TW201011036A - Polymeric chiral compound - Google Patents

Abstract

The object of this invention is to provide a polymeric chiral compound having strong HTP and low melting point. This invention provides a polymeric chiral compound represented by the general formula (I). The compound of this invention has strong HTP and low melting point, and has excellent solubility with other crystal liquid compounds due to the low melting point, therefore, it can be used as a construction component of a polymeric crystal liquid composition. The polymeric crystal liquid composition that uses the polymeric chiral compound of this invention as the construction component may have higher content of the polymeric chiral compound, and therefore, the optical anisotropic body having excellent optical features can be produced. The optical anisotropic body of this invention can be used for deflection plates, phase contrast plates and so on.

Description

[Technical Field] The present invention relates to a polymerizable chiral compound, a polybrominated liquid crystal composition containing the compound, and an optical substance as a cured product of the polymerizable liquid crystal composition. To the opposite sex. [Prior Art] In recent years, with the development of the information society, the importance of optical anisotropic bodies used in deflection plates, phase difference plates, and the like necessary for liquid crystal displays has been increasing. The optical characteristics necessary for the optical anisotropic body vary depending on the purpose, and a compound having a property suitable for the purpose is required. Further, not only the optical properties, but also the polymerization rate, solubility, melting point of the compound, glass transition point, transparency of the polymer, mechanical strength of the polymer, and the like are important factors. In recent years, a circular polarization separation function using a polymerizable cholesteric liquid crystal has been effectively used as a brightness enhancement film. The cholesteric liquid crystal can usually be prepared by adding an optically active compound (hereinafter referred to as a chiral compound) to a nematic liquid crystal. As the optical compensation film of the liquid crystal element, in order to obtain a circular polarization separation function from the ultraviolet region to the visible region, it is necessary to form a spiral structure in which the pitch (p) is not short. The pitch p of the molecular helix is inversely proportional to the concentration e of the chiral compound in the liquid crystal group according to the formula u). The proportionality constant is the helical torque (HTP) of chiralization =. In order to obtain a short pitch, it is possible to increase the concentration of the chiral compound or to increase the torsion. (8) 丄•丄

HTP C 201011036 However, when a large amount of a chiral compound is blended, it is not preferable because of a decrease in optical properties such as liquid crystallinity, solubility, transparency of a polyvalent substance, and an intercostal cost due to a high-priced chiral compound. Therefore, it is desirable to use a liquid crystal composition of a chiral Q material having a strong HTP (spiral torque). As a compound which exhibits a strong Hyp as described above, a chiral compound having an optically active site having a ring structure has been proposed (see Patent Documents i and 2). It is disclosed in these patent documents that optically active compounds based on 1,4:3,6·di-dehydrated mannitol (isomannitol), di-dehydrated-D-sorbitol (isoamyl 4 alcohol) are strong. Polymeric hand wow compound of HTp. However, the above-mentioned optically active compounds have a high melting point, a poor solubility, and a low compatibility with a partial liquid crystal compound (Patent Document 1). Further, in order to improve solubility, a compound having an asymmetric structure is dissolved. In the case of the degree of improvement, the degree of improvement has become a problem that is a major cause of the increase in the price of optical anisotropic bodies (Patent Document 2). [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. A polymeric chiral compound having a strong Ητρ and a low melting point. Means for Solving the Problem The inventors of the present application conducted research on various substituents in the compound of the genus 彳 人 7 取 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 聚合 聚合 聚合 聚合 聚合 聚合 聚合The compound can solve the above problems of 201011036, thereby completing the present invention. The present invention provides a polymerizable chiral compound represented by the formula (I), and provides a liquid crystal composition containing the compound as a constituent member, and an optical anisotropic body using the liquid crystal composition. The above formula (I) is: R1-S1-Y1-A1<B1 - Α, χΐ-〇 η m

A o-x2(a3-b24-a4-y2-s2-r2 (I) (wherein R1 and R2 are independent of each other, indicating a polymerizable group, and S1 and S2 are independent of each other' represent a spacer group, Y1 And γ2 are independent of each other, and represent -CH2CH2COO-, -OCOCH2CH2-, -0C00S30-, -OS3OCOO-, -CH=CH-COO-, and -OCOCH=CH-, and S3 represents an alkyl group and an alkoxy group having a chlorine atom number of 2-6. The groups, A1 and A4 independently represent i, 4_phenylene and naphthalene-2,6-diyl, and A2 and A3 are independent of each other, indicating 1,4-cyclohexylene,

1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetra-weathered Tsai-2,6-diyl, 1,3- Dioxo- 2,5-diyl' A1, A2, A3 and A4 may each be substituted by an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group or a nitro group, and B1 and B2 are independent of each other, indicating -〇 -, -S-, -OCH2-, -CH20-, -CO-, -COO-, -OCO-, -OCOO-, -CO-NR11-, -NRn-CO-, -SCH2-, -CH2S-, -CH=CH-COO-, -OCO-CH=CH-, -CH2CH2-COO-, -OOC-CH2CH2-, -NRu-CO-, -CO-NR11-, -CO-CH=CH_, -CH2- , _C2H4-, -CF2-, -CF20-, -〇CF2-, -CF2CH2-, -CH2CF2-, -CF2CF2_, -CH=N-, -N=CH-, -N=N·, -CH=CH -, - CF=CH -, - CH=CF _, - CF = CF -, C ξ C - or single bond, 5 201011036 X1 represents -CO-, -CH=CH-CO-, -CH2CH2-CO-, -CH2·, -C2H4-'-CF2-, -NRn.CO- or single bond, X2 represents -〇C_, -OC-CHsCH-, -OC-CH2CH2-, -CH2-, ·〇2Η4-, -CF2 -, -CO-NR11· or a single bond (in B1, B2, X1 and X2, Rii is independent of each other and represents a hydrogen atom or a carbon atom of 1-4), and m and η represent 〇, 1 or 2). EFFECTS OF THE INVENTION The polymerizable chiral compound of the present invention has a strong Ητρ and a low melting point, and has excellent solubility in compatibility with other liquid crystal compounds because of its low melting point, and is effective as a constituent member of a polymerizable liquid crystal composition. Moreover, since the manufacturing method is simple, there is an advantage that it can be manufactured inexpensively. The conjugated chiral compound of the present invention is a polymerizable liquid crystal composition constituting a member. The content of the chiral compound can be large, and an optical anisotropic body having excellent two optical properties can be produced. The optical orientation of the present invention The heterogeneous body can be effectively used for a deflecting plate, a phase difference plate, a selective reflection plate, etc. [Embodiment] It is independent of each other, and the polymerizable group has the structure shown below. R1 and r2 in the general formula (I) Examples of the polymerizable group are 201011036 ❹ ^Y° ο (Rl) H3C, (R-6)

(R-4) cr cr (R-9) (R-5) h3c, HaCV (R-10)

