TW200946649A - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystalline polymer, and optical isomer - Google Patents

Abstract

This invention provides a polymerizable liquid crystal compound represented by the following formula (I), a polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound and a polymerizable chiral compound, a liquid crystalline polymer produced by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition, and an optical isomer comprising the liquid crystalline polymer as a constituent material. The polymerizable liquid crystal compound has a broader temperature range in which a liquid crystal phase is developed, is chemically stable, can be produced at low cost, and has a broad selective reflection wavelength band ?? (i.e., has large ?n). The polymerizable liquid crystal composition contains this compound. The liquid crystalline polymer is produced by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition. The optical isomer comprises the liquid crystalline polymer as a constituent material. In formula (I), M represents a C1-30 divalent organic group or the like; Y1 to Y8 represent -O-C(=O)-, -C(=O)-O- or the like; G1 and G2 represent a C1-20 divalent aliphatic group or the like; Z1 and Z2 represent a C2-10 alkenyl group or the like; A1 and A2 represent a C1-30 divalent organic group (A); X1 and X16 represent a hydrogen atom or the like; and a, b, c and d are 0 or 1.

Description

[Technical Field] The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound and a polymerizable chelate compound, and a liquid crystal obtained by polymerizing these. A polymer and an optical anisotropy using the liquid crystalline polymer as a constituent material. [Prior Art] In recent years, as an optical film used for an optical compensation plate or the like of a liquid crystal display, a liquid crystal alignment film which is subjected to alignment treatment with a liquid crystal compound having a liquid crystal polymer or a polymerizable functional group has been developed. The film is capable of achieving a more highly oriented state, i.e., tilt orientation, twist orientation, and orientation which is impossible to achieve with a double-refractive film using a polymer film extension technique. In addition, a liquid crystal alignment film (selective reflection film) obtained by discoloring and aligning a composition of a polymerizable liquid crystal compound such as a liquid crystal polymer or a liquid crystalline (meth) acryl acid ester compound and a chelating compound The color-changing polarizer system used for the selective reflection characteristics is also put into practical use. The selective reflection center wavelength λ of the selective reflection characteristic is represented by λ = η x P U for the average refractive index, and ρ for the color-changing pitch. Further, the selective reflection wavelength region Δ λ is Δ long = Δ nxp [in the formula] Δ η (ne — ηο ), respectively, so that ne represents a constant refractive index of the ,, and represents a positive < refractive index of light. Said. Therefore, in order to widen the selective wavelength region Δλ of the selective 2209-10153-pf 6 200946649, Δ n, that is, a material having an increased optical anisotropy is required. Further, in order to use a selective reflection film as a color-changing polarizer for a liquid crystal display, selective reflection must be generated in the visible light region. Generally, the selective reflection wavelength region Δ of the ruthenium layer of the selective reflection film is further narrower than the visible light region, and therefore, a plurality of layers of the selective reflection film are laminated for wide-regionalization of the selective reflection wavelength region Δλ. . Therefore, in the case where the selective reflection wavelength region Δ ^ is used to narrow the material, the selective reflection thin m of the material changes the number of layers, and there is a problem that the productivity is lowered. Therefore, from this point of view, it is required to selectively reflect a material in which the wavelength region Δ is widened, that is, a material which becomes large (polymerizable liquid crystal compound or the like). However, in the case of a conventional polymerizable compound or the like, Δη becomes large, which is lacking in calculus, coatability, and orientation, and it is impossible to form a film uniformly or it is not easy to obtain an orientation which can be supplied for use. The state of the selective reflection film occurs. On the other hand, as the liquid crystal compound, the following chemical formula (la) is known: -(10) (In the chemical formula, 'Ra represents an alkyl group, and Rb represents an alkyl group, a cyano group, a ruin atom, a trimethoxy group, etc.). The n丫嘻 class represented. - the compound is a liquid crystal material having a characteristic that the temperature range of the liquid crystal phase is widened and relatively stable, and the composition is cheap and easy to manufacture.

2209-10153-PF 7 200946649. However, the 'compatibility of these azines in the liquid crystal compounds which are common to the others is not necessarily satisfactory. Further, in the above chemical formula (la), when the number of carbon atoms in the side chain base group becomes large, the compatibility can be slightly improved, but there is also a problem that the temperature range in which the liquid crystal phase is displayed is narrowed. In order to solve such a problem, 13⁄4) + by ^ Therefore, in Patent Document 1, it is proposed by the following chemical formula (1b):

(In the chemical formula, R represents a hydrogen atom or an alkyl group having a carbon atom number of 丨2, and in the state where R is an alkyl group, a double bond is transferred and arranged. The p system represents an integer of ～10. Or 1, W, χ and Y represent a fluorine atom, a chlorine atom, a methyl group, a cyano group or a hydrogen atom, and 2 represents a fluorine atom, a chlorine atom, a gas group, a Xuan base of 1 to 12 or a hospital oxygen Base, carbon number 3~12

The alkenyl group or the alkenyloxy group, but one or more of the nitrogen atoms contained in these groups may be substituted with a fluorine atom. ) the liquid crystal compound represented. This compound is chemically stable to heat, light, etc., has good liquid crystallinity, and is easily industrially produced. Further, since the compatibility with the conventional liquid crystal compound or liquid crystal composition is good, the response time of the obtained liquid crystal can be greatly improved by using this. Therefore, it is practically a structural component of a liquid crystal material for a liquid crystal display element having a wide w range and capable of high-speed response.

2209-10153—PF 8 200946649 c In recent years, liquid crystal display devices have become more and more high-performance. Currently, it is required to display a wider temperature range of liquid crystal phases, which can be chemically, stably, and inexpensively manufactured. Liquid crystal material. [Patent Document 11] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymerized liquid helium compound containing a compound which is broader in range, stable in chemistry, and which can be manufactured inexpensively and which has a widening wavelength range, that is, Δη becomes large. a polymerizable liquid crystal composition, poly octa/θ, a liquid crystal polymer of 4 to 4, and a liquid heterogeneous body as a constituent material, As a lesson [means to solve the problem] ❹ The inventor of the inventor is to understand, ^^, +, #Τ巧ί% to decide the topic, so the whole research is carried out, and it is found that: ;^ | Shishi is a polymerized liquid with a chain structure

The center of the chain of the crystalline compound and the A-carrying liquid is called the central source. The linear atomic group of the common source is suitable for the specific compound of the 秦°Qin bone lattice. It is stable for heat or light. 々 σ σ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 So that the present invention is completed. As described above, the polymerizable liquid crystal compound of the following (j) 2209-10153-ρρ 9 200946649 (5) is provided by the brother of the present invention. (1) A polymerizable liquid crystal compound is obtained by the following chemical formula Z! + Y "Yg-A々a:

Xe

❹ ❹ [In the chemical formula, lanthanide represents an organic group having a carbon number of 1 to 3 Å which may have a substituent. Υ, ~ γβ system independently represents chemical single bond ~ 〇 ~, -S-, - 〇-c (= 〇) -, one - 〇 - c (two 〇) " ° NRI ~ C (= 〇) ——C(=〇)—NR1—, —〇—c( =G) — NK,---NR^-CC =〇) -0——NR1-c( ^ 〇) — NR1—, one— NRl—or an NRl 〇__. Here, it means a halogen atom or an alkyl group having 1 to 6 carbon atoms. Gi and Gz are each independently represented by an aliphatic group of carbon having a carbon number of 丨~2〇2 in the aliphatic group, in the group -〇S-, a 0-C(=0) 〇 ) —〇〇~c(=0) —0, _NR2—c(=0)C (=0) — NR2—, — NR2_^_c(=〇) _ (1st and S: 2 adjacent to each other) Except for the above, R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L and 22 independently represent a carbon number of 2 to 1 〇 2 C which can be substituted with a fang atom. Separately, the Al and A2 systems independently represent the carbon number of the carbon number: 30, and the A4~ series independently represent the carbon atom number 1 to 1G of the ruthenium atom, the dentate atom, the organic group, and the cyanide. Base, stone xiaoji, ιΓ

2209-10153-PF 10 200946649 -c(=(m -c(=0) - 0R3, -〇-c〇) - (10), -NR4- C ( = 0) - r C ( = 0) - N ( R3) R4 or - 〇-c (dioxin) - N (R3) R4. Here, R3 represents a hydrogen atom or a county which may have a substituent of "1 to 1Q", in the state where R3 is a filament , in the alkyl group, in the - 〇 - s - 〇 - c (= 〇) -, -c (=0) - 〇 -, - 〇 - c (= 〇) -0-, -_-c (=0) —, _c(=0) — NR5~, -(10)― or ―c( = 0) _ (However, ❹ Ο —〇_ and one S—are adjacent to each other by 2 or more, except for the state R4 and R5 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Each of a and d is independently represented by hydrazine or 1. (7) The polymerizable liquid crystal compound according to (1), wherein the secret system may have a substitution. a naphthyl group which may have a substituent, a naphthylene group which may have a substituent or a substituent which may have a substituent: - (1) Polymerizability as described in (1) 4 (2) The liquid crystal compound, Liz, Z, and Z2 are independently CH2==CH-'cH2=c(ch3)-, CH2=C(C1)Kch... CH〇CH2—, CHfC(CH0—CH2—CH2—, (CH〇2C = -, CH3-CH=CH— or CH3—CH=CH—CH2-—(4) The polymerizable liquid crystal as described in (1) The compound, the aforementioned phenylene group which may have a substituent, becomes ! k ', α-1, c=〇, Υι 'Y 3~Y 6 , Y 8 are each independently -C ( = Q ) __ Q Ο - Or -I 'Gl~G2 series* do not independently become -(CH:)= -UH2) "' can be in these bases H 0 - in

C 2209-10153-PF 11 200946649 o- 0—c(=〇) ~ or 〇) — ‘ Zi and Z2 are independently ch2=ch— , , L C CH3)- or CH2= C ( Cl )-, respectively. (5) As described in (4), the n-core polymerizable liquid crystal compound, wherein the M-based group can be substituted with a hydrocarbon group having 1 to 1 carbon number, and the hydrocarbon group 0-c ( =o) ~ or base, in a 0 ——, __ c ( = 〇) 0 〇 a c ( = 0) —, & verb 2 are all CH2=ch (6) as described in (4) The liquid crystal compound, the aforementioned μ system can be substituted with a C (= 〇) - 〇 R3 (R3 you 矣 - < κ 表 is not the same as described above) to replace the phenylene group. According to the second Λ Λ Ζ 本 of the present invention, the following polymer liquid crystal composition of (7) is provided. (7) The polymerizable liquid crystal group according to any one of the above (1) to (6), wherein the polymerizable liquid crystal group and the polymerizable chelate compound are contained in the polymerizable liquid crystal group. According to the third aspect of the present invention, the liquid crystal polymer of the following (8) is provided. (8) A liquid crystalline polymer-based polymerizable liquid crystal composition according to any one of the above (1) to (6), wherein the polymerizable liquid crystal composition described in (3) get. According to the fourth aspect of the present invention, the following optical anisotropy of (9) is provided. (9) An optically heterogeneous system 1. The liquid crystal surface molecule 'described in (8) is used as a constituent material. 2209-10153-PF 12 200946649 [Embodiment] Hereinafter, the present invention is divided into 1) a polymerizable liquid crystal compound, 2) a la 1 &quot; a raw liquid μ composition, 3) a liquid crystalline south molecule, and 4) an optical anisotropic body. The project will be described in detail. 1) Polymerizable liquid crystal compound The polymerizable liquid crystal compound of the present invention is a compound represented by the chemical formula (1) in the form of a compound of the formula (1). Μ indicates that it can be used as an organic basis

In the above chemical formula (I), the organic group carbon number of the carbon number of 1 to 30 having a substituent in the chemical formula is preferably 6 to 2 0. There is no particular limitation on the organic basis of the μ a a 甘 u u 但是 但是 但是 但是 但是 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ The following description is given as a specific example of the series.

