) was dissolved in 15 ml of dichloromethane, and then 10 ml of difluoroacetic acid was added dropwise thereto, and the mixture was stirred at room temperature for 3 minutes. . Then, pure water was added to precipitate a solid. The solid was dissolved in 15 mL of ethyl acetate, EtOAc (EtOAc) and EtOAc. The solvent was distilled off to give 5-7 g of a compound of formula (1).

(10) Next, 'In a reaction vessel equipped with a stirrer' cooler and a thermometer, '5.7 g (11.6 mmol) of the compound represented by the above formula (10), 1.6 g (11.6 mmol) of 2-fluoro A 4-hydroxybenzonitrile, i5 〇 mg decylamino october, 100 ml of dichloromethane, and the reaction vessel was maintained at 5 with an ice bath. Below you. Ug (22 mmol) of diisopropylcarbodiimide was slowly added dropwise under a nitrogen atmosphere. After the completion of the dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction mixture was filtered, 200 ml of dioxane was added to the filtrate, and the mixture was washed with aq. After distilling off the solvent, it was purified by a two-fold (by weight) silica gel column, and recrystallized from dioxane/methanol to obtain

4 g of the target compound represented by the formula (11). This compound exhibits a nematic liquid crystal phase in a wide range of from 136 ° C to 220 ° C:.

(physical value) 54 201124510 iH-NMR (solvent: deuterated gas): 5: 1.47 - 1.51 (m, 4H), 1.71- 1.75 (m, 2H), 1.83 - 1.85 (m, 2H), 4.05 (t , 2H), 4.1 7(t, 2H), 5_82(dd, 1H), 6.09-6_16(m,1H), 6.39- 6.43(dd, 1H) ' 6.71 (d,1H), 6.97 — 7.01 (m, 2H), 7.15-7.21 (m, 2H), 7.41 (dd, 1H), 7.65 - 7.75 (m, 3H), 7.85 - 7_95 (m, 2H), 8.02 - 8.07 (m, 2H), 8.16 - 8.20 ( m, 2H) 13C - NMR (solvent: deuterated gas): <5: 25.6, 28.5, 28_9, 64.4, 68.1, 110.7, 110.9, 113.5, 114.3, 115.8, 118.9, 121.2, 122.6, 124.0, 128.5, 128.7, 130.2, 130.5, 130.9, 131.1, 132.3, 134.0, 135.1, 148.2, 150.3, 155.5, 163.6, 164.8, 166.2 Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652 — 1622 * 809cm'1 Melting point: 136 ° C (Example 5) A polymerizable liquid crystal composition (composition 1) having the composition shown below was prepared. 55 201124510 0(CH2)3—〇 "^0(CH2)3-0 ^〇(CH2)3-o^^^3^〇-〇-(CH2)2-〇-^== 20%

25% ~^o-(ch2)6o-^^-^-Cn i〇% The polymerizable liquid crystal composition' has good compatibility and exhibits a nematic liquid crystal phase. To the composition, 3% of Irgarcure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to prepare a polymerizable liquid crystal composition (composition 2). The cyclohexanone solution of the composition 2 was spin-coated on a glass with polyimine, and it was irradiated with ultraviolet rays of 4 mW/cm 2 for 20 seconds using a still-pressure mercury lamp, and as a result, the composition 2 was maintained in a uniform alignment state. The polymerization is carried out to obtain an optical anisotropic body. The surface hardness of the optically anisotropic body (according to jIS_S - κ - 5400) is Η. When the phase difference before the heating of the obtained optical anisotropic body was 1 〇〇%, the phase difference after heating at 240 ° C for 1 hour was 84%, and the phase difference reduction rate was 16%. (Comparative Example 1) A polymerizable liquid crystal composition (composition 3) having the composition shown below was prepared. 56 10%201124510 > (CH2)3-〇- CH, p

o 7-o(ch2)3-o-〇^^-} -〇-(CH2)3〇- 15% -〇(CH2)6-〇- N=/ oo -〇(CH2)3-〇-〇 (ch2)6-o

O-iCH^O-^ 0-(CH wonderful f 25% 15% 25% 10% -〇-(CH2)6-〇-polymerizable liquid crystal composition exhibits a nematic liquid crystal phase, but has poor solubility" Crystals were precipitated on the next day. (Comparative Example 2) A polymerizable liquid crystal composition (composition 4) having the composition shown below was prepared. 45% ^〇(CH2)6O^0^'O^〇^〇-〇-( CH2)6〇-^= 45% -(ch2v