^ ύν· (Rn) (4) Heart, 0 (R") (Rl 5) These polymeric groups are hardened by free radical combination, ionic polymerization and anionic polymerization. Especially when θ 2 is polymerized, positive = linear polymerization is compared.佳为•.2 = Formula (R-5), Formula R-4), Formula (R-7) 4(R_U), Formula (R_ More preferably (U), Formula (R_2) ' (R-13) 〇, formula (R) 或 or formula HS-S and S are independent of each other, indicating that the spacer group is preferably Λ magnetic calendar uncle ο c @ between feg base is "the number of 2 to 6 extension base, the extension The carbon atom of the group may be substituted by an atom to form a group which does not directly bond between the oxygen atoms, and is preferably a stretching group having 2 to 4 carbon atoms from the viewpoint of liquid crystallinity and compatibility with other liquid crystal compounds. Y and γ2 Independent of each other, preferably _Ch2CH2C〇〇_, 〇C〇CH2CH2--OCOOS3O--OS3OCOO--CH=CH-COO- > 〇C〇CH=CH-, S3 represents an alkane having 2 to 6 carbon atoms And alkoxy groups, more 201011036 preferably -CH2CH2COO-, -OCOCH2CH2-, -CH=CH-COO-, -OCOCH=CH-. From the perspective of increasing HTP and utilizing unsaturated bonds, especially -CH= CH-COO-, -OCOCH=CH-. A1~A4 are two having a ring structure The groups, A1 and A4 are preferably 1,4-phenylene and naphthalene-2,6-diyl' A2 and A3 are preferably 1,4-cyclohexylene, 1,4-phenylene, naphthalene- 2,6-diyl, tetrahydronaphthalene-2,6-diyl. B1 and B2 are preferably -0-, -S-, -OCH2-, -CH20-, -COO-, -OCO-, -C2H4COO -, -COOC2H4-, -OC2H4O-, -OC3H6-, or -C^HUO-' is more preferably -COO-, -OCO-, -OCH2-, or -CH20 from the viewpoint of inexpensive production and liquid crystal alignment. X1 represents a bonding group, preferably -CO-, -CH=CH-CO-, -CH2CH2-CO-, -CH2-, and X2 is preferably -OC-, -OC-CH=CH-' - OC-CH2CH2-, -CH2-. Especially when X1 is -CO- and X2 is -oc-, the torque is stronger, so it is better. m and n represent 0, 1 or 2, and m and n are preferably ο or 1. More specifically, the compound represented by the formula (I) is preferably a compound represented by the following formula (1-1) to (1-17).

(Μ)

201011036

CH2=CHCOO(CH2)p-〇 /~\ /==%/-° °-\_T

P—(CH2)q OCOCH^CHz (1-9) CH2=CHC00(CH2)p-0 3~〇^coo^O~

CO

C〇〇^〇^c 0—(CH2)q OCOCH=CH2 Λ

(1-10)

(1-12) (M3) (M4) (1-15) CH2=CHCOO(CH2)p-〇v 6

C〇〇V H

CH2=CHC00(CH2)p-0v // 〇

〇〇〇"Cy H bo

P—(CH2)q OCOCH=CH2 b (M6)

CO〇V H

H i)C«

(◦2 (CH2)q OCOCH=CH2 b (M7) (wherein p and q are independent of each other and represent an integer of 2 to 8.) 10 201011036 The compound of the present invention can be synthesized by the synthesis method described below. (Production Method 1) Production of a compound represented by the formula (1-1): a hydrazylation reaction of p-bromobenzoic acid and isosorbide using a dehydrating condensing agent such as dicyclohexylcarbodiamine, and further a product and an acrylic acid The isosorbide derivative (S-2) was obtained from acetonitrile by using Heck Reactions of the catalyst.

Then, the isosorbide derivative (S-2) and the glycerin chloride are subjected to a acetalization reaction in the presence of triethylamine to obtain a target compound (1-1) having p = 2.

(Production Process 2) Production of a compound represented by the formula (1-7): 6-hydroxy-2-naphthoic acid and a trifluoromethanesulfonate gas are further reacted with a dehydrating condensing agent such as dicyclohexylcarbodiimide to make an isosorbent Alcohol for esterification inverse 11 201011036 should 'get isosorbide derivative (s_3) β

Further, the isosorbide derivative (S_3) and hydroxyethyl acrylate are obtained by a heck reaction using a palladium catalyst to obtain an isosorbide derivative (s_4), which is subjected to a hydrazine reaction by palladium carbon to obtain an isosorbide derivative ( S_5). HO(CH2)p-〇

)-(CH2)q 〇H (S-5) ❿

CH2=CHCOOC2H4〇H P(J/C (S-4)

Pd(OAc)2 DMF/NEt3 Next, an isosorbide derivative (s_5) and a propylene oxime gas are subjected to an esterification reaction in the presence of triethylamine to obtain a target compound (ι_7) of p=2.

(1-7) (Production Process 3) Production of a compound represented by the formula (1-9), in the presence of a suitable base such as sodium hydroxide, an etherification reaction of p-hydroxybenzoic acid and a benzyl group to a phenol-binding protecting group Thereafter, the esterification reaction is carried out using a dehydrating condensing agent such as dicyclohexylcarbodiimide, and the product is removed from the phenol protecting group by a reduction reaction using hydrogenation of a palladium=chemical agent to obtain an isoamyl 12 201011036 sorbitol derivative. (S-7Or CH2C!

COOH

NaOH/KI C2H5OH q^°~〇-c〇〇h

HO

H2Pd/C -►

DCC/DMAP (S-6)

OH 瘳 Further, an isosorbide derivative (S-7) and a diethylene glycol mono-tert-butyl group are obtained by a Mitsunnobu reaction using triphenylphosphine and diisopropylazodicarboxylate. The ether is subjected to an etherification reaction, and the third butyl group is deprotected by trifluoroacetic acid to obtain a hydroxyl group-containing isosorbide derivative (S-8).

Next, an esterification reaction of a hydroxyl group-containing isosorbide derivative (S-8) and acryloxyethyl chloroformate in the presence of acridine is carried out to obtain a target compound (1-9) of p=2. .八 入 1 CH2=CHC00(CH2)p-0 /=\ ^t^〇Aci 0^° °-〇-' (S-8) -► Pyridine/THF

(1-9) 13 201011036 (Production Process 4) Production of a compound represented by the formula (1-16): an esterification reaction of p-nitrobenzoic acid and isosorbide is carried out using a dehydrating condensing agent such as monocyclohexylcarbodiimide. Further, the nitro group is reduced by palladium carbon or the like to obtain an isosorbide derivative (S-9) having an amino group.

Further, an isosorbide derivative (s_9) and a non-benzidine gas are subjected to an esterification reaction in the presence of triethylamine to obtain a guanamine compound (S_1〇), followed by a product and a hydroxybutyl acrylate. The heck reaction of the catalyst, and further esterification of propylene oxide in the presence of triethylamine, gives the target compound (1-16) of p=4.

CH2: CHCOOC4He〇H

Pd(〇Ac)2 DMF/NEt3 ^ra THF/NEt3

BrCOCI (S-9) -► THF/NEt3

(S-10)

-o-1

P-{CH2)4 〇C〇CH*CH2 0-16) (Production Process 5) The production of the compound represented by the formula (1-17) is carried out by using a dehydration condensing agent such as dicyclohexylcarbodiimide (3). Synthetic isosorbide derivative (S-7) 1 molar and 6-bromo-2-naphthoic acid i mole 201011036 'Know an isosorbide derivative, and then react with trifluoromethanesulfonic acid to obtain an asymmetric In the middle, 丨丨赳公公二丄 & / 〇,. ,

Esterification reaction,

Pd(OAc)2 DMF/NEt: The isosorbide derivative (S_12) and hydroxyethyl acrylate are used to carry out the heck reaction of the catalyst, and the propylene gas is subjected to acetation in the presence of triethylamine. , the target compound (1_17) with p = 2 can be obtained.