2209-10153-PF 13 200946649

2209-10153-PF 14 200946649

The organic group which is a specific example of the above-mentioned oxime may be mentioned, and has a substituent at any position. The substituent series is a hydrocarbon group having a carbon number of 1 to fluorene, an alkoxy group having 1 to 6 carbon atoms, a dentate atom, a cyano group, a hydroxyl group, a nitro group, a C (= 〇) - 〇R3 (r3 system). It is the same as the meaning of r3 described later. In the meantime, it is preferable that the lanthanoid system may be a phenylene group which may have a substituent, a biphenylene group which may have a substituent, or the like, in view of the effect of the present invention. a naphthalene group which may have a substituent or a triphenylene group which may have a substituent, more preferably a phenylene group which may have a substituent represented by the following chemical formula (Μι) and by (Μζ) In general, the 4'-biphenylene group is particularly preferably a ρ-stupidyl group represented by the following chemical formula (Μ!). ❹

The substituent which may have a substituent (phenylene group, biphenylene group, naphthalene group or triphenylene group) is preferably a hydrocarbon group having a carbon number of 1 to 1 fluorene.

2209-10153-PF 15 200946649 or a C ( = 〇 ) _ 〇 R3 (R3 is the same as the meaning of v described later). The hydrocarbon group having a carbon number of 1 to 10 is a group having a carbon number of 1 to i, a chain having a carbon number of 2 to 10, a group having a carbon number of 2 to 10, and the like. Further, in these hydrocarbon groups, it may be referred to as -C(=〇)-〇-, one-〇-c(=〇), one or one C(=〇), and the like.

~Y8 series independently represent chemical single bonds - 〇-, _s_, -0-C (two 0)---C(=〇) -〇-〇-C(=〇) -〇-, -Nr -c(=〇) —, —c(=0)—legs——,—π — 〇) — NR1-, - Nr- c ( = 0) - 〇1, NR1— '-〇_NRl—or— NRl - 〇 -. Here, 'R! means hydrogen atom or methyl, ethyl, propyl, isopropyl, η-butyl, s-butyl, 3 gan &amp; The special carbon number 丨 ~6 Fanji. Even among these, the R system is preferably a hydrogen atom or w 0 - C (= NR1- C (-0)-

Even in this case, φ ^ - Tian, as Y丨 ~ γ8 is also best 〇 - '0-C ( ^ r\\ .. 〇 - c (. 0) - or -0 C ( = 〇 As an ideal gamma, 'the mouth is better from the hair and the required effect of the invention, and the γ7 is a C(=0)~〇2, each of which becomes Yi, γ3, γ4 ♦, human and H, Y6 and ^ are a combination of Oscv. ^(=0) 1 and G2 are independently 矣20 of the two-valent aliphatic group π, which may have a number of κ groups after the substituent. 'It is good to take the carbon price of 1~12.

2209-10153-PF 16 200946649 As the carbon number of G1 and G2]~9λ ^ ^ 2 (), the divalent aliphatic group series is an alkylene group having 1 to 20 alkyl groups and an alkenyl group having a carbon number of -20. Chain fat

Family base. Even in the case of the middle and the middle, the carbon number of the vinyl, tetramethylene, hexamethylene, octamethyl, etc. is the most preferable. 2 to 2. Alkylene group. The substituent of the aliphatic group of Gd G2 is exemplified by a sulfonyl atom, an alkoxy group of ❹ 2 to 6 or the like. The halogen atom is preferably a fluorine atom, and the alkoxy group is preferably a methoxy group or an ethoxy group. Helium atoms can be added to the aforementioned aliphatic group.

-S 〇—c(=〇)—,—厂广—八, (―〇) —0---〇-C(=〇) _〇_, — NR2-C (=〇) —, —Γ , C ( = 0) A welcoming 2, - nr2 - or a ((=0)&gt;- (but, - and - s - except for two or more adjacent states, except for the state.) It is not a hydrogen atom or an alkyl group having a number of from 1 to 6 which is the same as that of the above-mentioned alkyl group having an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom or a mercapto group. Even among these , Α Γ ^, Tian Ma Ma Gl ~ can also be independently known in - Cf Λ ) 〇 -, - 〇-c ( = ο) - or _ c (= - 'is best - (CH. 6 - or one (CH2) 4 - and the anthracene each independently represent an alkenyl group having a carbon atom number of 2 to 10 as a halogen atom. The desired effect of Z and the invention is the number of carbon atoms of the alkenyl group which is Zi and Δ. It is preferable that it is 2 to 6 from the viewpoint of more well-founded. In addition, the halogen atom of the substituent of the alkenyl group is preferably 220 9^-1 〇i53-pp 17 200946649 chlorine atom As an alkyl group of z and 1 which can be substituted with a halogen atom and having a carbon number of 2 to 1 fluorene Consider the specific example series CH2=ch_, CH2=C(CH3) CH2= c ( Cl ) - &gt; ch2= CH~ CH2- ^ ch2= c ( ch3)- ch2-, CH2=C(CH3) —CH2 —CIi2—, (CH3) 2C=CH—CH2 is such that, as the z] and Z2 systems, it is preferable to use j—, CH3—CH=CH~ or CH3—CH-CH2~, respectively. CH2=CH-, ch2=c(CH3)- or CHfC ((1) is particularly preferably CH2=CH-. X-~Xu each independently represents a hydrogen atom, a halogen atom, and a carbon number which may have a substituent 1 to 10 alkyl, cyano 'nitro, _ 0R3, 0 - C (=0) - R3, - C (= 〇) - 0R3, - 0 - C (=0) - 0R3, -NR, C(=0) — R3, —c(=〇) — n(r3) “ —〇—c (=〇) ~ N ( R3) R4.

Here, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. A series of alkyl groups having 1 to 10 carbon atoms which may have a substituent as R: methylethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl, fluorenyl and the like. In addition, the substituent of the alkyl group having a carbon number of 丨~1〇 which may have a substituent may be a halogen atom such as a fluorine atom or a chlorine atom; and an alkoxy group having a carbon number of 甲6 or the like of a methoxy group or an ethoxy group; A phenyl group or the like which may have a substituent such as a phenyl group or a 4-tolyl group.

2209-10153-PF 18 200946649 This ο outer 'in the state where R3 is an alkyl group, ς 『在在烧基,介右' -oc ( =0) &quot; at Ο C ( =0)~〇—, —nr5_c (2.), 0) 〇, ,~c --- or —c(=〇) _ (However, 2〇^C(=0)~肫5 is connected to 2 or more except for the state). And S are adjacent to each other. Here, β and R5 represent an alkyl group having a halogen atom or a carbon number of ~6.疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋Xl5 is Ά m^ or (2) white is a 虱 atom and Xl, χ" &amp; ^ is an OR3 or C (p3, + and Χ! 6 at least ~ 〇-R (here, r3 face description The meaning of .) and in the χ], ', the table - the same as before and B 6 is the hydrogen atom. And (: (=0) ~ 0 is more ideal is 卩 y C ^ Xl Xl6 are Hydrogen atom, bite 0 / X] 3 and b are both Wei Tagong = v „ 1 4 test 疋 (4) χ 2, ❹

X4~X〗 3 and Xl5 are all chlorine eyebrows $ 疋 (wearing as 虱 atoms and Xl, X3, Xl4 L - 0CH3, - 0C2H5, -Ci - Ω to 乂 - one is 匕 0) - 〇 - C{J3 , . —c2H5,-(:(=〇, nn c == 0) ϋ) ~〇' CH2CH2CH3 ^ ~ c, CH2CH2〇CH3A ϋ)~〇~CH2CH2〇CH2C —ο—ch2CH2〇CH2CH2CH3 and in Χι,χ3,及" and L (1) -, -c( wCH3, -c( = 〇)i non-bird c(=0)-0~CH2CH2CH3 CA,, C ( = 0 ) - ο r, H2CH2〇Ch~ CH2CH2 〇CH2CH3 and -c (= n, CH2CH2〇CH2CH2CH3 are hydrogen atoms. υ)~0, and Α2 are independent of carbon number 3.4. 2 organic 2209-10153-PF 0 19 200946649 base as A! And a specific example of the organic group of a2, such as methylene, ethyl, acryl, trimethylene, tetradecyl, pentamethylene, hexamethylene, sinoin, octadecyl, etc. Carbon number 别~ other alkylene group; a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a naphthylene group which may have a substituent, and the like, a vinyl group having a carbon number of 6 to 3 fluorene And a combination of an alkylene group and a propynyl group as shown below.

Even in the case where the effect of the present invention is more satisfactorily found, the core and the oxime 2 are preferably an alkylene group having 1 to 30 carbon atoms, more preferably a carbon number of 1 to 30. 10 alkylene groups. a, b, C, and d are independently 〇 or i, respectively. In the above chemical formula (I), as a basis for the combination of Ai&amp; A2 by a chemical formula: a γ2 - (G, - Yd a - z! and a chemical formula: - γ7_ (g2 - Ya) d ~ Z2 The following series are given. 22〇9-1〇153-pF 20 200946649 In addition, the above a and d are the repetition numbers of (G1 - Υ1) units and (G 2 _ Ya) units, respectively, and a and d are independent. The ground is 0 or 1. As a particularly desirable combination of a and d, from the viewpoint of more easily finding the synthesis and the desired effect of the present invention, both a and d become 1,1) and (3 become First, the general form in which a or d becomes 1, that is, the structure represented by the following chemical formula (α), is mentioned below.

In the chemical formula, Υ2 or Υτ is equivalent to a C (= 0) — 0 —, Gi or G2 is equivalent to a hexammine group, and Y! or Y8 is equivalent to a 0—C (= 0) —, Z] or The Z2 system is equivalent to the B-bake base.

2209-10153-PF 21 200946649

%

Ih^·^

2209-10153-PF 22 200946649

2209-10153-PF 23 200946649 Next, the general example of a to d2, that is, the structure represented by the following chemical formula (call), is mentioned below.

Or I In the chemical formula, Υ3 or Ye is equivalent to a C(=0) — Ο— ’Ζι 0 or z2 is equivalent to a vinyl group. Further, specific examples thereof are shown below.