The 10% polymerizable liquid crystal composition has good compatibility stability and exhibits a nematic liquid crystal phase. To the composition, 3% Irgarcure 9〇7 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to prepare a polymerizable liquid crystal composition (composition 5 " the % hexanyl solution of the composition 5 was spin-coated with polypyrene On the glass of the amine, it was irradiated with ultraviolet light of 4 mW/em2 for 120 seconds using a high-pressure mercury lamp, and as a result, the composition of the polymer was obtained by polymerizing in the state of maintaining a uniform alignment. The surface hardness of the optical anisotropic body was obtained. According to JIS-SK-5400, it is 2B. When the phase difference of the obtained optical anisotropic body before heating is 100%, the phase difference after heating at 24 ° C for 1 hour is 75%, and the phase difference reduction rate is It is understood that the composition 5 of Comparative Example 2 has a larger phase difference reduction ratio than that of the composition 2 of the present invention, and the retardation rate is large, and the surface heat is poor. 2B is not sufficient. (Example 6) In a reaction vessel equipped with a stirring device, a cooler and a temperature meter, 20 g (90 mmol) of 6-bromo-2-naphthol and 17 g (134 m) were charged. Mole) butyl acrylate, 13.5 g (134 mmol) triethylamine, lg acetate palladium, 3 〇〇m l Dimercaptocarhamamine, heat the reactor to 1 〇 (TC) under nitrogen atmosphere. After the reaction, add ethyl acetate and THF, then use ι〇% hydrochloric acid solution, pure water, saturated salt. The organic layer was washed with water, and the solvent was removed from the obtained organic layer, and then purified by using a double-strength (weight ratio) Shishi rubber column to obtain 1 3.5 g of the compound represented by the formula (1 2 ).

Next, in a reaction vessel equipped with a stirring device, a cooler, and a thermometer, 4 g (15 mmol) of the compound represented by the above formula (12), LSgd? millimolar) argon helium, 50 ml of two gas were charged. Methane was cooled to 5 ° C or lower under a nitrogen atmosphere while stirring. Next, 1.8 g (18 mmol) of triethylamine was slowly added dropwise. After the completion of the dropwise addition, the reaction was further carried out at 2 (rc for 3 hours. After the completion of the reaction, 'the second image was added; the decane was sequentially purified from the obtained organic compound by using 丨〇% salt 58 201124510 to obtain an aqueous acid solution, pure water, and saturated salt. The organic layer was washed with water. After the solvent was removed from the layer, '2 times (by weight) of the Shixi gum column was used to 4.0 g of the compound represented by the formula (13).

(13) Next, in a reaction vessel equipped with a mixing device, a cooler, and a thermometer, 4 g of the compound represented by the formula (13) is dissolved in 15 m of a gas-fired product, and while stirring, the mixture is poured into the crucible. Trifluoroacetic acid, further at room temperature; stirred for 30 minutes. Then, pure water was added to precipitate a solid. This solid was dissolved in a mixed solvent of 150 ml of ethyl acetate and 150 ml of (f)hydrofuran, and the layer was washed with saturated brine. In the obtained organic layer, the solvent was obtained, and 2.9 g of the compound represented by the formula (14) was obtained. Further, 2.5 g (9 mmol) of the compound represented by the above formula (14) and 1.8 g (10 mmol) of p-hydroxyphenyl fluorenyl group were charged in a reaction vessel equipped with a stirring device, a cooler and a thermometer. Acrylate, 122 mg of dimethylaminopyridine, 50 ml of di-methane, while slowly maintaining the reaction vessel below 5 ° C with an ice bath, while slowly dropping 14 g (11 mmol) of diisopropyl carbon in a nitrogen atmosphere. Imine. After the completion of the dropwise addition, the reaction vessel was returned to room temperature for further reaction for 5 hours. After filtering the reaction solution, 1 〇〇ml of di-methane was added to the filtrate, and the mixture was washed successively with a 5% aqueous hydrochloric acid solution and brine, and then the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent from the obtained organic layer, it was purified by a 2 column S (weight ratio) alumina column, and obtained by recrystallization from a mixed solvent of dioxane/hexane to obtain 2 2 g of the formula 5). Target 59 201124510 Polymeric compounds. The polymerizable compound exhibits a nematic liquid crystal phase in a wide temperature range of 169 ° C to 22 (TC or more.