The compound of the present invention can be suitably used for a chiral nematic, chiral near-quinone and cholesteric liquid crystal composition. The amount of the polymerizable chiral compound to be added to the liquid crystal composition containing the compound of the present invention as a constituent member is preferably 〇 ^ 40 40% by mass, more preferably 3 to 25% by mass. The configuration of the liquid crystal composition containing the polymerizable chiral compound of the present invention is not limited except for the compound represented by the formula (j). However, as the polymerizable liquid crystal compound used in combination, it is preferred to have propylene in the compound. The person having a decyloxy group (R-1) or a methacryloxy group (R_2) is more preferably a compound having two or more polymerizable functional groups in the molecule, 15 201011036. As the bifunctional polymerizable liquid crystal compound to be used in combination, it is preferable to select a compound represented by the formula (Π), which is 'CH.CHCOO(CHA-W^YH〇^) ^w2_(CH2)8〇c〇CHeCH2(II) where w1 and w2 are independent of each other, indicating a single bond, -〇-, -C〇〇- or -OCO-, Y3 and Y4 are independent of each other, indicating -COO- or -OCO-, r and s are independent of each other, and represent an integer of 2 to 18, and the 1,4-phenylene group present in the formula is an alkyl group having 1 to 7 carbon atoms and an alkoxy group having 1 to 7 carbon atoms. One or more substitutions of alkanoyl group, a cyano group or a halogen atom having a number of broken atoms of 1 to 7, and a compound represented by the formula (II) is specifically preferably a compound of the formula (II-1). a compound represented by the formula (II-8): CH2=CHCOO(CH2)r〇-(^>-COO-<^)-A^ OCO-<^-〇(CH2)s〇COCH= CH2 (II-l) CH2=CHCOO(CH2)r〇-<^)^COCM^>-A^ F OCCH^^O(CH2)s〇COCH=CH2 (II-2) CH2=CHCOO(CH2 )r〇-<^-COCM^>-ch3o" OCO-^Q>-0(CH2)s〇COCH=CH2 (II-3) CH2=CHCOO(CH2)rCM^>-COO^P> ~^ cr OCO-^Q^O(CH2)s〇COCH=CH2 (11-4) CH^CHCOO(CH2)r^n>-C〇〇-<nV^ ^ w V〇CCM^)-(CH2)sOCOCH=CH2 (11-5) CH2=CHCOO(CH2)H〇Vc〇0-/nV-^ \-OCO-<Q)-(CH2)s〇COCH=CH2 (II-6) CH^CHCOOiCHaJn^-COOHp)-^^ CH3d^ )CO-h^-(CH2)s〇C〇CH=CH2 (II-7) CHz^CHCOOiCH^r-^^COCHO^ c Factory DCO-^-(CH2)s〇C〇CH=CH2 (11-8) (wherein r and s have the same meanings as in the formula (II). 16 201011036 'In the formula (ΙΙ-l)~ In the general formula (II-8), r*s is independently an A & preferably an integer of 3 to 6. The bifunctional polymerizable liquid crystal compound used in combination is specifically preferably represented by the formula (πι). a compound wherein the formula (111) is (III) wherein W3 and W4 are independent of each other, and represent a single bond, -Ο-, -COO- or -OCO-, and γ5 are independent of each other, and represent coo- or -〇c〇. _, p and q are mutually independent: an integer of 2 to 18, and the hydrogen atoms of the three 1,4-phenylene groups present in the formula may be alkyl, alkoxy or alkane having 1 to 7 carbon atoms. The thiol' cyano group or a halogen atom is substituted by one or more. The compound represented by the formula (III) is specifically preferably a compound represented by (III 1 , , beer type; to formula (ΙΙΙ-10). 参17 201011036 CH.CHCOO(CH2)pO-^^ OC〇A_^〇(cH2)q〇c〇cH=cH2 CH2=CHCOO(CH2)pO-^^COO^_^〇(cH2)q〇c〇cH=cH2CH2=CHC〇〇(CH2)po^^ 〇c〇^^〇(cH2)q〇c〇cH=cH2CH2=CHC〇〇(CH2)p〇普翁CH^CHCOO(CH2)pO-<p^COO-Y^〇(cH2)q〇c 〇cH==cH2CH-CHC00(CH2)p0^D~€^C00^^0(CH2)q—

CH2=CHCOO(CH2)P〇-<^>—〇CO

CH2=CHCOO(CH2)pO-<^>-〇C〇 CH2=CHCOO(CH2)pO-^>-Q>- COO 0(CH2)q0C0CH=CH2 CH3

0(CH2)q0C0CH=CH2 CH3 l_CH2=CHCOO(CH2)pO-<^-coo ^-〇>- 〇(CH2)q〇COCH= ch3 :ch2

0(CH2)q〇COCH=CH2 CH3 (III-l) (III-2) (III-3) (II1-4) (III-5) (II1-6) (III-7) (III-8) (III-9) (III-10)

(In the formula, P and q have the same meanings as in the formula (III).) From the viewpoint of heat resistance and durability, among these compounds, the formula (III-2) and the formula (III-5) are preferred. The compound of the formula (III-6), the formula (ΙΠ-9), and the formula (III-10) is more preferably a compound of the formula (III-2). The compound having two or more polymerizable functional groups in the molecule which is a guest-type liquid crystal may contain a compound represented by the formula (a-1) to the formula (a-1). 18 201011036 CH2=CCOO(CH2)u〇-(^>-COO-(^>=((())) -COO-<^)-OCO-^^)-0(CH2)v〇COC=CH2 (a-2)

H H CH3 CH2=CCOO(CH2)u〇-(^^--C〇〇-^^)-〇CO-^^-0(CH2)v〇C〇C=CH2 (a-3)

CH2=CCOO(CH2)u〇-H;^^- coo oco H^)-〇(CH2)v〇C〇9=CH2 (a_4) CHz=CCOO(CH2)u〇-^^>-<^>-OCO-<^)-0(CH2)v〇C〇9=CH2 (a-5)

CH2=9COO(CH2)u〇-^)-<^>-COO-<Q)-0(CH2)v〇COC=CH2 (a-6) HFH CH?=CCOO(CH2)u-( ^h-〇>-COO-^^>-(CH2)v〇C〇C=CH2 (a-7)

H H

F F CH2=CCOO(CH2)u COO-^^-(CH2)v〇C〇9=CH2 (a*8)

Η H

F CH2=CCOO(CH2)u-(^—<^-C〇〇-<^-(CH2)v〇C〇9=CH2 (a 9) CH2=CCOO(CH2)u

(CH2)v〇c〇9=CH2 (a-10) (wherein u and V are independent of each other, representing an integer of 2 to 18 ° ^ , ( α \ among these compounds is preferably added by the formula (a-2) Or a compound of the formula a Λ t zr , particularly preferably, the ratio of u and V is preferably 3 to 18, more preferably 4 to 6 to 12 〇 in order to adjust the liquid crystal temperature range and the birefringence, and to lower the viscosity. The polymerizable liquid crystal compound used in the liquid crystal composition is also 叮p %, , +, and the monofunctional polymerizable liquid crystal compound represented by the formula (IV) is represented by the formula (IV): 19 201011036 0Η2=0Η000(0Η2)β0 ^^γ6_^γ7_^>_γ^ζ (10) g where e represents an integer from 0 to 18, and when 6 is 〇 or 1, [indicates 〇, when e is 2 to 18, f represents an integer of 0 or 1, and i represents 〇 An integer of 〜2, c, D and E are independent of each other', meaning 1,4-phenylene, 1, cardenylcyclohexyl, 1-cyclohexenyl, tetrahydropyran-2,5-diyl, 1, 3_Dioxane-2,5-diyl, tetrahydrothiopyran-2,5-diyl, 1,4-bicyclo(2,2,2) octylene, decalin-2,6-diyl Pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl, tetrahydrogen

Naphthalene-2,6-diyl, 2,6-anthranyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene, 2,2-diyl, 1,2,3,4, 4冱,9,10&-octahydrophenanthrene, 2,7-diyl or 苐_2,7-diyl, the 1,4-phenylene, 1,2,3,4-tetrahydronaphthalene-2 ,6-diyl, 2,6-anthranyl, phenanthrene-2,7-diyl, 9,10-diphenanthrene-2,7-diyl, 1,2,3,4,4&,9 , 10&-octahydrophenanthrene, 2,7-diyl or indole-2,7-diyl is unsubstituted or may have 1 or more of F, Cl, CF3, OCF3 or CH3 as a substituent, γ6 And γ7 are independent of each other, indicating a single bond, -COO-, -OCO- ' -CH=N-, _N=CH-, -CE c-, -ch2ch2-, -ch2ch2ch2ch2-, -ch2ch2ch2o-, -OCH2CH2CH2-' - CH20- ' -OCH2- ' -CF20- ' -OCF2- ' -CH=NN=CH-, -CF=CF-, -CH=CH-, -CH2CH2CH=CH-, -CH=CHCH2-, -CH= CHCOO_, -〇COCH=CH-, -CH2CH2OCO- or -CO〇CH2CH2-, Y8 represents a single bond, -〇-, -CO-, -COO-, -oco, -CH2-, -〇ch2-, -CH20 -, -CONH-, -NHCO-, -CH2COO- or -CH2〇C〇-, z represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 2 carbon atoms, a halogen atom, a cyano group or an NCS. The alkyl or alkenyl group is unsubstituted or may have 1 One or two or more F, C-cyano, CH3 or CF3 as a substituent, and one or more of the 201011036 ch2 groups present in the alkyl or alkenyl group may be substituted by hydrazine, CO or coo to form an oxygen atom. There are no groups that are directly bonded to each other. The amount of the compound represented by the formula (IV) is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 15% by mass or less. The compound represented by the formula (IV) is specifically preferably a compound represented by the formula (IV-1) to the formula (IV-11). CH2=CHCOO(CH2)e〇MQ^ C= OR (IV-l)