In the polymerizable liquid crystal compound represented by the chemical formula (I) of the present invention, the two base systems represented by the following chemical formulas may be the same or different. Ζλ - Yi~ G1 - Υ2~ Αι~ Υ3 ί _ ja

2209-10153-PF 24 200946649 -γ6—α2- 丫7+g2- d

(In the &quot;i 匕学学, Zl, Ζ2, Yl Υ3, Ye Υ8, Αΐ, Α2, Gl, G2, a, and d are the same meanings as described above.) As the above chemical formula (I) The preferred specific examples of the polymerizable liquid crystal compound of the present invention are as follows. However, the polymerizable liquid crystal compound of the present invention is not limited to the following compounds.

2209-10153-PF 25 200946649

聚合 The polymerizable liquid crystal compounds of the present invention may be combined to form a ο —, a S —, an NH — C (= 0 ) _, a C (=0) — ΝΗ —, an NH—C (=0) − NH a conventional method of -, -0 - C (=0) -, a C (two 0) -0 -, a C (=0) - 0 - C (=0) - and other chemical bonds (for example, reference different Sandura Caro's organic compound synthesis method [I], [ Π ]: Hirokawa Bookstore, issued in 1986, was manufactured. The polymerizable liquid crystal compound of the present invention can be arbitrarily and arbitrarily

2209-10153-PF 26 200946649 Combination key (0 _ r Γ / ΠΛ , - 曰 key (一 C ( =0) — o-), guanamine bond (―c (=0) simplification -), acid chloride The preparation of the compound 〇Ch〇)_(1) and =2 (the formation reaction of Wc(,-), moderately '., s s · Senna has the requirement - a few of the conventional compounds constituting a few of them. The formation of a bond can be carried out, for example, as follows: ) &quot; Compound represented by the chemical formula: Q1 - x (x represents an atom of an atom. The same is given by ❹ )) and by a chemical formula: Q2 - 〇M" Ma is an alkali metal (main Ib &amp;, ^ main squid). The condensation is carried out in the same manner as the compound shown below. In addition, in the chemical formula, Q1 and Q2 represent an arbitrary organic group (between the following phases).兮 "〆Π". This reaction is generally referred to as Wiiliam S0n's synthesis. ,) Condensation is carried out by mixing a compound represented by the chemical formula 'Q1 X and a compound represented by the chemical formula: Q2 - 〇H in the presence of 'oxidized steel, potassium hydroxide or the like. a base such as sodium hydroxide or potassium oxyhydroxide is present, and a compound represented by Chemical Formula 11-E (E is an epoxy group) and a compound represented by a chemical formula of 'Q2 - 0H are mixed. Condensation is carried out. 4) In the presence of hydroxide steel and hydroxide, mix the compound represented by the chemical formula .Q1 ~ 〇FN (the 0FN system, which represents the group having an unsaturated bond) and by the chemical formula: Q2— The compound is represented by an addition reaction. 5) In the presence of copper or chlorinated steel, mixing is carried out by a compound represented by the chemical formula: ^ - X and a compound represented by the chemical formula Q2 - 〇 Ma 2209-10153-PF 27 200946649 . This reaction is commonly referred to as Ullmann (I) ι condensation. The formation of the s j vinegar bond and the guanamine bond can be carried out, for example, as follows. 6) In the presence of a dehydrating condensing agent (N,N~dicyclohexylcarbodiimide), the compound represented by the chemical formula: Q1~c bribe is chemically converted: q2—0H啖〇2_ does not condense. ^ Q2 The compound represented by 2 is subjected to dehydration Ο υ 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸In the presence of the test, react this to the chemical formula:

Q2 - a compound represented by NH2. S δ) is a compound represented by the chemical formula: Q2 - 0H or Q2 - NH2 after the acid anhydride is used as a compound represented by the chemical formula: Q1 - c〇〇H. 9) Dehydration condensation is carried out in the presence of an acid catalyst or a test catalyst for a compound represented by the chemical n C〇〇H and a compound represented by the chemical formula: Q2-〇H or Q2-NH2. The acid chloride system can be produced by a conventional method. For example, a method in which (a) is a carboxylic acid represented by a chemical formula: Q1 - c〇〇H, and a chlorinating agent such as a tetrachloroplatinium disc, a vaporized sulfinium sulfonium, or a vaporized ethanediazine is used. '(/5 ) 化学 a chemical formula: a silver carboxylic acid represented by Q1 _(3)_|a method of acting gas; a method of using a compound represented by the chemical formula: Ql-C00H to act on a red carbon oxide carbon tetrachloride solution; . It can be synthesized in the synthesis of the polymerizable liquid crystal compound of the present invention.

2209-10153-PF 28 200946649 Presents in the hydroxyl group of the intermediate to increase the yield. The method for protecting the hydroxyl group can be carried out by a conventional method (for example, referring to Greene's Protective Groups in Organic Synthesis Green ❹ (Greene, s protective group for organic synthesis), 3rd edition: Wiley-lnterscience, issued in 1999) Manufacturing. Zhao Jizhi's protection system can be carried out more specifically as follows. a) A compound represented by the formula: μ of 卯-Si-X and a compound represented by the chemical formula: Q4 - 〇H are mixed in the presence of a base such as imidazole or pyridine. Further, in the chemical formula, Q3 and Q4 represent an arbitrary organic group B (the same applies hereinafter). a vinyl ether compound such as σ 3,4-diindole-2H-pyran and a compound represented by Q2-0H in the presence of an acid such as p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt or hydrogen chloride; Carry out the reaction. c) The reaction is carried out by mixing a compound of the formula and a compound represented by the chemical formula: Q4-0H in the presence of a base such as ethylamine or pyridine. d) Mixing with chemical formula. 〇 广 广 / / / / / / Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q The compound represented by H is mixed with a chemical formula: Q in the presence of a base of sodium dioxoxide, triethylamine or the like, an anhydride 4, a human oxime) - 0 - C (=0) - an S phthalic anhydride compound represented by Q2 To chemicalize and react. To a. Q3 - the compound represented by 卯 is carried out e) in sodium hydroxide, two

In the presence of the indicated compound and the amine, the mixture is mixed with the compound represented by Q1 - X 匕: Q2 - 〇H

2209-10153-PF 29 200946649 Reaction. 〇 In the presence of a base of sodium hydride, sodium hydroxide, tri-, Q-amine, acridine, etc., δ is compounded by the chemical formula: Q1~ch2-X-- and the chemical formula, Q2-0H The compound is reacted. g) In the presence of (iv) potassium, sodium hydroxide, etc., the compound represented by Q1 - 〇 (10) - C (= 〇) - X and the compound represented by the chemical formula: h) mixing in the presence of a base such as triethylamine or pyridine

Q4- 0H ❹

The reaction is carried out by a chemical formula: Q1, a compound represented by the chemical formula: Q2 - 0H - C C ( = 〇) - X, and a compound represented by

The deprotection reading of the protecting group of the base is carried out at At fA丄A, and the deprotection is carried out by means of a conventional method due to the structure and species of the protecting group. (j) The tetrabutyl group is mixed with a fluoride such as fluoride to perform wrist protection. (11) Mixing and deprotecting in the presence of an acid such as p-toluic acid, p-toluene, hydrogen chloride or acetic acid. (iii) mixing and deprotection in the presence of hydrogen money, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid, triethylamine, hydrazine, and the like. / Deprotection by hydrogenation in the presence of a catalyst such as Pd-C. The compound of the present invention can be synthesized more specifically as follows. 2209-10153-PF 30 200946649

CHO

Ο

N-N

Y4-M-YS' X? )3⁄4 Xl1 Xi2 (!2)

15 Λ16 (13a} (13b)

1~}α2-Υ7|^[θ2-Υ84^Ζ2 © (In the chemical formula, M, Yl ~ Y8, Gl, G2, Zl, Z2, Al, A2, Xl ~ Xie, a, b, c and d The meanings are the same as those described above. Li and L2 represent a leaving group, Y3' means a reaction to L! to form a group of Y3, and Y6' means a group which reacts with L2 to form a Ye. For example, Li is C0C1 and Ys In the state of a C (= 0) - 0 -, Y3' is a 0H base, and in the state where L! is 0H and Y3 is 0 - C (= 0) - Y3' is C00H, in L In the state of ΝΗ2 base and Υ3 is an NHC (= 0)-, Υ3' is a C00H group. The state of Υ6' is also the same.) 2209-10153-PF 31 200946649 That is, 'reaction is chemical formula (1)盘) the disc compound (Jun compound (10)) represented by the formula (11 a ) and the formula (1 ib ) (醯肼 compound (Ha), 醯肼 compound (llb)), After obtaining the compound represented by the chemical formula (1 2 ) (compound (丨2)) (process 1) ' can be reacted by this and the compound represented by the chemical formula (13a) and the chemical formula (13b) (compound (丨) 3a) Further, the compound (13b)) is obtained by the compound of the present invention (the compound of the present invention) represented by the chemical formula (!) (Process 2). The reaction of Process 1 can be carried out by mixing and stirring the aldehyde compound UG) and the hydrazine compound (Ua) (and the hydrazine compound (11b)) in a suitable solvent. In this state, the reaction can be carried out sequentially in the state in which the ruthenium compound (lia) and the ruthenium compound (11b) are *the same compound. Further, in the same state in which the ruthenium compound (Ua) and the ruthenium compound (nb) are the same, a multiple amount or more may be used. In the process 1, the hydrazine compound (lla) is usually formed relative to the compound (10).

And the usage amount of (lib) is 0.5 to 5 times the Mohr number. The heart-pressing series of decyl alcohol is used in alcohol-based solvents such as process alcohols, iso(tetra), and butanol; ether-based solvents such as di(10), tetrahydrogenated dimethoxyethane, etc.; ethyl acetate, propylene acetate , propionate, §, etc. _ = material group (four) solvent + Qian Geng aliphatic smoke solvent; N, N ~ dimercapto acid amine, n - fluorenyl.醢 系 溶 各 各 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;

2209-10153-PF 32 200946649 A sulfur-containing solvent such as a butyl ketone or the like; and a mixed solvent composed of two or more of these. The reaction of the coat 1 is smoothly carried out in a temperature range from a temperature of from 1 °C to the boiling point of the solvent used. The reaction time is also based on the reaction scale, but is usually from several minutes to several hours. The reaction liquid containing the compound (12) was obtained as above. In the present invention, the compound (12) can be isolated from the obtained reaction liquid, and the isolated compound (丨2) can be supplied to the next process 2, and the compound (12) can be isolated without containing the compound (12). 12) The reaction solution 'is supplied directly to Process 2. The aldehyde compound (1 〇 ) is a conventional compound which can be produced by a conventional method. Further, the 'brewed compounds (Ha) and (lib) can be obtained by reacting hydrazine with a benzaldehyde derivative (14a, 14b) as shown in the following description.