(physical value) NMR (solvent: deuterated chloroform) δ : 2.07 (s, 3H), 5.77 (m, 1H), 6.06 (dd, 1H), 6.35 - 6.42 (m, 2H), 6_62- 6.71 (m, 2H), 7.15- 7.25 (m, 4H), 7.34 (dd, 1H), 7.64 (d, 1H), 7.75 (dd, 1H), 7_83 (m, 1H), 7.90 (d, 1H), 8.00 - 8.06 (m, 2H) 13C - NMR (solvent: deuterated gas): (5: 18.3, 117.3, 1 18.6, 122.0, 124.2, 127.4, 128.5, 130", 131.2, 131.5, 134.8, 135.7, 146.5, 148.1, 148.2, 149.9, 164.4, 165.2, 165.7 Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652 - 1622, 809 cm-1 Melting point: 169 ° C (Example 7) except 1.5 g of Example 6. (17 mmol) of ytterbium acrylate was changed to I* 1 _8 g of yttrium methacrylate, and 2.4 g of the target compound represented by the formula (16) was obtained by the same method "The compound was at 160 ° C to 2 2 A nematic liquid crystal phase is exhibited in a wide range of 0 ° C or more.

(physical value) NMR (solvent: deuterated gas imitation): occupies: 2. 〇 6 (s, 3H), 2.10 (s, 3H) ' 5.76 - 5.83 (m, 2H) ' 6.35 — 6.42 (m, 2H) , 6.71 (d, 1H), 201124510 7.15- 7.25 (m, 4H), 7.34 (dd, 1H), 7.64 (d, 1H), 7.75 (dd, 1H), 7_83 (m, 1H), 7.90 (d, 1H), 8.00- 8.06 (m, 2H) 13C-NMR (solvent: deuterated gas): (5: 18_3, 117.3, 118.7, 122.2, 124.2, 127.3, 128.5, 13 (M, 131.2, 131.5, 134.9, 135.7, 146.5, 148.1, 148.2, 149.9, 165.2, 165.7, 165.8 Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652 - 1622 > 809 cm '1 Melting point: 160 ° C (Example 8) Preparation The following liquid crystal composition LC-1. The composition of the compound and the ratio of the content are as follows.

10% 10% 10% 15% c3h7-^Jh 15% θ~°5Η» 15% c3h7-(^>- ^y^c2H5 5% C5Hn^}- -〇-CH3 10% O~0^ch3 10 % The physical properties of the above liquid crystal composition LC-1 are shown in Table 1. [Table 1]