CH2=CHCOO(CH2)e〇fHQ>-C=C-^)-R (IV-2) CH2=CHCOO(CH2)e〇lHQ>-C=C-^y-CN (iV-3) CH2= CHCOO(CH2)e〇M^^COO-H(^)-OR (iv-4) CH^CHCOO(CH2)e〇f-<Q>-COO-<Q^R (IV-5) CH ^CHC00(CH2)e0f-^>-C00-^^CN (iv-6) CH2=CHCOO(CH2)e〇f-^gM^^R (IV-7) CH^CHCOO(CH2)e〇f -^^-<^>-R (IV_8) CH2=CHCOO(CH2)e〇f-<Q^COO-^MQ^R (IV-9) CH2=CHCOO(CH2)e〇HQ>- COO-<p>-^p>-CN (IV-i〇) CH2=CHCOO(CH2)e〇<-^hC〇〇-^^Q>-R (IV-n) (where e and f is the same as the general formula (IV), and R represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms. Further, the polymerizable liquid crystal composition of the present invention may be added thereto. A compound which does not exhibit liquid crystallinity as a compound of a polymerizable functional group. As such a compound, a compound which is considered to be a polymer-forming monomer or a polymer-forming oligomer in the technical field can be used without limitation, but the amount of addition thereof needs to be adjusted until the composition exhibits liquid crystallinity. 21 201011036 The concentration of the photoinitiator of the present invention in the polymerizable liquid crystal composition of the present invention is preferably from 0.1 to 10% by mass, more preferably from 2 to 5% by mass, particularly preferably from 4 to 3% by mass. Further, other photoinitiators may be added in addition to the photoinitiator of the present invention. Examples of the photoinitiator include benzoin, benzophenones, acetophenones, benzoin and fluorenes, and fluorenylphosphine oxides. Further, in order to improve the storage stability, a stabilizer may be added to the polymerizable liquid crystal composition of the present invention. Examples of stabilizers that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, and naphthylamines. Point-naphthol quinones, fluorene, and the like. The amount of the stabilizer used is preferably in the range of 0.005 M 胄 % relative to the liquid crystal composition, more preferably (4) 〇 2 〇 5% by mass, particularly preferably 0.03 〇 〇. Further, when the polymerizable liquid crystal composition of the present invention is used for a raw material of a polarizing film and an alignment film, or a printing ink, a coating material, a protective film or the like, a metal, a metal complex, a dye, or a pigment may be added depending on the purpose. - Fluorescent materials, dish materials, surfactants, leveling agents, thixotropy polysaccharides, UV absorbers, infrared absorbers, antimony oxidants, ion exchange resins, metal oxides such as titanium oxide, etc. . Next, the optical anisotropic body of the present invention will be described. The optical anisotropy produced by polymerizing the inventive polymerizable liquid crystal composition is used for various purposes. For example, when the polymerizable liquid crystal composition of the present invention is polymerized in an aligned state, it can be used as a light-scattering plate or a polarizing-eliminating sheet. Further, the optical anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in a state of being in an original state has optical anisotropy in physical properties 22 201011036 2 and is therefore useful. Such an optical anisotropic body can be subjected to a rubbing treatment on the surface of the substrate on which the organic thin film is formed by, for example, supporting the surface of the polymerizable liquid crystal composition of the present invention on a substrate subjected to rubbing treatment with a cloth or the like. The substrate or the substrate having the oblique vapor-deposited alignment film or the liquid crystal obtained by sandwiching between the substrates is polymerized and produced. Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing, and the like. . Further, an organic solvent can be added to the polymerizable liquid crystal composition at the time of coating. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylacetamide, digastric, isopropanol, acetone, methyl ethyl hydrazine: acetonitrile, cellosolve, The ring is left, r_丁内酷, ethoxylated 2-_2 ethoxyethane, propylene glycol monomethyl acetate vinegar. These solvents may be used singly or in combination, and may be appropriately selected in consideration of the vapor a and the polymerizable liquid crystal cleavable property. Further, the amount of addition is preferably % by weight or less. 方法 The method for volatilizing the added organic solvent can be dried naturally, added, dried, reduced, and dried under reduced pressure. In order to further improve the coatability of the polymerized L liquid crystal material, it is effective to provide a medium such as a poly(tetra) film on the substrate, or to add a leveling agent to the polymerizable liquid crystal material. In the method of disposing an intermediate layer such as a ruthenium (tetra) film on the base 2, when the optical anisotropic body of the polymerizable liquid crystal material is inferior in adhesion to the substrate, it is also effective as a means for improving the adhesion. As a method of sandwiching a polymerizable liquid crystal composition between substrates, 23 201011036: an injection method using a capillary phenomenon. It is also effective to reduce the space formed between the substrates and then inject the polymerizable liquid crystal material. .卞 is the rubbing treatment or the alignment treatment other than the oblique steaming of Sl02, and the use of the flow alignment of the liquid Ba material, the use of an electric field or a magnetic field. These alignment means can be used singly or in combination. Further, as an alignment treatment method instead of friction, a photo-alignment method can also be employed. The method is, for example, an organic thin film having a functional group for photodimerization reaction in a molecule such as a polyethylene cinnamate, an organic thin film having a functional group which is anisotropically reacted with light, or a polyacrylonitrile or the like. When the organic film is irradiated, polarized light is generated, and polarized ultraviolet rays are preferably generated to form an alignment enthalpy. In the photo-alignment method, alignment of the alignment can be easily achieved by applying a photomask, and the molecular alignment inside the optical anisotropic body can be precisely controlled. The shape of the substrate may have a curved surface as a constituent portion in addition to the flat plate. As the material constituting the substrate, an organic material or an inorganic material can be used. Examples of the organic material to be a substrate material include polyethylene terephthalate, polycarbonate, polyacrylamide, polyamine, polymethyl methacrylate, polystyrene, and gas. Ethylene, polytetrafluoroethylene, polygas trifluoroethylene, Q polyacrylic acid vinegar, polyglycol, triethyl cellulose, cellulose, polyfluoride and the like. Further, examples of the inorganic material include bismuth, glass, calcite, and the like. When the substrate is rubbed with a cloth or the like and an appropriate alignment property is not obtained, 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, or may be formed by a cloth or the like. friction. In addition, the pre-tilt polyimine oxime used in the conventional twisted nematic (TN) element or super twisted nematic (STN) element can be more precisely controlled by the internal anisotropic body of 24 201011036. The molecular alignment structure is particularly excellent. In addition, when the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferred to form an organic thin film such as the above-mentioned polyimide film on the electrode. Since the composition to which the polymerizable chiral compound of the present invention is added exhibits a helical structure, a phase difference plate having a helical structure can be produced by polymerizing its alignment in a liquid crystal state. The pitch of the spiral can be selectively reflected by the Bragg's law as long as it is 1/2 of the wavelength of the light to the extent of the wavelength. It can be used, for example, as a circularly polarized light separating functional element. As a method of polymerizing the polymerizable liquid crystal composition of the present invention, since it is desired to carry out polymerization rapidly, it is preferred to carry out polymerization by irradiation with an active energy ray such as ultraviolet rays or electron beams. When using ultraviolet light, a polarized light source or a non-polarized light source can be used. When the polymerization is carried out in a state where the liquid crystal composition is sandwiched between the two substrates, at least the Lu substrate on the irradiation surface side must have appropriate transparency to the active energy ray. Further, in the case of light irradiation, only a specific portion is polymerized by the photomask, and the alignment state of the unpolymerized portion is changed by changing conditions such as an electric field, a magnetic field or a degree, and a means for irradiating the active energy ray to polymerize may be employed. Further, the temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention can be maintained. In particular, in the case where an optical anisotropic body is to be produced by photopolymerization, it is preferably at a temperature as close as possible to room temperature, that is, a temperature of typically 2, c, from the viewpoint of avoiding the induction of undesired thermal polymerization. The strength of the polynosed/tongue energy ray is better. 〇"~ 25 201011036 2W/cm ° When the intensity is below O.lmW/cm2, it takes a lot of time to complete the photopolymerization, and the productivity is deteriorated; In the case of 2 W/cm 2 or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition may be deteriorated. The optical anisotropic body of the present invention obtained by polymerization can also be subjected to heat treatment to reduce initial characteristic changes and to exhibit stable characteristics. The heat treatment temperature is preferably in the range of 50 to 25 (rc), 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 such a method can be peeled off from the substrate. The monomer may be used without being peeled off, and the obtained optical anisotropic body may be laminated or used by being adhered to another substrate.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples and comparative examples means "% by mass". Example 1) In a reaction vessel equipped with a stirring device, a cooler and a thermometer, 33.2 g (240 mmol) of 3 (p-phenyl)benzoic acid, 4 g of potassium bromide, lg of tetrabutylammonium bromide, and 400 m of ethanol were added. Stirring was carried out at room temperature, and 24 g of a 25% aqueous solution of sodium hydroxide was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 50 ° C, and 50 g of benzyl bromide (288 mm 〇 1) was slowly added dropwise. Further, the reaction vessel was heated to 70 ° C and further reacted for 3 hours. 26 201011036 After the reaction was completed, it was neutralized with 1 G% hydrochloric acid, extracted with acetic acid s, and dried with sulfur (tetra) to concentrate (4). The compound shown is in the range of 〇-y〇-V>COOH (1). Next, in the reaction vessel having the stirring device, the cooler and the thermometer, the above-mentioned synthesized formula (28 g (123 mm〇i),