Further, as the benzaldehyde derivative to be used, a compound in which a protecting group is bonded to γ3', 2209-10153-PF 33 200946649 γ6' can be used, and the deprotection of the sulfhydryl group is carried out before the reaction of Process 2 is carried out. After the ruthenium compounds (Ua) and (Ub), the reaction of Process 2 is carried out. For example, in the case where Y3' and Υ6 are in the form of a hydroxyl group, the process can be carried out by using a protecting group such as t-butyl dimethyl methacrylate or the like to protect the benzofuran derivative of the thiol group. After the reaction, deprotection was carried out in accordance with a usual method to obtain hydrazine compounds (Ua) and (丨 lb). Then, the compound (I) (13a) and (13b) are reacted by the compound (12) obtained in Process 1, to obtain the object compound (I) of the present invention (Process 2). The reaction of the product 2 can be carried out by mixing the compound (12) and the compound (13a) (and the compound (13b)) in a suitable solvent. In this state, the reaction can be carried out sequentially in the state where the compound (13a) and the compound (13b) are different compounds. Further, in the state in which the chemical substance (1) 3a) and the compound (13b) are the same, the amount of 〇 or more may be used. In the preparation of the oxime 2, the compound (1 3a ) and the compound (丨3b) are used in an amount of from 5 to 5 times the molar number of the compound (12). As a solvent series used in Process 2, an ether solvent such as diethyl hydrazine, tetrahydrofuran 1 '2-methoxyethane or 1,4-dioxane; ethyl acetate, acetonitrile acetate, and propyl acetate A solvent such as acid vinegar or the like; an aromatic hydrocarbon solvent such as benzene, toluene or dimethyl benzene; a hydrocarbon solvent such as pentane, η-hexane or n-heptane; N-dimethyl decylamine, methyl methacrylate

2209-10153-PF 34 200946649 A guanamine-based solvent such as saponin or hexamethylphosphoric acid; a sulphur-containing solvent such as a dimethyl meth or a cyclobutyl; and two or more of these A mixed solvent composed of the like. Further, in the case where the compounds (13a) and (13b) are in the form of an acid chloride or an anhydride, the reaction can be carried out more smoothly by adding a test to the reaction system. Examples of the base to be used include an organic base such as pyridine, triethylamine or diisopropylethylamine, and an inorganic base such as sodium cerium oxide, potassium oxyhydroxide, sodium carbonate or potassium carbonate. The amount of the base used is usually 1 to 3 times the molar number of the compound (丨3a) and (丨3b). The reaction of Process 2 proceeds smoothly over the temperature range from one 丨〇&lt;t to the $point of the media used. The reaction time is also usually from several minutes to several hours depending on the reaction rule i_疋'. Many of the compounds (13a) and (13b) are known compounds which can be produced by a conventional method. 〇 As a compound (13a, the following compounds. Of course, a series of specific examples of (13a) and (13b) are preferred. The present invention is not limited to these compounds.

2209-10153-PF 35 200946649 *10 Ο ο h2c: ο 2 (In the chemical formula, Γ and s each independently represent an integer of 1 to 6, [ represents a chlorine atom or a hydroxyl group, and Rl () represents a hydrogen atom or Methyl.) In any reaction, after the completion of the reaction, the conventional separation operation of the hydrazine organic synthesis chemistry can be carried out, and the conventional separation such as column chromatography, recrystallization, distillation, etc. can be carried out as required. Refined means, and isolate the target. The structure of the target can be identified by measurement of NMR spectrum, IR spectrum, mass spectrometry, etc., elemental analysis, and the like. 2) Polymerizable liquid crystal composition The second aspect of the present invention contains the polymerizable liquid crystal compound of the present invention and

A polymerizable liquid crystal composition which is a polymerizable compound (hereinafter referred to as "polymerizable integrated compound"). The composition of the present invention contains, as an essential component, one or two or more kinds of the polymerizable liquid crystal compounds of the present invention. The composition of the present invention is in addition to the polymerizable liquid crystal compound of the present invention, as disclosed in Japanese Laid-Open Patent Publication No. Hei 11-130729, Japanese Patent Application Laid-Open No. Hei. No. 7G, Japanese Patent Publication No. 2 (10) 263 ? 9 9 δ 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 883 883 883 883 883 883 883 883 883 883 883 883 883 883 883 883 883 As described in Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. The content of the other polymerizable liquid crystal compound to be added to the polymerizable liquid crystal compound of the present invention is preferably 50% by weight or less, more preferably the following, based on the total amount of the polymerizable liquid crystal compound of the present invention. 'The polymerizable t compound used in the composition of the present invention can be polymerized in the polymerizable property of the present invention if it has an integrated carbon atom in the oxime; and the polymerizable liquid crystal compound of the present invention is not scattered. In the case of ambiguity, there is no particular restriction.矣_, this 'polymerization' is not limited to the usual polymerization reaction, but also represents a broad chemical reaction involving a crosslinking reaction. In the composition of the present invention, the polymerizable chelate compound can be used in combination or in combination of two or more kinds. The polymerizable liquid crystal composition constituting the present invention is a liquid crystal compound system - a polymerizable color-changing phase capable of praising the moon. The polymerizable chelate compound is found as a polymerizable chelate compound, for example, as described in the publication of the specification.

The series of compounds are, for example, "chelating", but are not limited to these. The compounds represented by the formula, 2209-10153-PF 37 200946649

In the formula a to the formula, V and R7 are methyl, methoxy and the like. ...J ♦ For example, 氲 atom, (_〇) 乍 is γ and r series, for example, -〇~, Ω r

-0 to c (W, etc.) Further, ^ C is independently 2, .... As a specific example of each of Wm and m2, the following compounds are shown.

PQ

X〇t〇c 0

2209-10153-PF 38 200946649 In the polymerizable liquid crystal composition of the present invention, the polymerizable chelate is: for example, based on the weight fraction of the polymerizable liquid crystal compound (10): from 1 to 100 parts by weight, preferably Yes. .5~U) parts by weight. In view of the fact that the polymerization reaction is carried out more efficiently, the polymerization polymerization liquid crystal composition of the present invention is generally described as a polymerization initiator, which is described later in the following. A polymerization initiator for the project "Liquid to the molecule". 〇❹ In the polymerizable liquid crystal composition of the present invention, the polymerization initiator is blended at a ratio of 1 to 30 parts by weight, preferably 〇.5, based on 1 part by weight of the polymerizable liquid crystal compound. ~(4) The amount of the liquid crystal composition is the same as that of the present month. For the purpose of adjustment, it is preferable to practice the surfactant. The tension & 舌 is the interface/tongue agent, but it is usually a nonionic surfactant. =, non-ionic W-surface activity (4) 钱 钱 钱 , , , , , , , , , , , , , , , 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非Wait. In the polymerizable liquid crystal composition of the present month, the surfactant is usually used in combination with the polymerizable liquid crystal. It is 10 parts by weight, preferably. . 2 parts by weight.丨~ ^ can be used in addition to the above-mentioned components in addition to the above-mentioned components, in the case where the polymerizable liquid crystal composition of the present invention is used for the use of a polarizing film or a raw material for a polarizing film, a printing ink, a paint, a protective film, or the like After the training, other copolymerizable monomers, metals, metal compounds, materials: materials, work materials, light filling materials, bridges, thixotropic agents, gelation / 2209-10153 -pf 39 200946649 Other additives such as polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide. In the polymerizable liquid crystal composition of the present invention, the ratio of the other additives is usually from 1 to 20 parts by weight based on the weight of the polymerizable liquid crystal compound i 。. φ φ The polymerizable liquid crystal composition of the present invention can be usually determined by the polymerizable liquid crystal compound, the polymerizable compound of the present invention, the photopolymerization initiator diionic surfactant, and other additives as required. It is prepared by dissolving in an appropriate organic solvent. Examples of the organic solvent used include ketones such as cyclopentanone, cyclohexanone, and mercaptohexanone; acetates such as butyl acetate and valeric acetate: methane, dichloromethane, and di-ethane The content of the polymerizable liquid crystal obtained as described above is useful as a color-changing liquid crystal layer or a color-changing liquid crystalline high-concentration raw material as described later. I. 3) Liquid crystalline polymer The third embodiment of the present invention is a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention. - Here, the term "polymerization" means a chemical reaction having a broad meaning including a crosslinking reaction, in addition to the usual polymerization reaction. The liquid crystalline polymer of the present invention is (1) a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention, or (2) a polymerizable liquid crystal composition of the present invention having a high liquid crystal property.

2209-10153-PF 40 200946649 Molecule. High liquid crystallinity (1) Polymerization of the polyromatic human I of the present invention, yongkouwang, and a night crystal compound to obtain a molecule as a poly. The liquid crystalline polymer obtained by the polymerizable liquid crystal compound of the present invention is a homopolymer of the polymerizable liquid crystal compound of the present invention, a copolymer composed of two or more kinds of the polyoral liquid crystal compounds of the present month, and the present month. The polynuclear liquid crystal compound and other polymerizable liquid crystal compound 、 、 ', a copolymer of the polymerizable liquid crystal compound of the present invention and another copolymerizable monomer, and the like. Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. 2(10)2—Nove (10), JP-A-2002-308832, 曰本特开2〇〇2—26542ι, Japanese Unexamined 62—〇7〇4〇6, Japan A polymerizable liquid crystal compound described in, for example, Japanese Patent Publication No. 00575. As the other copolymerizable single system, there is no stipulation, for example, 4-(2-f-propenyl hydrazide hydroxyethyl oxide) benzoic acid-4, methoxyphenyl, 4-(6-A Acrylhydrazine is hexyl oxidized) benzoic acid biphenyl, 4-(2-propenylhydrazino hydroxyethyl oxide) benzoic acid-4,-cyanobiphenyl, 4-(2-methylpropene hydroxyethyl) Oxidation) benzoic acid-4'-cyanobiphenyl, 4-(2-f-propyl propylene oxide) benzoic acid-3' '4'-difluorophenyl, 4-(2-methylpropene)醯 hydroxyethyl oxide) benzoic acid naphthyl, 4-propenyl fluorenyl-4, a fluorenyl 2209-10153-PF 41 200946649 biphenyl, 4-propenyl fluorenyl-4,-cyanobiphenyl, Propylene oxime is oxidized by ethyl) 1,-cyanobiphenyl, (2~~ propyl oxime via ethyl oxy)-methoxybiphenyl, nail: propylene oxime via ethyl oxyhydroxide) - 4 ' _ (4" - fluorinated oxy-oxidation): conjugated base, 4 propylene saponin #; _ thiol emulsification _ 4' monopropyl cyclohexyl phenyl, 4~ methacryl oxime 4' Ding | β, base two children's base '4 - C-women ——, — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Benzoic acid (4-pentyl basic), 4-(2-propenylhydroxyethyl)benzoic acid (4-", monopropylcyclohexyl)phenyl), etc. The liquid crystalline polymer of the present invention is The polymerizable liquid crystal of the present invention describes other polymerizable liquid crystal compounds or other copolymerizable ones.