Tn-i (C) 72 Δ £ -3.3 Δη 0.086 Relative to 99.7% of the liquid crystal composition LC-1' by the addition of 〇_3% 实61 201124510 The polymerizable compound shown in Example 6 is uniformly dissolved to prepare a polymerization. Liquid crystal composition CLC-1. The physical properties of CLC-1 are almost indistinguishable from the physical properties of Lc_丨 above. The CLC-1 was injected into the cell gap by a vacuum injection method and was placed in a box of IT crucible coated with a polyimine alignment film that induces vertical alignment (H〇me〇tr〇pic alignment). The liquid crystal cell was irradiated with ultraviolet light by a high-pressure mercury lamp while applying a 1.8 V rectangular wave having a frequency of ΙΚΗζ while passing through a filter for filtering ultraviolet rays of 31 〇 nm or less. The irradiation intensity adjusted to the surface of the cell was irradiated for 100 sec., and the vertical alignment liquid crystal display element which polymerized the polymerizable compound in the polymerizable liquid crystal composition was obtained. Then, the amount of the monomer remaining in the liquid crystal composition was measured by high performance liquid chromatography (HPLc: solvent: acetonitrile), and the results are shown in Table 2. Further, while applying a voltage of 5 V to the obtained vertical alignment liquid crystal display element, the film was heated at 70 ° C for 24 hours, and the pretilt angles before and after the change were shown in Table 2. [Table 2] The amount of the monomer before the ultraviolet irradiation was 0.3%. The monomer 詈 after the ultraviolet irradiation was 0.01%. From the above results, it was found that the polymerizable compound of Example 6 can be sufficiently polymerized without a photopolymerization initiator. Further, the pretilt angle (crystal rotation method) of the liquid crystal element before and after the ultraviolet irradiation and the heating at 24 ° C for 24 hours and the measurement results of the electrooptical characteristics of the device are shown in Table 62 201124510 [Table 3] Before the ultraviolet irradiation The pretilt angle is 89.0. Pre-tilt angle after UV irradiation 87.5° Pre-tilt angle after 24 hours at 70°C 87.2° Threshold voltage (V) 2.40V Voltage retention rate (applied voltage IV, held for 16 67ms, 97.5%) As a result of the above pretilt angle, it is known that When the polymerizable compound is condensed, the pretilt angle is changed to obtain a vertical alignment liquid crystal display element which imparts a pretilt to the liquid crystal molecules. Further, after the heating test (7 〇〇 c, 24 hours), the pretilt change is small. From this, it is understood that the liquid crystal display element using the polymerizable compound of the present invention has excellent stability. (Comparative Example 3) With respect to 99.7 % of the liquid crystal composition 1 C - 1 ' by adding 〇3 % formula (1 7 The polymerizable compound shown is uniformly dissolved to prepare a polymerizable liquid crystal composition CLC-2. The physical properties of CLC-2 are almost indistinguishable from the physical properties of the above LC_丨. The CLC-2 is injected into the box using a vacuum injection method. The gap is 1 〇# m and is packed in a box of IT〇 coated with a polyimide film which induces vertical alignment. A 1.8V rectangular wave having a frequency of 1 施加 is applied, and 3 l 〇 nm or less is used. Ultraviolet The filter is made of a high-pressure mercury lamp to the liquid crystal cell, and emits ultraviolet rays. The irradiation intensity of the surface of the cell is adjusted to 1 〇niW/cm2, and the irradiation is performed for 600 seconds to obtain a vertical alignment in which the polymerizable compound in the polymerizable liquid crystal composition is polymerized. The liquid crystal display element was then decomposed, and the amount of the monomer remaining in the liquid crystal composition was measured by high performance liquid chromatography (HPLC: solvent: acetonitrile). The results are shown in Table 4. 63 201124510