Isosorbide 7.7 g (55 mm 〇l), trimethylamino guanidine 18 g, methylene chloride 500 ml, and the reaction vessel was kept at 5 < t or less in an ice bath. 19 g (15 〇 mm 〇 1) 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 allowed to react for 5 hours. After the reaction mixture was filtered, the mixture was washed with aq. After distilling off the solvent, it is passed through a 5 times by weight (by weight) column.

Then, the compound iig (i7_7 mmol) represented by the above formula (2), sigma lg, and ethanol 150 ml were added to a high-pressure helium vessel equipped with a stirring device, and the reduction reaction was carried out with hydrogen of o.iMPa (reaction temperature: 5 〇t >;c, ^ hours). After filtering the reaction liquid, the reaction solvent was distilled off to obtain 7.5 g of the compound of the formula (3).

HQ-f V-CO

OH (3) 27 201011036 Next, 4.5 g (38 mmol) of ethylene glycol mono-tert-butyl ether and 6.2 g of the compound represented by the above formula (3) were placed in a reaction vessel equipped with a stirring device, a cooler and a thermometer. 16 mmol), triphenylphosphine 9.6 g (37 mmol), and THF 200 m were cooled to below 5 ° C under a nitrogen atmosphere. Next, 7 g (35 mmol) of diisopropylazodicarboxylic acid was slowly added dropwise. After the completion of the dropwise addition, the mixture was reacted at room temperature for 4 hours. After the reaction was completed, THF 100 nU was distilled off.

The concentrated reaction droplets were added to a solution of sterol/pure water = 300/60 ml cooled to below 5 ° C, and then reprecipitated. The precipitate was filtered and dried to synthesize 8 g of the compound of the formula (4).

Next, the reactor was cooled to 5 ° C or lower under the atmosphere of a nitrogen atmosphere by adding 40 ml of trifluoroacetic acid to a reaction vessel having a stirring device. Further, 8 g of the compound represented by the above formula (4) was added little by little. After the end of the addition, the reaction was stirred at such a temperature for 30 minutes. After completion of the reaction, extraction was carried out with methylene chloride/pure water, and then washed with pure water 'saturated sodium hydrogencarbonate, and the organic layer was concentrated to give 6 g. Then, 6 g of the above alcohol, 6 g (77 mmol) of hexane and 50 ml of THF 1 were placed in a reaction vessel equipped with a stirring device, a cooler and a thermometer, and the reactor was cooled to 5 〇c or less under a nitrogen atmosphere. Then, 5.5 g (31 mm 〇 1) of propylene methoxyethyl chloroformate was slowly added dropwise. After the completion of the dropwise addition, the mixture was reacted at room temperature for 4 hours. After completion of the reaction, ethyl acetate was added, and the organic layer was washed with a hydrazine aqueous solution of hydrochloric acid, purified water, and brine. After distilling off the solvent, 28 201011036 Purified by a 5 times by weight (by weight) silica gel column.

(physical property value) 0*-(CH2)2〇C〇CH=:CH2 (5) jH-NMR (solvent: heavy gas imitation) of the formula (5): occupies .4 κ jλ , 0 . 4.26-4.10 ( m,4Η), 4.40 ( m,2H) , 4.42 ( s,8H) . 4 , 4.54(m,4H),4 66 (m, • 1H) , 5.03 ( m,1H) , 5.45 ( m,9U, Φ 2H) > 5.84 ( d . 2H) > 5.86 ( m, 2H), 6.14 ( m ' 2H), 6 』 6.45 (d, 2H), 6.93 (m, 4H), 7.98 ( d ' 2H), 8.04 (d, 2H). 13c-nmr (solvent: heavy gas imitation) · ;δ : 62.0 , 65.7 , 66.0 , 70.7 ' 74.3 , 78.3 ' 81.1 , 86 " , ι ] 4 π U4.l, 122.3, 127.7, 131.4, 131.7, 154.6, 162.1, 165.5. 2925, 2855, 1760, infrared absorption spectroscopy (IR) ( ΚΒΓ ) 1652-1622 , 809 .

The HTP was calculated from the pitch added to the liquid crystal-forming nematic liquid crystal composition, and the compound represented by the formula (5) was excellent in solubility of the binder. As shown below, 1·〇% was added and the value shown by the optical microscope was as high as HTP=30. 29 18%201011036 CH2=CHCOO(CH2)3· CH2=CHCOO(CH2)r〇 ch2=chcoo

0—(CH2)3 ococh=ch2 —(CH2)6 ococh=ch2 ch2=chcoo -^^-coo-^^-c3h7 22% 33% 22% 5% CH2=CHC0Q(CH2)g-0—COO— C2Hs

In a reaction vessel equipped with a stirring device, a cooler and a thermometer, 25 g (124 mmol) of bromobenzoic acid, 9 g (62 mmol) of isosorbide, 1.8 g of dimethylaminopyridine and 200 ml of dichloromethane were added in an ice bath. The reaction vessel was kept at 5 ° C or lower, and 18.8 g (149 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 allowed to react for 5 hours. After the reaction mixture was filtered, the mixture was washed with aq. After distilling off the solvent and washing the target with methanol, 25 g of the compound of the formula (6) was obtained by recrystallization from dichloromethane / methanol.