Grass (in the following, gland, gentleman L

The content of the polymerizable liquid crystal compound of the present invention is not particularly limited in the state of the polymer of the NV unit such as the other polymerizable liquid crystal compound, but it is preferable to use the composition in the early position. The rabbit ς η ρ .. on '&quot;, I I above, more preferably 70% by weight, if the 疋 position is in this range, then the liquid crystal polymer's glass transition temperature (change it ^ In the case of the film hardness of the scent, it is desirable to carry out the conversion. The polymerizable liquid crystal compound of the month and the (co)polymerization system such as the 液晶-5 liquid crystal compound which is used in combination with the need thereof are carried out, In the presence of a hydrazine initiator, the ratio of use as a polymerization initiator, and the ratio of the same as that of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition. 2209-10153-ρρ 42 200946649 The polymerization initiator can be used by being selected in accordance with the type of the polymerizable group of the poly-amplified liquid crystal compound to be used. For example, if the polymerizable group is radically polymerizable In the case of an anionic polymerizable group, a radical polymerization initiator is used, and if it is a cationic polymerizable group, a cationic polymerization initiator is used. Any one of the radical 产生 radical generating agent and the photo radical generating agent may be used as the agent, but a photoradical generating agent is suitably used. As a series of the above-mentioned photoradical generating agent, the benzoin methyl group Stupid cause of ether and benzoin propyl ether; acetamidine, 2 _ -2-phenyl acetophenone, 2, 2 bis ethoxy-2] dimethoxy fluorene 2 Toluene, 1,1 -dicyclohexamethylenebenzene, 1-hydroxycyclohexyl phenyl ketone, 2~subunit mono-(methylthio)phenyl]-2-morpholine-propion-formin , N-dimethylamino acetophenone benzene, etc.; 2-methyl onion, i-chlorine, and 2-pentyl hydrazine; 2,4-dimethylthiophene Ketone, 2, indenyl 2-thioxanthone, 2-chlorothioxan a and thioxanthone such as 2,4-diisopropylthioxanthene; acetophenone ketal and segment Dimethyl a ketal such as a ketal; a benzophenone, a methyl benzophenone, a 4,4-dichlorobenzophenone, a 4, 4-diethylaminobenzophenone, a rice bran g And a benzophenone such as 4-benzoquinone-4-methyl-phenyl sulfide; a specific example series of methyl benzoquinone such as 2, 4 6 phenylphosphine oxide as a photoradical polymerization initiator; Trade name: Specialty Chemicals: "rgacure 9〇7, trade name: Irgacure 184, trade name: Irgacure 369 and 2209-10153-PF 43 200946649 Trade name · Irgacure 651, etc. Specific examples of the above-mentioned anionic surfactants include a polyfunctional initiator such as a monolithium salt such as a biphenyl group or a monolithium salt such as naphthyl or naphthalene. The specific examples of the cation polymerization initiators are citrate, dish acid, perchloric acid, trifluoromethane (tetra), etc.; tri-sharpening ^ ❹ = Ming, tetrachlorination A Lewis acid of titanium or tin tetrachloride; a combination of an aromatic aromatic rust salt and a reducing agent. 4 These polymerization initiators may be used singly or in combination. In addition, when the (co)polymerization of the above-mentioned polymerizable liquid crystal compound and other polymerizable liquid crystal compound to be used as needed is carried out, an ultraviolet absorber or an infrared absorber inhibitor may be added as needed. Functional compounds such as those. The liquid crystalline polymer of the invention may be more specifically used in the presence of a polymerization initiator in the presence of a polymerization initiator in a suitable organic solvent, and the polymerizable liquid crystal compound may be used as needed. (co)polymerization method of other polymerizable liquid crystal compound or the like; (1) polymerization polymerization liquid crystal compound and other polymerizable liquid crystal compound to be used in combination with a conventional coating method, and polymerization initiation The first agent is dissolved in a solution of an organic solvent, and after being applied onto a support, the solvent is removed in a state of being removed, and then heated or irradiated (manufactured by a method of ray irradiation). The organic solvent used in the method of the above (A) is not particularly limited if it is inert 2209-10153-Pf 44 200946649 &amp; ^, and the aromatic hydrocarbons such as toluene are listed as examples; Stupid, uniform ternary; butyl acetate, pentyl oxime, thiol ethyl ketone, etc. such as ethyl bromide, such as ethyl chloroform, dichloroethane, etc.; , difuran, tetrahydropyridinium π Isochemical t, % amyl methyl ether, tetrahydroglycol scorpion 箄. gp handleability is good, so that in these, it is more desirable to be 60~l5tc 6〇~2 grab, _ in the polymerization conditions described by (a), t, + +:: should be the next example, according to the latter liquid, to isolate the target to dissolve the polymerization reaction In a suitable organic solvent, the liquid crystallinity of the peri-week/separation is highly distributed on a suitable support to obtain a smectic liquid, and after drying the solution for liquid crystal temperature or higher, it is heated to a display for dissolution. The liquid crystalline polymer is in the m state. The organic solvent is ketone ethyl ketone, methyl isobutyl 8 , cyclopentanyl, and cyclic ketone; butyl acetate, amyl acetate, etc. Is a solvent of solvazine; a toothed hydrocarbon solvent such as dichlorodioxane or dichloroethane -: 吼口南, 1,2-di-oxyl morphine, ^匕夫南, 四风化, etc. The scale is a solvent, etc., and the sulfonyl-l-ether ether is used as the aforementioned support system, whether organic or inorganic, and mussels. A substrate for the substrate is a dihydrocarbon (for example, ΖΕΌΝΕΧ, ZE0N0R (registered quot; ^ ^ + poly olefin), ΖΕΟΝ 1 1, Λ _ (registered trademark, · company h and position ( Registration ^Mitsui Chemical Co., Ltd.)], Polyethylene to Stupid - Shangyu' Benzoate, Polycarbonate, 2209-J0253-PF 45 200946649 Polyimine, Polyamide, Polymethylmethacrylate Ethylene, polytetraethylene, cellulose, cellulose triacetate, polychlorinated glass, calcite, Λ-^, dream, calculus, as the shape of the substrate, except for having a curved surface. It can also reflect the anti-reflection function and the reflection function. ^Electrode layer, as liquid crystal (four) w (four) cloth is cut into the square to use the conventional method, the enumeration method is ❹ ❹ 滚筒 Roll coating method, spin coating method, dipping coating two:: pressure coating method, shot coating method , sliding (four) method, printing::::: bar coating method, mouth as the method used in the above (B), methyl ethyl ketone, methyl iso- τ Αυ list acetone, solvent; acetic acid butyl vinegar, B _ (cyclo) ketone, etc. (4) Chloroquinone, II I solvent; dichloromethane 'Sanhua 吼 q q'2-dimethoxy, / weathered 吱, tetrahydrogen ethane, 1,4~2 Oxane, ether-specific ether solvent, and the like.戍基曱基 As a support system for ❹, there is no special job, but for example, this spoon is used to coat the liquid crystal polymer. In addition, in the method of the above (B), the method for the polymerization reaction is not particularly limited, and a conventional method can be used, for example, as the liquid crystal ancient workmanship, 4 and the day 〗 〖Study of the molecular solution of the molecule on the support on the support series is the same as the column reporter. Preferably, the method of the second (B) is directed to the polymerization of the attacking compound on the support. The method of the above-mentioned polymerizable liquid crystal compound is 2209-10153-pf 46 200946649. For example, in the prior art, the method of applying the treatment to the support is used as a series of methods for performing the orientation treatment on the support. The liquid crystal alignment layer formed by the polyimide-based oriented film or the polyethylene-baked alcohol-based oriented film is placed on the support, and the method of friction research is performed: in the support body, the coffee is obliquely steamed. It is formed by plating: it is an organic film having a functional group in which a dimerization reaction is carried out, or a method having a functional group which is optically asymmetrical, and a method of irradiating a polarized light or a non-biased light. The polymerization method of the polymerizable liquid/ruthenium compound can be obtained by molecularly polymerizing the polymerizable liquid crystal composition of the present invention according to the polymerization reaction conditions described later, and the liquid crystal property can be high by the polymerization initiator. In the presence of the liquid crystal composition of the present invention, the liquid crystal polymer of the present invention is obtained by polymerizing the liquid crystal composition of the present invention, and the liquid crystal polymer of the present invention is obtained. Efficiently enter the "reverse; ^ view from the more ..., & should be the point of view' is best to use before = starter, especially photopolymerization initiator and package:: polymerized liquid crystal In the following, the form of such a polymerizable liquid crystal composition will be described. The properties can be obtained by, for example, the directional liquid obtained by the method of directional treatment. The composition of the present invention is coated with the polymer of the present invention, and the polymerized liquid crystal compound in the composition of the poly(m). The liquid crystal ancient eight-knife of the present invention can be used as a support system.

2209-10153-PF 47 200946649. Your month 1J trace _ ^ 7-like evil, therefore, in the net to give the twisted nematic used in the hanging 彳% ^ a UWJ 7L pieces or super twist (STN) components of the pre-tilt angle of the β-amine When used, the orientation state of the polymerizable liquid crystal compound can be easily controlled. In the state in which the support having the orientation function contacts the liquid crystal composition, the liquid crystal compound is in the direction of the support 矣% and the charge, along the direction of the orientation treatment of the support ❹, Lieutenant, Liuyi / Α ^ Wood into the book. The liquid crystal compound is oriented horizontally on the surface of the support or oriented obliquely or vertically because the effect on the orientation treatment of the support surface becomes large. For example, if used in planar wide-angle exchange (lps) In the case where the alignment film having a very small pretilt angle of the liquid crystal display is provided on the support, a polymerizable liquid crystal layer which is oriented almost horizontally is obtained. Further, in the alignment film used for the TN type liquid crystal display element, the state of being applied to the support is obtained, and a polymerizable liquid crystal layer having a slightly inclined orientation is obtained when the alignment film for the liquid crystal display element of the STN mode is used. A polymerizable liquid crystal layer having a substantially oblique orientation is obtained. Further, when the polymerizable liquid crystal composition of the present invention is brought into contact with a support body having a horizontal orientation function having a pretilt angle, it is obtained to change the same or continuously from the surface of the support body to the vicinity of the air interface. The angle is used to perform an obliquely oriented optical anisotropy. Further, 'if an organic thin film having a functional group for photodimerization in a molecule or a functional group having a functional group which is heterogenized by light is used, 2209-10153-pf 48 200946649 organic film (hereinafter, simply referred to as "light orientation" When the film is irradiated with a polarized light or a non-polarized light (photo-alignment method), a substrate in which regions in different orientation directions are distributed in a pattern can be produced. First, on the support on which the photo-alignment film is disposed, light having a wavelength at the absorption band of the photo-alignment film is irradiated to prepare a support of the same orientation. Then, in the support, covering the mask, starting from the top of the mask, illuminating the light different from the state of the ith illumination at the absorption wavelength of the photo-alignment film, such as light of a different polarization state or It is a light in which the irradiation angle and the direction are different, 'only in the irradiated portion, and has an orientation function different from the portion obtained by the first irradiation. In the case where the support which is distributed in a pattern in which the orientation function is distributed in a pattern as described above does not contact the polymerizable liquid crystal composition, it is distributed in a pattern like the fixed gate entanglement of the support. The direction of the direction. If you take a person to take a ^ ^ 木 木 木 木 木 木 木 木 木 木 木 木 木 木 木 木 木 木 。 。 。 。 。 。 。 。 。 。 / The liquid crystal polymer having a slanting pattern can be obtained as a support body of the other right I if it is a rectangular body having a substantially horizontal orientation t of a region in which the pattern is distributed in a different direction. The foregoing supports a retardation film. Liquid crystal polymer film, in addition, as an orientation pattern

(Atomic Force Microscopy) Α '' can also be used: AFM • ^ stylus to the method; and, etched Opal Dragon '疋 to the film for friction grinding. The method of the method of living body cage + Τ m; however, the method of using light ~ Zuo Temple does not use light to direct 臈 膜 ° membrane is simple and ideal.