[Table 4] The amount of the monomer before the ultraviolet ray irradiation was 0.3%. The amount of the monomer after the ultraviolet ray irradiation was 0.15%. As a result of the above, it was found that the polymerizable compound of Comparative Example 3 had a large amount of residual monomers in the liquid crystal composition. Further, the results of measurement of the pretilt angle (crystal rotation method) of the liquid crystal element before and after the ultraviolet irradiation and the electrooptical characteristics of the element are shown in Table 5. [Table 5] Pretilt angle before ultraviolet irradiation 89.0. The pretilt angle after UV irradiation was 88.9. The pretilt after 24 hours at 70 ° C was 85.5. Threshold voltage (V) — - 2.80V Voltage holding ratio (applied voltage IV, held at 16.67ms) 97.1% As a result of the above pretilt angle, it is known that the pretilt angle hardly changes before and after the ultraviolet irradiation. Therefore, in the absence of the initiation (4), the polymerization of the polymerizable compound represented by the formula ((7) cannot be sufficiently performed, so the pretilt has a weak restriction force on the liquid crystal molecules. In addition, the pretilt changes greatly after the heating test. Example 4) The polymer composition Ley was prepared by adding 3% of the polymerizable compound represented by the formula (9) and 15% of the photopolymerization initiator as a photopolymerization initiator. Liquid day and day group money CLC-3. The physical properties of CLC-3 are almost the same as those of the LC. The space injection method is used to inject CLC-3 into the box gap of 1 〇ym with coating induction. In a box of IT0 of a vertically aligned polyimide film, a 1.8V rectangular wave having a frequency of ΙΚΗζ is applied, and the liquid crystal cell is irradiated with ultraviolet light by a high pressure mercury lamp by filtering a filter of ultraviolet rays of 31 〇 nm or less. The irradiation intensity to the surface of the cell was 10 μm/cm 2 and the irradiation was performed for 600 seconds to obtain a vertical alignment liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The amount of the monomer remaining in the liquid crystal composition was measured by high performance liquid chromatography (HPLC: solvent: acetonitrile), and the results are shown in Table 6. [Table 6] The amount of monomer before ultraviolet irradiation was 0.3%. From the above results, it is understood that the polymerizable compound of Comparative Example (2) is polymerized by adding a photopolymerization initiator, and the pretilt angle (crystal rotation method) of the liquid crystal element before and after ultraviolet irradiation and the electric power of the element. The measurement results of the optical characteristics are shown in Table 7. [Table 7] The pretilt angle before ultraviolet irradiation was 89.0° The pretilt angle after ultraviolet irradiation was 87.9. The pretilt after 8 hours at 70 ° C was 87.0. Threshold voltage (V) 2.88V Voltage holding ratio (applied voltage IV, held for 16 67 ms) 89.5% From the above results, it was found that the system using a photopolymerization initiator lowered the voltage holding ratio. Thus, it was found that the addition of the photopolymerization initiator 'reliability side 65 201124510 exists. The problem is that, like the compound represented by the formula (i), even if a polymerization initiator is not used, polymerization can be carried out, and it is possible to exhibit a compound which can control the alignment of the liquid crystal material. Usability. [Simple diagram description] None [Main component symbol description] None 66