Next, 25 g (48-8 mmol) of the compound represented by the above formula (6), 18 g (126 mmol) of hydroxybutyl acrylate, 14 g (146 mmol) of triethylamine, and tetrabutyl group were placed in a reaction vessel equipped with a stirring device, a cooler and a thermometer. Ammonium bromide 31 g (97 mmol), palladium acetate lg, dimethylformamide 30 201011036 300 ml 'The reactor was heated to 9 ° C under a nitrogen atmosphere to carry out a reaction. After the reaction, ethyl acetate and THF were added, and 1% aqueous hydrochloric acid solution, pure water,

The organic layer was washed with saturated brine. After distilling off the solvent, it was purified by a 5-fold amount (weight ratio of Shishijiao column to obtain 20 g of the compound represented by the formula (7). hoc4h8o〇c-/(7) cooc4h8oh

Then, the compound i〇g (1. 6 mmol) represented by the above formula (7), propylene chloride 3 g (33.8 mmol), and dioxane 200 ml were added to a reaction vessel equipped with a stirring device, a cooler and a thermometer. The reactor was cooled to below 5 ° C under a nitrogen atmosphere. Then, 34 g (3 3.8 mmol) of triethylamine was slowly added dropwise. After the completion of the dropwise addition, the reaction was carried out for 1 hour. (The reaction was carried out for 1 hour. After the completion of the reaction, dichlorosilane was added, and the organic layer was washed with a 10% aqueous hydrochloric acid solution, purified water and saturated brine. (weight ratio)

❹ (physical value) H_NMR (solvent: heavy gas imitation): 5 : 1.83 ( s, 8H) , 4.08 (m ' 4Η) ' 4·27 ( m, 8H) ' 4.71 ( d ' 1H), 5.09 ( m, 1H) '5.44(m,2H), 5.84(d,2H), 6.17(m,2H), 6.43 (d,9W, , n) ,6·55 ( dd,2H) , 7.60 ( m,4H) J 7.72 31 201011036 (m'2H), 8.04 (d, 2H), 8.10 (d, 2H). 13C-NMR (solvent: heavy chloroform): (5: 25.2, 63.7, 64.0, 70.5, 73), 74.5, 78.4, 80.9, 85.8, 120.3, 120.4, 127.6, 128.0, 129.8, 130.2, 130.3, 138, 5, 138.6, 142.7, 142.8, 162.7, 164.4, 164.7, 165.6, 165.8 〇 Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 (melting point) 82 ° C. From equation (8) The compound shown has a melting point as low as 82 〇c, and is excellent in solubility with other liquid crystal@ compounds. HTP was calculated in the same manner as in Example 1, and as a result, it was found to be as high as HTP = 41. (Example 3) To the reaction vessel of the cooler and the thermometer, 26.5 g (48.8 mmol) of the compound represented by the formula (6) synthesized in Example 2, 14.6 g (126 mmol) of butyl acrylate, and 14 g of triethylamine (146 mmol) were added. ), tetrabutylammonium bromide 31 g (97 mmol), palladium acetate lg, dimethylformamide 3 〇〇 ml, and the reactor was heated to 9 ° C under a nitrogen atmosphere to carry out the reaction. Ethyl acetate and THF were washed with 10% aqueous hydrochloric acid, pure water and saturated brine. After the solvent was removed, it was purified by a 5 times by weight (by weight) silica gel column to obtain 16 g of the compound represented by the formula (9). 32 201011036

Next, 10 g (1. 3 mmol) of the compound represented by the above formula (9), 10 g of ethyl acetate, 100 ml of ethanol, and 100 ml of ethanol were placed in an autoclave vessel equipped with a stirring apparatus, and then reduced with hydrogen of 0.1 MPa. Reaction (reaction temperature: 50 ° C, 3 hours). The reaction liquid was filtered, and the reaction solvent was evaporated to give the compound (y.

Cooc2h4oh (10) Next, in the reaction vessel equipped with a stirring device, a cooler and a thermometer, 8 g (13 mm 〇l) of the compound represented by the above formula (10), 2.8 g (31 mmol) of propylene oxide, and 200 ml of methane methane were added. The reactor was cooled to below 5 ° C under a nitrogen atmosphere. Next, 3.1 g (3 lmmol) of triethylamine was slowly added dropwise. After the completion of the dropwise addition, the reaction was carried out for 1 hour at 1 (rc). After the reaction was completed, the mixture was purged with a second gas, and the organic layer was washed with a 10% aqueous hydrochloric acid solution, purified water and saturated brine. The weight ratio of the tannin column was purified to obtain the target compound 6e represented by the formula (〗 〖).

(physical value) lH_NMR (solvent: heavy gas imitation): (5: 2.67 (m, 4H), 3.02 33 201011036 (Μ, 4H), 4.04 (Μ, 4Η), 4.34 ( s, 8Η), 4.66 (Μ, 1Η), 5.〇4(Μ,1Η), 5·40(Μ,2Η), 5.84(d,2H), 6.15 (Μ,2Η), 6.44 ( dd,2Η), 7.28 (Μ,4Η), 7.94 (d, 2Η ), 7.99 ( d ' 2Η). 13C-NMR (solvent: heavy gas imitation): 5 : 25.2,63.7,64.0, 70.5,73.1,74.5,78.4,80.9,85.8,120.3,120.4,127.6 , 128.0, 129.8, 130.2, 130.3, 138.5, 138.6, 142.7, 142.8, 162.7, 164.4, 164.7, 165.6, 165.8. Infrared Absorption Spectroscopy (IR) (KBR): 2925, 2855, 1760, © 1652-1622, 809. The compound represented by the formula (11) is a viscous liquid and is excellent in solubility with other liquid crystal compounds. HTP was calculated in the same manner as in Example 1, and as a result, it was found to be as high as HTP = 34. (Example 4) With stirring Add 4-bromo-2-failed biphenyl 30g (120mmol) and dioxane 120g to the reaction vessel of the device, cooler and thermometer. Cool to 〇❹ C and add 17.3g of gasification. 16.7 g of grass cockroach gas was slowly added dropwise while the heat was added, and after the completion of the dropwise addition, the reaction was carried out at 20 ° C for 1 hour. After the completion of the reaction, the hydrazine gas was decomposed with water, and the organic phase was washed with saturated brine and the solvent was distilled off to obtain A compound of the formula (丨2).

F

Then, in the reaction vessel having the stirring device, the cooler and the thermometer, 35 g (111 mmol) of the compound represented by the above formula (12), bismuth 34 201011036 sorbitol 8.1 g (56 mmol), and dioxane 200 m were added. In the ice bath, triethylamine i3.4 g (133 mmol) was slowly added dropwise while keeping the reaction vessel below 5 C. After the completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction mixture was filtered, the filtrate was added to a solution of 200 ml of chloroform, and washed with a 10% aqueous solution of hydrochloric acid, and washed with a saturated aqueous solution of sodium chloride. After distilling off the solvent and washing the target with methanol, 34 g of the compound of the formula (13) was obtained by recrystallization from dioxane/methanol.

34 g (47.5 mmol) of the compound represented by the above formula (13), 16.5 g (li 5 mmol) of butyl vinegar, 14 g (146 mmol) of triethylamine, tetrabutyl ketone 31 g (97 mmol), and acetic acid were added thereto. Lg, dimethylformamide 300 ml, the reactor was heated to 9 under a nitrogen atmosphere (Γ:: reaction. After the reaction was completed, ethyl acetate, Thf, 10% hydrochloric acid aqueous solution, pure water, saturated salt Wash the organic layer with water, distill off the solvent and pass 5 times the amount (weight ratio)

35 201011036 100 ml of ethanol, and reduction reaction (hydrogen reaction of 5 MPa: 3 hours) was carried out with hydrogen (MMPa). The reaction liquid was filtered, and the reaction solvent was evaporated to give 30 g of the compound of formula (5).

30 g (40 nnn〇l) of the compound represented by the above formula (15), 7.9 g (88 mmol) of propylene helium gas and 200 ml of methane methane were added thereto, and the reactor was cooled to 5 ° C or lower under a nitrogen atmosphere. Then, 8.8 g (88 mmol) of triethylamine was slowly added dropwise. After the completion of the dropwise addition, the mixture was reacted for 1 hour at 1 (rc). After the completion of the reaction, di-methane was added, and the organic layer was washed with a hydrazine aqueous solution of hydrochloric acid, pure water, and saturated brine. The solvent was distilled off and passed 5 times by weight. The tannin column was purified to obtain 28 g of the target compound represented by the formula (16).