2209-10153-PF 49 200946649 乍The coating of the polymerizable liquid crystal composition of the present invention is applied to the support. The coating, the roller coating, and the gravure printing are: two-shot coating, die coating, A cover cloth coating method, a dipping method, and the like. At this time, in order to improve the coatability, the second:: polymerizable liquid crystal composition 'Adds a conventionally used organic solvent. Preferably, the polymerizable liquid crystal composition of the present invention is applied to a support, and W, , and the organic solvent are removed by natural drying, heat drying, dry-pressure dry welding, heat drying under reduced pressure, and the like. . Fortunately, after coating, it is preferable to uniformly fix the liquid crystal compound in the polymerizable liquid crystal composition of the present invention in a state in which the color changing layer is maintained. Specifically, the heat treatment for promoting the orientation of the liquid crystal can be performed. Further, the orientation is promoted. ❹ As a heat treatment method, for example, after the polymerizable liquid crystal composition of the present invention/soil is placed on a support, 'heating to the liquid phase of the liquid crystal composition】-N (nematic phase) transfer temperature (In the following, simply referred to as "(i) transfer temperature"), the polymerizable liquid crystal composition is in a liquid crystal phase or an iso-phase liquid state. From this point on, the gradual cooling is carried out in accordance with the need, and the discoloration phase is found. At this time, it is preferable to sufficiently grow the liquid crystal phase region once it is maintained at the temperature at which the liquid crystal phase is present, and it becomes a single region. Further, after the polymerizable liquid crystal composition of the invention is applied to the support, the heat treatment for maintaining the temperature for a predetermined period of time can be carried out within the temperature range in which the color-changing layer of the polymerizable liquid crystal composition of the present invention is found. When the heating temperature is excessively high, it may cause deterioration due to polymerization reaction which is not suitable for the polymerizable liquid crystal compound. Further, in the excessive cooling 2209-10153-PF 50 200946649, the secondary liquid crystal composition causes phase separation, It was found that the precipitation of crystals and the phase-order liquid crystal phase of one phase were impossible, and orientation treatment was impossible. By performing such heat treatment, C i is a homogeneous liquid crystal polymer film having less orientation defects than coating by simple application. A Π Π ' can be made by homogenizing the directional treatment like this, the miscellaneous 曰 "the lowest temperature that does not cause phase separation, that is, become too cold, the heart: stop at this temperature to align the liquid crystal phase In the state of 'polymerization ❹ 仵 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶The method or the heat polymerization is preferably a method of activating the energy ray after the anti-syntax is performed at room temperature. Even if it is a name and is completed by 耵w 疋 in /, it is easy to operate, Therefore, it is preferable to irradiate light such as an ultraviolet ray. The temperature at the time of irradiation is such that the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention can maintain the temperature of the liquid crystal phase, and in order to avoid the polymerizable liquid crystal compound or the polymerizable liquid crystal. In the excitation of the thermal polymerization of the composition, it is preferable to be 3 cc or less as much as possible. Further, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition is usually in a heating process. (I) transfer start temperature, the N (nematic phase) transition temperature -I (isotropic liquid phase) (below, simply referred to as "Bu! Transition temperature.") Within the range of liquid crystal phase is not significant. On the other hand, in the cooling process, it is thermodynamically non-equilibrium. Therefore, even if it is below the C-N transition temperature, it does not solidify and the liquid state is maintained by 2209-10153-PF 51 200946649. This state is referred to as a supercooled bear. According to the invention, the polymerizable liquid crystal compound or the crystal composition which is in a supercooled state is also contained in a state in which the liquid crystal phase is maintained. The ultraviolet irradiation intensity is usually in the range of 1 w/m 2 to 1 〇 kW / / m 2 , preferably 5 W / m 2 to 2 kW / m 2 . Further, after the material is irradiated with ultraviolet rays to polymerize only a specific portion, and the orientation state 1 of the unpolymerized portion is changed by applying an electric field, a magnetic field, a temperature, or the like, when the unpolymerized portion is polymerized, it is possible to obtain = Liquid crystal 13⁄4 molecular film with a plurality of regions having different orientation directions. In addition, when a portion irradiated with ultraviolet rays is irradiated with a mask, an electric field, a magnetic field, a temperature, or the like is applied to the polymerizable liquid crystal compound liquid crystal composition in an unpolymerized state to restrict the orientation even if the state is maintained. Next, starting directly from the mask, the light is emitted and polymerized, and a liquid crystal polymer film having different orientation directions and a plurality of regions may be obtained. J. The polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the month is obtained, and the right a/曰曰-supplementary molecular system can be peeled off by the support to make ms# 5 * - can be directly removed without being supported by the support. It is used as an optical anisotropy. In particular, the liquid crystal high-concentration early wax β/color liquid crystal film obtained by combining the polymerizable liquid crystal composition of the present invention has an extremely high reflectance, so that σ becomes a polarizer of the liquid crystal display element. . In addition to the ancient 思思思, it is also possible to laminate this liquid by the layering method.

- PF 2209-10153 52 200946649 The selected wavelength is appropriately selected' to obtain a multilayer polarizer covering all the light of the visible spectrum (refer to EP0720041). Further, it is also possible to use a so-called broad-band polarizer instead of the above-mentioned multilayer polarizer in combination with appropriate compounds and processing conditions. As a method for carrying out such a method, for example, the methods described in the introductory manuals of WO 9898/8, 8, EP 0 606 940, GB 231.2529, and the introductory manual of WO 096 / 0 20 16 are exemplified. Further, a color filter may be produced by using the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention. Thus, those skilled in the art can suitably impart the desired wavelength by conventional coating methods. In addition, the thermal discoloration of the color liquid crystal can also be improved. The color of the color changing layer is changed from red to green through the adjustment of the temperature. The mask can be used to define the temperature at a defined temperature. The number average molecular weight of the liquid crystalline polymer of the present invention obtained as described above is preferably 5 GG to - just, more preferably 5, _ 〜 〇〇 000, if the number average molecular weight is in such a range , the film hardness is obtained at a high degree, and the handleability is also good, and m is ideal. The liquid crystal south molecular teaching Pinggu 八 2 x tens of knives can be monodispersed polyphenylene as a standard sample, tetrachloro ^ ^ ^ ^ ^ ^ L 夭 夭 (THF) as a dissolving solution, hunted by gel permeation chromatography (Gpc) (4). The liquid crystalline polymer of this genus speculates that the cross-linking point is uniformly present in the molecule. The polymerization is based on only one person in the Ming and Qing dynasty. / The polymerizable liquid crystal compound of the month is obtained, and the liquid crystal property is obtained. Therefore, the crosslinking efficiency is high and the hardness is good.

2209-10153-PF 53 200946649 The liquid crystalline polymer of the present invention can be used as a phase difference plate or a liquid crystal display element by utilizing the orientation property and the anisotropy of the physical properties such as the refractive index, the dielectric constant, and the magnetic susceptibility. A constituent material of an optical anisotropic body such as a film, a polarizing plate, a viewing angle expansion plate, a color filter, a low-pass filter, a light polarizing plate, and various optical filters. 4) Optically anisotropic body The fourth aspect of the present invention is a liquid crystal polymer of the present invention as an optical anisotropy of a constituent material. Examples of the optically anisotropic system of the present invention include a phase difference plate, an alignment film for a liquid crystal display element, a polarizing plate, a viewing angle expansion plate, a color filter, a light sheet, a low-pass filter, a photo-polarizer, various light-emitting sheets, and the like. . The optically-isotropic system of the present invention is obtained by polymerizing the polymerizable liquid crystal material of the present invention to form a liquid crystalline polymer as a constituent material, and therefore has uniform and high-quality liquid crystal orientation. [Embodiment] The manufacturing method of the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, "weight injury" and "%" are not specifically stated, and they all represent weight. (Example 1) Synthesis of Compound 1

2209-10153-PF 54 200946649

HO

^o OH

(Intermediate A) In 2,5-di-based benzoic acid 4 (1 6.1111110丨) and propylene 2 per base ethyl 9.04g (77.9mmol) dissolved in tetrahydrogenethane (in the following ' Referred to as "THF".) 50ml solution, at room temperature, added dicyclohexylcarbodiimide 6. 69g (32. 4mmo 1 ) dissolved in THF 70ml o

The solution was stirred for 5 hours. The reaction solution was filtered with a fluorite, and the filtrate was concentrated by a rotary evaporator to obtain a crude chromatograph as a viscous, colorless oil (toluene: acetic acid B was obtained as a viscous material-free product 18.94 g. 2_95 g of Intermediate A of this color oil was refined by cerium oxide gel column ester = 80:20 (volume ratio). (Good yield: 45%) (1H-NMR spectrum data of Intermediate A) 'H-NMR (400 MHz, CDCla, TMS, d Dditi λ. n ypm) . 9. 969 ( s, 1H), 7. 272 ( d,1H,J = 3. 0Hz), 7 022 Γ u “ Ud,1H,j = 3. 〇,

9.2 Hz), 6.877 (d, 1H, J = 9 Hz), 6.450 (d T u' 1H, J = 17. 2 Hz), 6. 150 ( dd, 1H, J = 10. 4, 17. 2 Hz ) , U8 〇( d,1H, J = 10.4Hz), 5.316 (br,1H), 4.599-4 sncw b09 ( m,4H) (Step 2) Synthesis of Intermediate B

(Intermediate B) 2209-10153-PF 55 200946649 1. In the intermediate A 1. 50g f β ηηι , ν , g C 6.0 difficult ο1) , 4 - carbaryl anti-rolling acid 2. 68g ( 17. 9ππηο1 ) 4 — — ^ — Τ 胺 amine.定Μ? (6.0 龙〇1) dissolved in THF 3 〇ml of dissolved tons

For an I-shirt, add W-methylaminopropyl-anthracene--"A soil-anaerobic diimine hydrochloride 2 U5.0 face D, and mix the whole volume for 5 hours. The organic layer was dried by washing with water and salt water, and the organic layer was dried by a rotary evaporator to obtain a viscous colorless oil intermediate B.仃d