Claims (1)

201124510 VII. Patent Application: 1. A polymerizable compound' is represented by the general formula (1) X1 X2 X6 ^-M1 - 1 R'-SVm'-L' X4 l4 (Ri represents any of the formulas (R_1) to (R-15) of T. Os O (R-i)"Vo (R-6) ch3 0- o (R-2) CFs O, O (R-3) (R-4) (R-5) K h3c, y h3c O' o o (R-7) H3C. ch3 (R-8) (R-9) (R-10) O 0 h3cQ^vo HS" (R-ll) (R-12) (R-13) O (R14) (R-15), X1, X2, X3, X4, X5 and X6 independently represent a hydrogen atom or an alkane a group, an alkyl group, an alkoxy group, a functional alkoxy group, an i element, a cyano group or a nitro group, and S1 represents that the oxygen atom is not directly bonded to each other, and the fluorenylene group may be an oxygen atom or a COO- , an OCO-, or _ OCOO-, a C-C-C-substituted slave group (alkylene group) of 1 to 12, or a single bond, L1 and L independently of each other, _ 〇 — s —, _ OCH2 —, a CH2O C〇—, a C2H4—, a COO—, _〇C〇一, an OCOOCH2—,—CH2〇CO〇-, —CO-NR丨丨—,—NRn— CO—, —SCH2-, -CH2S-, -CH=CH-COO-, -0C0-CH = CH—, — CO〇—ch=CH—, —CH=CH—OCO—, — 67 # #201124510 COOC2H4 - '-OCOC2H4- ' -C2H4OCO- ^ - C2H4COO I, -ococh2-, a CH2COO-, a cooch2- '- ch2oco —, a CH=CH-, a CF=CF- '-CF=CH-, a CH =CF -, -CF2 -, _ CF2 〇 -, _ 〇 CF2 -, -: CF2CH2-, _ CH2CF2 -, a CF2CF2 - or a CeC - (where, R" An alkyl group having a carbon atom of 1 to 4)' L2 represents a CH=CH-COO- or a C2H4COO_, and Μ1 and Μ2 represent a 1,4-extension group, a 1,4-cyclohexylene group, a pyridyl-2,5-diyl group, Pyrimidine _ 2,5 _diyl, naphthalene-2,6-diyl, tetrahydronaphthalene _ 2,6-diyl or 1,3-dicrolinyl-2,5-diyl, Μ3 represents 1,4_ Phenyl, 1,3,5-benzenetriyl, 1,4,5-benzenetriyl, iota, 3,4,5-phenyltetrayl, 1,4-cyclohexylene, 1,3,5 — Cyclohexane triyl, i,3,4-cyclohexanetriyl, iota, 3,4,5-cyclohexanetetrayl, pyridyl-2,5-diyl, pyrimidine-2,5-diyl, Naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or 1,3-dicrosin-2,5-diyl, oxime, M2 and Μ3 are independently unsubstituted or can be Alkyled, halogenated alkyl, alkoxy, halogen, cyano or nitro substituted, m represents 0, '1, 2 and 3, η represents 0, 1, 2 and 3, when m and η represent 2 or 3 When present, two or three L1, Ρ'Μ1 and/or Μ2 may be the same or different, and ζ represents a hydrogen atom, a fluorine atom, a gas atom, a cyano group, a thiocyanate group, a trifluoromethoxy group, Has 1 to 12 carbons The alkyl group 'the alkyl group as an oxygen atom is not directly bonded to each other', and its methylene group may be an oxygen atom, a sulfur atom, _C〇-, a C00-, -0C0-'-0C00-, -CH=CH_ , - CEC is substituted, or Z represents a L4 - s2- R2 (where R2, S2, and L4 represent the same meaning as Rl, S1, and L1, respectively), k represents Bu 2 or 3, and k represents 2 or 3 When Z can be the same or different). 68 201124510 2. Polymeric compound of the 1st JS as claimed in the patent range, wherein in the general formula (1), 'L1, the mouth and L4 are independent of each other - 〇, _, -CH2〇-, -C00-, -〇c〇 ,—C2H4—cm or a single bond, M1 and M2 represent M—stretched cyclohexyl, phenyl, C—2,6-diyl or tetrahydronaphthalene—2,6-diyl, and Μ3 represents l,4-extension Phenyl, M-extension, I- 2,6-diyl, stupyltriyl, 13,4-benzenetriyl, Μ1, Μ2, and Μ3, independently of each other, can be burned, functionalized, burned Substituted by a dentate, alkoxy group, a cyano group, a cyano group or a sulfo group, m represents 1 or 2, η represents 0 or 1, and k represents 1 specific 2 . 3. The polymerizable compound according to claim 1, wherein in the formula (1), M3 represents unsubstituted or may be alkyl, dentated alkylalkoxy, halogenated alkoxy, halogen, cyano Or nitro substituted by 1,4 -phenyl, naphthalene-2,6-diyl or 1,3,4~ stupidyl. 4) The polymerizable compound of claim 2, wherein, in the formula (I), M3 represents unsubstituted or may be alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, _ 1,4-phenyl-naphthyl-2,6-diyl or 1,3,4-benzenetriyl substituted by cyanide or nitro. 5. The polymerizable compound 'wherein' in the general formula (1), Ri and R2 each independently represent a formula (R- or formula (R-2). The polymerizable compound of any one of claims 1 to 4 wherein 'n' represents 〇. 7. The polymerizable compound of claim 5, wherein ^ represents 0. 69 201124510 8. If applied The patent range is from the third to the middle, which are independent of each other? - a polymerizable compound, a coo-, - oc〇- or a single bond. The polymerizable compound of the ch2〇5 item - 〇ch2-, ~CH2〇 - , L1 , -COO-. , wherein L1 -COO- 9. If the scope of application patents L· and L· are independent of each other - OCO - or single bond. Η) · Polymerization according to item 6 of the patent application scope Compounds L3 and L4 independently of each other represent _ 〇CH2 —, — ^ — Π-2 〇 —, —OCO — or a single bond. 11. If the patent application ranges L and L are independent of each other - an OCO - or a single bond. The polymerizable compound of the seventh item, och2-—ch2〇-, wherein, L1-coo- i z. A polymerizable liquid crystal composition containing the polymerizable compound according to any one of claims 1 to 11. 13_- kind of optical anisotropic body' is composed of a polymerizable liquid crystal containing a polymerizable compound in the 12th article of the patent application, and a polymer of the product. A liquid crystal display element characterized by an optical anisotropic body of claim 13 in use. 15. A polymer-stabilized liquid crystal display region in which a liquid crystal compound of any kind or two or more of the above-mentioned patent scopes is added to a non-polymerizable liquid crystal composition, and then liquid crystal is used. The polymerizable compound represented by the formula (1) in the composition is obtained by polymerization. 70