(physical value) lH_NMR (solvent: heavy gas imitation): 5 : 1·71 ( μ, 8H) 2.68 (Μ'4Η), 2·99 (Μ, 4Η), 4.09-4.18 (Μ, 12Η), 4.70 ( d, lH), 5.09 (t, lH), 5.46 (t, lH), 5.52 (Μ, 1Η), 5.84 (dd'2H), 6.11 (Μ, 2H), 6.37 (dd, 2H), 7.01-7.10 (Μ' 4H), 7.35-7.41 (Μ, 2H), 7.59-7.64 (Μ, 4H) 8.07-8.1 5 36 201011036 (d, 2H). 13C-NMR (solvent: heavy chloroform): occupies: 25 2, 30.3, 35.2, 63·9, 64. Bu 70.7 ' 74.5, 78.5, 81.2, 115.9, 116.2, 124.5, 128·4, 128.9, 129.8, 129.9, 130.5, 130.8, 166.1, 172_5. Infrared Absorption Spectrum (IR) (KBR): 2925, 2855, 1760, 1652-1622, 809 ° (melting point) 64 °C. The compound represented by the formula (16) has a melting point as low as 64 〇 c, and is excellent in solubility with other liquid crystalline inert compounds. HTP was calculated in the same manner as in Example 1, and as a result, a value as high as HTP = 5 1 was displayed. (Comparative Example 1) 21.4 g (100 mmol) of 4-(4-hydroxyphenyl)benzoic acid, 2.5 g of potassium iodide, and tetrabutylammonium bromide 〇7 g were added to a reaction vessel equipped with a stirrer, a cooler and a thermometer. The ethanol was stirred at room temperature for 400 m. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After the completion of the dropwise addition, 20 g of chloropropanol (150 mmol) was slowly added dropwise while maintaining the reaction vessel at 50 °C. After the completion of the dropwise addition, the reaction vessel was further heated to 70 ° C, and further reacted for 3 hours. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate and concentrated to give 22 g of Compound 4 of formula (17).

COOH (17) Next, 22 g (71 mmol) of the compound represented by the above formula (17), 10 g of acrylic acid (140 mmol), and p-toluene were added to a reaction reactor of 37 201011036 equipped with a stirring device, a cooler and a Dean_stark apparatus. The acid lg and toluene were heated to a reaction vessel to reflux the toluene, and the reaction was continued for 4 hours. After the completion of the reaction, the reaction mixture was washed with saturated sodium bicarbonate, and then neutralized with a 10% aqueous hydrochloric acid solution, and then washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off to give 19 g of the compound of formula (18).

Next, '19g (51 mmol) of the compound of the above formula (18), 3.8 g of isosorbide (27 mmol), and dimethylaminopyridinium were added to a reaction vessel having a stirring device, a cooler and a thermometer. 9 g, two gas toluene 200 ml 'The reaction vessel was kept at 5 or less in an ice bath. 9 g (6.3 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 the reaction was allowed to proceed for 5 hours. After filtering the reaction mixture, 1 ml of di-methane was added to the filtrate, and the mixture was washed with a 1% aqueous solution of hydrochloric acid, and then washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate. After the solvent is distilled off, it is purified by a silica gel column and recrystallization to obtain the target compound Ug represented by the formula (19). The compound has a melting point of 15 Å. 〇© Above, it cannot be measured. [化42]

(physical value) W-NMR (solvent: heavy gas imitation): occupies: h55_l45 (M, 8h 38 201011036 1.71 (Μ, 4Η), 1.83 (Μ, 4Η), 2.66 (M, 4H), 2.96 (M , 4H), 3.93 (Μ, 2H), 3.98 (Μ ' 2H), 4.03 ( s, 4Η) ' 4.30 ( t,4Η), 4.50 ( t,4Η), 5.35 ( s,2Η), 5.65 ( dd, 2H), 5.85 (d, 2H), 5.85 (d, 2H), 6.15 (q ' 2H), 6.55 ( d, 2H), 7.10 ( d, 4H), 7.50 ( M, 4H) » 8.12 ( d, 4H » 8.13 ( d > 4H) ° Infrared Absorption Spectrum (IR) (KBR): 2925, 2855, 1760, 1652-1622, 809. © (Melting Point) > 15 (TC. The formula (Comparative Example 1) The compound represented by 丨9) does not have the feature of the compound of the present invention, that is, a spacer containing an ester bond. Therefore, the melting point is high and the solubility with other compounds is also problematic. The liquid crystal composition similar to that of Example 1 is calculated. HTP, the result shows a value as high as HTP = 33, but due to poor solubility, only 〇 5% can be added. (Comparative Example 2) ® & A reaction vessel with a mixing device, a cooler and a thermometer is added 3-( P-hydroxyphenyl) propionic acid 2〇g (i2〇mm〇i), 2 g of potassium, 0.5 g of tetrabutylammonium bromide, and 400 ml of ethanol were stirred at room temperature, and 12 g @ 25% aqueous solution of emulsified sodium was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 5 (TC, slowly). Adding 25g (144mm〇l) to the dropping base. After the addition, the reaction vessel is heated to the thief and further reacted for 3 hours. After the reaction, the 10% hydrochloric acid is neutralized and extracted with ethyl acetate. After drying the sodium, the solvent is concentrated to synthesize the compound represented by the formula (20). 201011036 (20) q_v°-〇^_cooh Next, the above-mentioned synthetic formula (20) is added to a reaction vessel having a stirring device, a cooler and a thermometer. 32g (123 mmol) of the compound shown, 7.7 g (55 mmol) of isosorbide, 1.8 g of dimethylaminopyridine, 500 ml of dimethylacetate, and kept the reaction vessel below 5 ° C in an ice bath. 19 g (150 mmol) of diisopropylcarbodiimide was slowly added dropwise under the atmosphere. After the completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After filtering the reaction solution, dioxane was added to the filtrate. 200ml, washed with 10% hydrochloric acid solution, and then full Washed with brine, and the organic layer was dried over anhydrous sodium sparse. After distilling off the solvent, it was purified by a 5 times by weight (by weight) silica gel column to obtain 27 g of the compound of the formula (21).

Next, the compound Hg (17. 7 mmol) represented by the above formula (21), 150 g of carbon and 150 ml of ethanol were added to an autoclave vessel equipped with a stirring apparatus, and reduction reaction was carried out with hydrogen at 1 atmosphere (reaction temperature 50 °). C, 3 hours). The reaction solution was filtered, and the reaction solvent was distilled off to obtain 7.8 g of the compound of the formula (22).

(22) Next, to the reaction vessel 201011036 with a stirring device, a cooler and a thermometer, 13.8 g (l〇〇mm〇i) of 4-hydroxybenzoic acid, 25 g of potassium iodide, 0.7 g of tetrabutylammonium bromide, and ethanol were added. 400 m was stirred at room temperature. 12 g of a 25% aqueous solution of sodium hydroxide was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 50 ° C, and 6 g of chlorohexanol (i5 〇 mm 〇 1) was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was further heated to 70 ° C and further reacted for 3 hours. After completion of the reaction, hydrochloric acid was used to carry out _ and ' extraction with ethyl acetate. After drying over sodium sulfate, the solvent was concentrated to give 17 g of the compound of formula (23). HO~ 0 \ Jr-co〇H (23)

Next, the compound i7g (71 mmol) represented by the above formula (23), 10 g of acrylic acid (140 mmol), p-toluene acid lg, toluene were added to a reaction vessel equipped with a stirring device, a cooler and a Dean-Stark apparatus. 100ml. The reaction vessel was heated to reflux the toluene, and the reaction was continued for 4 hours. After the completion of the reaction, the reaction mixture was washed with saturated sodium hydrogencarbonate and then 1 〇 〇 /. The aqueous hydrochloric acid solution was neutralized, washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 22 g of a compound of the formula (24).