The product 5 RR was purified by ruthenium dioxide gel column chromatography (M.K. ethyl ester = 90:1 product ratio) to obtain a helmet (body 1.44g (good product) The rate of 47%). The title of β (the intermediate Β1Η - NMR spectrum data) NMR (400MHz, CDCh, TMS λ, d just): 10. u 2Η), 8. 045 (d, 2Η, J = 8. 4 Hz), 8. 39 〇 [ η CS, . v α, 2H, J = gx 8. 053 ( d, 2H, J = 8.4 Hz) &gt; 8. 〇 5l ( d 0lI Hz), 5 2H, J = 8_ 4n 8- 〇ll( d, 1H, J = 2. 8Hz) &gt; 7. 544( dd m T ), ,! H, J = 2. 8,8 rti 7- 339 ( d, 1H, J = 8. 8Hz) ^ 6. 376 ( h ln · flz), v α» 1H, J = i7 6. 040 ( dd, 1H , J:10·4,17. 2Hz ), ), 5.810 ( j 288 ( 2H, J = l〇. 4Hz), 4. 450 ( t, 2H, J = 7· 〇Hz) ^ 5 J = 7. 0 Hz) · (Step 3) Synthesis of Intermediate C (Step 3-1) Synthesis of Intermediate D 2209-10153-pf 56 200946649

VT compartment D) (In the chemical formula, 4 士, you mean 1: monobutyl fluorenyl decyl. The same is true below.) At the temperature, 4, 'butyl dimethyl fluorenyl methacrylate benzene Methanol ❹ ❾ 2. 64g (11, lmninl n ethanol 30ml solution, drip to hydrazine hydrate 2·8〇g (55., ) ethanol 3〇mi solution. After the end of the drop, stir at room temperature for 3 hours After the ' Μ rotary evaporator, to concentrate the reaction solution, after removing the ethanol and excess hydrate, the residue is dissolved in 3 0 Om 1 trichloromethane, to the rest An aqueous solution of hydrogen is used for washing. In the organic layer, triethylamine is added, and after being dried by a flash of magnesium sulfate, the mixture is condensed by a shovel and then concentrated. It becomes the middle of the viscous brown oil n # ^ . The crude birth is 3. 06g. The rough product is not refined into the lamp, and is supplied to the next step 2-3. (Step 2-3) Intermediate c Synthesis

Om (Intermediate C) In the middle of the boat obtained in step 2, 9.6 Β 3 3. 06 §, at room temperature, the solution of the intermediate 乙心^ which is extended in step 3-1 is Μ hg ( 2·8,) Dissolve in the sputum, and stir at the same temperature for one night.

2209-10153-PF 57

200946649 After concentrating the reaction solution with a rotary evaporator, the solution was diluted with 5 〇〇ml of ethyl acetate, and washed with 50 ml of water followed by 5 〇 ml of saturated plate water. After drying the organic layer with magnesium sulfate anhydride, it was concentrated by a rotary evaporator to obtain a pale yellow oil (5 g). This was purified by silica gel column chromatography (toluene: ethyl acetate = 95:5 (volume ratio)) to obtain the intermediate of the viscous pale yellow oil. 〇4g (good yield 38%) . (NMR Spectra of Intermediate C) Ή-NMR (400 MHz, CDCls, TMS, δ ppm): 8. 717 (s, 2H), 8. 658 (s, 2H), 8. 288 (d, 4H, J = 8' 4Hz), 8. 005 —7.990 (m,5H), 7.770 (d,4H,J = 8.4Hz), 7.551 (d, 1H' J = 8. 4Hz) ' 7. 340 ( d,1H, J = 8. 4Hz), 6. 927 ( d,4H, J = 8. 4Hz), 6. 3 78 ( d,1H, J = 17. 2Hz), 6. 〇41 ( dd' 1H' J = l 〇.4,17.2Hz), 5.809 (d,1H' J=l〇-4Hz), 4.449 (t,2H, J = 7.0Hz), 4.289 (t,2H,J = 7.〇Hz), 1.026 ( s, 18H), 0. 256 (s, 12H), (Step 4) Synthesis of Compound 1 (Step 4-1) Synthesis of Intermediate E

(1. 4mm (1. 4mm〇1) The solution of the succinic acid mono(2-propenylhydroxyethyl) hydrazine. 58g (2.7 〇 1) dissolved in toluene 5ml, at room temperature, drip 1. 7g ( 13. 4mm〇1 2209-10153-PF 58 200946649 The gasification grasshopper, at the same temperature, compensated for 3 hours. Cry in % vol.

For the reaction liquid, the wall is willing to enter the wall, the song w TO 仃 仃 仃 , , , , , , , , , , , 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及Product 〇. 6 This system is not refined, for the library in the moon clothing should be in the next step 2. (Step 4-2) Synthesis of the compound

D0~丫Ο ❹ (Compound 1) In the intermediate C 1 · ( 1. lmmol ) dissolved in THF of 1 〇mi solution 'at room temperature, drop fluorinated tetra-n- τ group according to lm〇l / L Then, the solution 3.0 ml 'stirred at the same temperature for 15 minutes. Next, at room temperature, the intermediate E t G. 68 g obtained in the step 4-1 was dissolved in a solution of 10 ml, and stirred at the same temperature for 3 minutes. The reaction solution was diluted with ethyl acetate, and washed with 5 mL of water and then 5 mL of brine. After drying the organic layer with magnesium sulfate, it was concentrated with a rotary evaporator to afford 2.21 g of pale yellow oil. This was purified by silica gel column chromatography (toluene: acetic acid BS| = 9G: 1G (volume ratio)) to obtain 478 img (yield rate 54%) of compound i which became a pale yellow solid. (1 Η NMR spectrum data of compound 1) !H-NMR (400 MHz, CDCla, TMS, 5 ppm): 8.714 (s, 2H), 8.675 (s, 2H), 8.291 (d, 4H, &gt; 6·8 Hz ), 7.988 (m, 5H), · 7.890 ((1,4H, J = 8.0Hz), 7.548 (d' 1H, 2209'10153-pp 59 200946649 J = 8. 4Hz), 7. 354 ( dd ,1H,J = 8· 4,13· 4Hz), 7. 223 ( d, 4H, J = 8.8Hz) ' 6. 458 - 6. 414 ( m, 3H) ' 6.1 65 - 6.009 (m, 3H) , 5.866 — 5.799 (m, 3H), 4.447- 4.278 (m, 12H) ' 2.925 (t, 4H, J = 6.4Hz) ' 2. 798 ( t, 4H, J = 6.4Hz) (Example 2) Compound Synthesis of 2

(Compound 2) 〇 (Step 1) Synthesis of Intermediate F

(Intermediate F) Except for the synthesis of the intermediate A in Example 1, the 2-ethyl hydroxyethyl acrylate was changed to be ethylene glycol mono-n-propyl ether, and the other was the same as the intermediate of Example 1. Intermediate F was synthesized in the same manner as in the synthesis (good yield 40%). (1H of the intermediate F - 匪R spectrum data) Ή-NMR (400MHz, CDCh, TMS, (5 ppm): 10. 210 (s, lH), 7.292 (d, lH, J = 2.8Hz), 6.984 ( Dd,lH,J = 2_8, 8.8Hz), 6.835 (d,1H, J = 8.8Hz), 5.827 (br, 1H), 4.481 (t, 2H, J = 4.8Hz) ' 3. 793 ( t, 2H , J = 4.8Hz) &gt; 3. 514 ( t, 2H, J = 6. 8Hz), 1. 6 73 — 1. 6 20 ( m, 2H), 0· 940 2209-10153-PF 60 200946649 (t , 3H, J = 7.4Hz) (Step 2) Synthesis of Intermediate G

In the same manner as in the synthesis of the intermediate B of Example 1, the intermediate G was synthesized in the same manner as the intermediate F (yield rate: 54%). (Intermediate G 4 NMR spectroscopy data) - ]H-NMR (400 MHz, CDCh, TMS, 5 ppm): 10. 166 (s, 1H) ' 10. 160 (s, 1H) ' 8. 047 (d , 2H, J = 8. 4Hz) ' 8. 385 (d, 2H, J = 8.4Hz) ' 8.056 (d, 2H, J = 8.4Hz) &gt;8.049 (d, 2H, J = 8.4Hz) ' 8.005 (d, 1H, J = 2.8Hz) '7.545 (dd, 1H, J = 2.8, 8.8Hz) ' 7. 340 ( d, 1H, J = 8.8Hz) ' ® 4.343 (t, 2H, J = 4.8Hz ) ' 3. 559 ( t, 2H, J = 4.8Hz) ' 3. 292 ( t, 2H, J = 6. 4Hz), 1. 564 — 1. 475 ( m,2H), 0. 8 78 (t , 3H, J = 6.4Hz) (Step 3) Synthesis of Intermediate H

(intermediate Η)

O-TBS 2209-10153-PF 61 200946649 What is the intermediate in Example 1. Synthesis, change intermediate B, and become intermediate G, +. In the same manner as in the synthesis, the intermediate of the example 1 was used to synthesize the intermediate Η (good yield 41%). (1H - NMR spectroscopy of the intermediate )) ^ Surface (_Hz, CDCl3'TMs, 5 ppm ) : 8 7i6(s, 2H), U59(S, 2H), 8 32q—8·27 (^, eg, 8 〇〇ι 7. 981 ( m, 5H) ' 7. 7 69 ( d, 4H, J = 8. 6Hz) &gt; 7. 5 32 ( dd, ❹ 1H, &gt; 2.8, 8, 4Hz), 7 328 (d, ih, Η.·), 6 926 U, 4H,] = δ·6Ηζ ), 4.344 (t, 2H, J = 4.8Hz), 3.532 (t, 2H, J = 4.8Hz) ^ 3.275 ( 1, 2H, J = 7.0Hz) '1.563 - 1.473 (ffl) 2H) . 1.004 (S , l8H) ^ 〇. 860 ( t, 3H, J: 7. 4Hz) ' 〇. 248 ( s,12H)

(Step 4) Synthesis of Compound 2

(Compound 2) In addition to the synthesis of the compound 1 of Example 1, the intermediate C was changed to be the intermediate oxime, and the compound 2 was synthesized by the same method as the synthesis of the compound 1 of Example 1. β 4 % ). (沱NMR spectroscopy data for Compound 2) Ή-NMR (400 MHz, CDCh, TMS, 5 ppm): 8. 719 ( s, 2H) &gt; 8.680 (s, 2H) ' 8. 288 ( d, 4H, J = 6. 8Hz ) '8.005 (m, 5H), 7.890 (d, 4H, J = 8.0Hz), 7.528 (d, 1H, 2209-10153—pf 62