COOH (24) Next, 7g (16 mmol) of the compound represented by the above formula (24) and 9.2 g (32 mmol) of the compound represented by the formula (22) were added to a reaction vessel having a stirring device, a cooler and a thermometer. , dimethylaminopyridine 0-43 g, methylene chloride 100 m Bu in the ice bath to keep the reaction vessel below 5 °C. 4.7 g (38 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 allowed to react for 5 hours. After the reaction mixture was filtered, 100 ml of methane methane 201011036 was added to the filtrate, and the mixture was washed with aq. After the solvent was distilled off, it was purified by a silica gel column and recrystallization to obtain 13 g of the target compound of the formula (25). CH2=CHCOO(CH2)e〇

C2H4CO

(25) H 〇C〇C2H4_\ // 〇〇〇~OCOCH=CH2 (physical value) W-NMR (solvent: heavy gas imitation): 5 : 1.55-1.45 ( Μ, 8H), 1.71 ( Μ, 4Η), 1.83 (Μ, 4Η), 2.66 (Μ, 4Η), 2.96 Ο (Μ, 4Η), 3.76 (Μ, 2Η), 3.90(s, 4H), 4.03(t, 4H), 4.17( t,4H), 4.29(t,lH),4.76(t,lH),5.18(d, 2H) « 5.78 ( d > 2H), 6.15(q,2H), 6.37(d,2H), 6.96 ( d, 4H) 7.23 ( d, 4H), 7.25 ( Μ, 4H), 8_12 ( d, 4H). 13C-NMR (solvent: heavy gas imitation): 5: 25.6, 28.4, 28.8, 30·1, 30·2, 35.3, 35.5, 64.3, 67.9, 73.0, 73.8, 80.6, 85.7, 114.0, 121.3, 121·5 , 128.3, 129.0, 130.2, 131.9, ® 137.1 ' 137.4, 149.2, 163.0, 164.5, 165.9, 171.3, 171.6. Infrared Absorption Spectrum (IR) (KBR): 2925, 2855, 1760, 1652-1622, 809 ° (melting point) 79 °C. The compound represented by the formula (25) has a melting point as low as 79 ° C and is excellent in solubility with other liquid crystal compounds. However, HTP was calculated in the same manner as in Example 1, and as a result, it was found to be as low as HTP = 12. 42 201011036 (Example 5) Preparation of polymerizable liquid crystal composition A polymerizable liquid crystal composition (composition 1) having the composition shown below was prepared.

0(CH2)30C0CH=CH2 20% 20%

Coo

50% CH2=CHC00(CH2)30

Liquid crystal phase. To the composition, a 1% photopolymerization initiator benzoin dimethyl ketal (trade name: IRGACURE 65 1 manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to prepare a polymerizable liquid crystal composition (composition 2). This composition 2 was injected into a chamber of polyimine having a length of 5 cm, a width of 5 cm, and a pitch of 5 μm by a vacuum injection method. The ultraviolet rays of 4 mW/cm2 were irradiated for 120 seconds using a high-pressure mercury lamp, and the composition 2 was uniformly polymerized to obtain an optical anisotropic body. The optical anisotropic body has good circular polarization characteristics. (Example 6) Preparation of polymerizable liquid crystal composition 43 20% 201011036 A polymerizable liquid crystal composition having the composition shown below (composition 3) was prepared.

0(CH2)3〇COCH=CH2 0(CH2)6〇COCH=CH2 CH2=CHCOO(CH2)3〇 20% 50% o(ch2)3ococh=ch2

10%

Q

The Q polymerizable liquid crystal composition has good compatibility and exhibits a cholesterol liquid crystal phase. To the composition, a 1% photopolymerization initiator Benzene dinonyl ketal (trade name: IRGACURE 65 1, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to prepare a polymerizable liquid crystal composition (composition 4). This composition 2 was injected into a chamber of polyimine having a length of 5 cm, a width of 5 cm, and a pitch of 5 μm by a vacuum injection method. The ultraviolet rays of 4 mW/cm2 were irradiated for 120 seconds using a high-pressure mercury lamp, and the composition 2 was uniformly polymerized to obtain an optical anisotropic body. The optical anisotropic body has good circular polarization characteristics. (Comparative Example 3) Preparation of Polymerizable Liquid Crystal Composition A polymerizable liquid crystal composition having the composition shown below was prepared (composition 5 44 201011036 CH2=CHCOO(CH2)3〇

Coo

o(ch2)3ococh*ch2 CH2=CHCOO(CH2)6〇

Coo

0(CH2)6〇COCH=CH2 20% 20% CHy=CHCOO(CH2)3〇

0(CH2)3OCOCH=CH; 50%

The polymerizable liquid crystal composition showed a cholesteric liquid crystal phase, but the alignment was poor and uneven. To the composition, a 1% photopolymerization initiator benzoin dimethyl ketal (trade name: IRGACURE 65 1, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to prepare a polymerizable liquid crystal composition (composition 6). This composition 2 was injected into a chamber of polyimine having a length of 5 cm, a width of 5 cm, and a pitch of 5 μm by a vacuum injection method. Ultraviolet rays of 4 mW/cm 2 were irradiated for 120 seconds using a high-pressure mercury lamp, and the optical anisotropic body had circular polarization characteristics, but became an optical anisotropic body which was cloudy and uneven. φ [Simple diagram description] None [Main component symbol description] None 45

Claims (1)

201011036 VII. Patent Application Range 1. A polymerizable chiral compound which is a compound represented by the following formula (I): (I) rn Wherein R1 and R2 are independent of each other, and represent a polymerizable group, and S1 and S2 are independent of each other, and represent a spacer group; Y1 and Y2 are independent of each other, and represent -CH2CH2COO-'-OCOCH2CH2-'-0C00S30-'-OS3OCOO-'-CH =CH-COO- and -OCOCH=CH-, S3 represents an alkyl group having 2 to 6 carbon atoms and an alkoxy group; A1 and A4 are independent of each other, and represent 1,4-phenylene and naphthalene-2,6- Dibasic; A2 and A3 are independent of each other, and represent 1,4-cyclohexylene, 1,4-phenylene, Pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, 1,3-dioxin-2,5- Dibasic; A1, A2, A3 and A4 are independent of each other and may be substituted by alkyl, dentate alkyl, alkoxy, dentate, cyano or nitro; B1 and B2 are independent of each other, indicating -〇-, -S -, -OCH2-, -CH20-, -CO-, -COO-, -OCO-, -OCOO-, -CO-NR11-' - NRu-CO-, -SCH2-, _CH2S-, _CH=CH-COO -, -OCO-CH=CH-, -CH2CH2-COO-, -OOC-CH2CH2-'-NRn-CO-, -CO-NR11-, -CO-CH=CH-, -CH2-'-C2H4-, -CF2-, -CF20-, -OCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, _CH=CH_, _CF=CH- , -CH=CF-, -CF=CF-, -C triple C- or single bond; X1 represents -CO-, -CH=CH-CO-, -CH2CH2-CO- '-CH2- > -C2H4- '-CF2- '-NRn-CO- or single bond; X2 means -OC-, -OC-CH=CH-, 46 201011036 Dibasic, tetrahydronaphthalene 2,6-diyl; oxime 2 and I hexyl, 1,4-phenylene, naphthalene 2,6-indole 3 are independent of each other and may be alkyl, haloalkyl, alkoxy, halogen , cyano or nitro substitution; β1*Β2 mutual Independent' means -0-, -och2-, -ch2〇 X2 represents -OC-, -OC-CH=CH-, _-CH=CH-CO_, _〇C-CH2CH2-; -OC-CH2CH2-; m and n represent 0, 1 or 2 〇3. The polymerizable chiral compound of the first or second aspect of the invention, wherein at least one of 'm and η represents hydrazine. A liquid crystal composition comprising the polymerizable chiral compound according to any one of claims 1 to 3. 5 · An optical anisotropic body using the liquid crystal composition of the fourth application of the patent application. Eight, schema: None 47