I 200946649 J = 8· 6Hz ), 7. 362 ( dd, 1H, J = 8. 6, l 3. 2Hz ), 7· 223 ( d, 4H, J = 8.8Hz), 6.498 (d, 2H, J = 17.2Hz), 6.131 (dd, 2H, J = 10.4, 17.2Hz), 5.858 (d, 2H, J = i〇.4Hz), 4.390 (s, 1 0H ), 3_ 536 ( t, 2H, J = 5·0Hz ), 3 278 ( 1: 2H J = 6.8Hz), 2. 926 ( t, 4H, J = 6. 4Hz), 2·793 (t, 4H, J = 6.4Hz), l_606 — 1.529 ( m, 2H), 0.890 (t, 3H, J = 7.4 Hz) &lt;Evaluation of compound&gt; 0 (1) Measurement of phase transition temperature The compound 1, 2 (test compound) 丨〇mg was separately measured to remain solid. The shape 13⁄4' was directly sandwiched between two glass substrates with a polyimide film oriented film which had been subjected to abrasive rubbing treatment. The substrate was heated on a hot plate and then cooled down to 3 Torr after starting from 30 ° C to 250 ° C. Oh, so far. The change in the structure of the structure at the time of temperature rise and temperature reduction was observed by a polarizing optical microscope (manufactured by Nikon Corporation, ECLIPSE LV1 00 P0L type). The measured phase transfer temperature is shown in Table 1. ® In Table 1, "C" indicates Crystal (crystal), "n" indicates Nematic, and "I" indicates Isotropic (isotropic). Here, 'Crysta 1 (crystal) means that the test compound becomes a solid phase, and Nematic (nematic) means that the test compound becomes a nematic liquid crystal phase, and Isotropic (isotropic) means that the test compound becomes an isotropic liquid phase. . (2) Measurement of optical anisotropy (Δn value) Each of 10 parts by weight of Compounds 1 and 2 was dissolved in 2 3 3 parts by weight of cyclopentanone to form a solution. In this case, a solution prepared by dissolving 2·7 parts by weight of 2209-10153-PF 63 200946649 photopolymerization initiator (Ig. Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to the liquid crystal compound. After coating a prepared solution on a glass substrate having a polyvinyl alcohol film subjected to a rubbing treatment, a bar coater (barperer R〇d Ν〇. 4, shaft diameter: 12.7 mm) was applied thereto. Dry on a hot plate for 2 minutes at 〇〇C. The obtained film is irradiated with a mercury lamp equivalent

紫外线 7〇〇mJ/cm2 of ultraviolet light to obtain a polymer cured film of thickness. With respect to the cured film, a turbulent flow (Re) having a wavelength of 545.3 nm was measured using an ellipsometer (J. 〇〇·W〇〇Uam &amp; 司, model -100). Then, from the film thickness (d) of the liquid crystal layer obtained separately, Δη is obtained by the calculation formula Δn = Re / d. The results of the heterogeneous results are shown in Table 1. (3) Formation of color-changing layer One part by weight of the compound 1 and 2 was dissolved in the cyclopentanone 153 parts to form a solution. In this 'modulation addition photopolymerization initiator ((3) Specialty Cheinicals, Inc.: !rgacure i9i9) &: parts, chelating agent 6.0 parts by weight, and surfactant (used as &quot;% by weight of cyclopentanone solution) U. 6 parts by weight of the solution to be dissolved. In order to make the KH-4G (SEIMI c leg ic / system) # as a chelating agent, the 1 ^ thing represented by the above chemical formula (1) is used as a surfactant, and is accompanied by a grinding and rubbing treatment. Imine; • After applying the bar solution to the glass substrate of the film (7 industry, system: wide - 203 - coffee, "..8, shaft diameter 12.7") On the 埶 埶 μ μ ^ 热 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 9-1〇i53—pF 64 200946649 Line, get the thickness of 4&quot;m hardened film. =Use the first photometer (made by Dairy Electronics Co., Ltd., instant MCPD-3000) and just pass the sacred pre-hardened film.光雄. 2 is the area where the test compound is obtained.)::: Selective reflection region (transmission rate becomes 50% to exhaust. It is known to form a color-changing layer. The width of the region is approximately the result of the measurement. It is shown in Table Ϊ ❹ ❹ (3) Solubility The solubility of the compound 2 is evaluated as follows. That is, if the king enters ~ &quot;°王If the solution is obtained, the test compound (compound 1, 2) obtained in an amount of 40% by weight of 裱 〇 、, ^ 裱 裱 酮 溶液 于 于 于 戊 戊 戊 , , , The test compound was dissolved in the form of cyclopentanone, and it was found to be insoluble in the form of oxime, and it was found that the solubility was determined by X. The evaluation results were shown in Table 丄. (4) Evaluation of compatibility The compatibility of the compounds 1 and 2 was evaluated as follows. In other words, the presence or absence of turbidity of the hardening medium of the test compound obtained as described above was observed by visual observation at 23 C ', so that the state in which no turbidity was observed by visual observation became 〇, the state in which turbidity occurs is X and the compatibility is evaluated. The S parity result is shown in the table.

2209-10153-PF 65 200946649 [Table 1] The phase transition temperature of the test compound shows the liquid crystal temperature range. The discoloration layer Δη is dissolved. The soluble compound 1 ------- C 250 ° C or more N -► 1 180 ° Above C, there are 0.143 〇〇 compound 2 ---- CM 25 (TC above 30 ° C below 182 ° C above 0.152 〇〇 is known from Table 1: Compounds 1 and 2 are not only showing the south of the solvent It has good solubility and good compatibility with additives such as a polymerization initiator, a chelating agent, etc., and has a good handling property. Moreover, the cured film system of any of the compounds exhibits good liquid crystallinity in a wide temperature range. The color-changing layer was obtained. The obtained liquid crystal film was used as the liquid crystal compound (Compound 3, manufactured by BASF Corporation). The product name: LC242) was evaluated in the same manner as in the evaluation of the compound 1 and 2, and the method of (1) to (4), and the evaluation results are shown in Table 2. (Comparative Example 2) In addition The phase transition temperature of a conventional pyridazine liquid crystal compound (Compound 4, a compound described in Example 2 of JP-A-147562) is shown in Table 2 of the Japanese Patent Publication No. Hei. No. 147562. 2209-10153-PF 66 200946649 [Table 2] The liquid crystal compound phase transition temperature shows the liquid crystal temperature range. The color change layer Δη solubility compatibility is compared. Comparative Example 1 Compound 3 C 60 ° C t N 123 ° Γ, t I When cooling From I directly to 30 ° C. 63 ° C has 0.100 〇〇 Comparative Example 2 Compound 4 C 57〇CN 116°CI -► -► 59〇C — — — — The structure of compounds 3 and 4 is shown in the following.

(Compound 3) /,, ΙΙ'Ί'ϋΚγ /τ · (Compound 4) ◎ [Industrial Applicability] The polymerizable liquid crystal compound of the present invention exhibits a wide temperature range of a liquid crystal phase, is chemically stable, and can be inexpensive. A liquid crystal material which is manufactured and selectively reflects a wavelength region Λλ, that is, Δη becomes large. According to the polymerizable liquid crystal composition of the present invention, it is possible to form a liquid crystal layer which exhibits a wide temperature range of the liquid crystal phase and which has a wide selective reflection wavelength region Δλ, that is, Δη becomes large. In the liquid crystalline polymer of the present invention, the optical anisotropy 2209-10153-PF 67 200946649 (Δη) is increased, so that it is used as a phase difference plate and orientation for a liquid crystal display element. Membrane, polarizing plate, ray-ray early I 4ι= ^ Λ _ Manufacture of raw materials for optical anisotropy such as wild angle expansion plate, color filter, low-pass filter, optically polarized light, and various light filters. The optically anisotropic system of the present invention is produced by using the polymerizable liquid crystal compound of the present invention. Therefore, it has uniform and high-quality liquid crystal orientation. [Simple description of the diagram] Μ [Description of main components] 益 〇 2209-10153-PF 68

Claims (1)

200946649 X. Patent application scope: 1. A polymeric liquid crystal compound characterized by the following chemical formula (I, Z11 V|~ Gt y Ya~. A, j Y8 〇-.13⁄4-命 [In the formula, M represents an organic group having a carbon number of 1 to ι 饧; γ, 〜I each independently represents one of chemical single bonds, —, _c(=〇) ——〇—c( = ) NR ~c(=〇) —, —(;(=〇)—nr1—, 0—C( =0)~NR1-, — NRl—c( = 〇) — 〇—, — NR1—c (二〇—NR1—or NR1—〇—, where R1 is 〇) ~ NR1-, wind atom or carbon number! ~6 burnt base; Gi and &amp; is an aliphatic group which independently represents a carbon number of 1 to 20 having a substituent, and may be in the aliphatic group, and may be in the group - s - 〇 - c ( = 〇 )___c(= 〇~C(=〇) —nr2 ◦(=〇) —, _ C_(=_°) — NR2---Wing 2- or -C(=〇) _ (However, -〇2 And ~s—except for two or more adjacent states, respectively. Here, the R system represents an atom or an alkyl group having 1 to 6 carbon atoms; Z! and Z2 are independently capable of being replaced by a prime atom. The chain of the Wei 2~10 chain; the Αι knives independently represent the organic base of the carbon number 丨~3〇; I, the knives independently represent the hydrogen source a halogen atom, an alkyl group having a carbon number of 1 to 10, a cyano group, a nitro group, a 〇r3, H (2 2209-10153-PF 69 200946649 0) -R3, -C (= 〇) 0R3, —〇—c ( = 〇) — 〇r3, a nr4 -C(=0) — R3, -C(:=〇) —n(r3)r4 or —〇_c(=〇) N(R R, Here, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and in the state where R3 is an alkyl group, the alkyl group may be in a 0-, -S-- , oc(=〇) _, — - 〇-, - 〇-C ( = 0) - 0-, - NR5-c ( = 0) _, a c Ο ❹ (=0) - NR5-, one NR5 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — &amp;, and c and d are each independently represented by 〇 or 1]. 2. The polymerizable liquid crystal compound according to the ninth aspect of the invention, wherein the lanthanoid group may have a substituent of a phenylene group, a biphenylene group having a substituent, a naphthalene group which may have a substituent or may have a substitution A polymerizable liquid crystal compound according to the first aspect of the invention, wherein the oxime and the oxime 2 are independently CH2==CH-, cH2=c (cH3&gt; CH2=C, respectively. (Cl) - . CH2=CH-CH2~ , CH2^C CCHa)- CH2-, ch2=c (CH3) — cm, (CH3) 2C=CH_CH2 I. CHs — CH= CH- or CHs — CH= Cli2 ~. 4. A polymerizable liquid crystal compound according to the fi range fi, wherein the lanthanoid group may have a substituent phenylene group, and a=d=i, b=c=0, I, Υ3~γ6, ^ system respectively Independently become -C ( = 〇) - 〇0-c( = 0)- or -〇-, g〗 ~g2 are independently - (CH2) 6 - or one (CH2) 4 -, which can be used in these Base, in -1, 2209-10153-PF 7 0 200946649 - C (=0) - 〇 -, 0 - C (= 〇) - or one (; (= q) __, z and z2 are independent The polymer is a CH2=CH-, CH2=c (CH〇~ or CIJ2=C(Cl)-. 5. The polymerizable liquid crystal compound of claim 4, wherein the lanthanide series can have a carbon number of 1 to 1 The hydrocarbon group of hydrazine is substituted for the stupid beauty. It may be in the above hydrocarbon group, in the first one, -C(=〇) 〇-, - 0)- or one C (〒〇)-, Zl and Z2 are all CH2 := CH— 6. As in the patented scope 4, the polymerizable liquid crystal compound, and To replace the phenylene group. The chelating compound polymerized according to any one of items 1 to 6. 7. A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to the application specification and Come as a constituent material. ❹ 2209-10153-PF 71 200946649 VII. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: no flaws. Chemical formula showing the characteristics of the invention: no 2209-10153-PF