JP5407870B2 - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optical anisotropic body - Google Patents

Description

  The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound and a polymerizable chiral compound, a liquid crystal polymer obtained by polymerizing these, and the liquid crystal polymer. The present invention relates to an optical anisotropic body as a material.

  In recent years, a liquid crystal alignment film obtained by aligning a liquid crystal polymer or a liquid crystal compound having a polymerizable functional group has been developed as an optical film such as an optical compensator used for a liquid crystal display. This film has been attracting attention as being capable of realizing a higher degree of orientation, that is, an orientation such as a tilt orientation and a twist orientation, which is impossible with a birefringent film utilizing a polymer film stretching technique.

  Also, cholesteric utilizing the selective reflection characteristics of a liquid crystal alignment film (selective reflection film) obtained by cholesteric alignment of a composition comprising a polymerizable liquid crystal compound such as a liquid crystal polymer or a liquid crystalline (meth) acrylate compound and a chiral compound. Polarizers have also been put into practical use.

  The selective reflection center wavelength λ of the selective reflection characteristic is represented by λ = n × P (where n is an average refractive index and P is a cholesteric pitch). The selective reflection wavelength band Δλ is Δλ = Δn × P, where Δn is (ne−no), ne is an extraordinary refractive index, and no is an ordinary refractive index. ] Is represented. Therefore, in order to widen the selective reflection wavelength band Δλ, a material having Δn, that is, a large optical anisotropy is required.

  Further, in order to use the selective reflection film as a cholesteric polarizer in a liquid crystal display, it is necessary that selective reflection occurs in the visible light region. Usually, the selective reflection wavelength band Δλ in one layer of the selective reflection film is narrower than the visible light region, and therefore a plurality of selective reflection films are laminated in order to widen the selective reflection wavelength band Δλ. Therefore, there is a problem that the selective reflection film using a material having a narrow selective reflection wavelength band Δλ has a large number of laminated layers and low productivity. Therefore, also from this point, a material having a wide selective reflection wavelength band Δλ, that is, a material having a large Δn (polymerizable liquid crystal compound or the like) is required.

  However, any conventionally known polymerizable compound having a large Δn is poor in solubility, coating property, and orientation, and has an orientation that can be used when it cannot be uniformly formed or used. It may be difficult to obtain a reflective film.

  On the other hand, as a liquid crystalline compound, the following formula (1a)

In the formula, Ra represents an alkyl group, and Rb represents an alkyl group, a cyano group, a fluorine atom, a trifluoromethoxy group, or the like.
This compound is an excellent liquid crystal material having characteristics such as a wide temperature range exhibiting a liquid crystal phase, chemical stability and inexpensive production.

  However, these azines are not always satisfactory in compatibility with currently used liquid crystal compounds. In the above formula (1a), the compatibility can be somewhat improved by increasing the number of carbon atoms of the side chain alkyl group, but there is also a problem that the temperature range showing the liquid crystal phase becomes narrow.

  In order to solve such a problem, Patent Document 1 discloses the following formula (1b):

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and when R is an alkyl group, the double bond is in a trans configuration. P represents an integer of 1 to 10 and q represents 0. Or W, X and Y represent a fluorine atom, a chlorine atom, a methyl group, a cyano group or a hydrogen atom, and Z represents a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms or An alkoxyl group, an alkenyl group having 3 to 12 carbon atoms, or an alkenyloxy group, wherein one or more hydrogen atoms contained in these groups may be substituted with fluorine atoms. Liquid crystal compounds have been proposed.

This compound is chemically stable to heat, light, etc., has excellent liquid crystallinity, and is easy to produce industrially. Moreover, since it is excellent in compatibility with conventional liquid crystal compounds and liquid crystal compositions, the response time of the obtained liquid crystal can be greatly improved by using this. Therefore, it is considered to be practical as a constituent component of a liquid crystal material for a liquid crystal display element capable of high-speed response over a wide temperature range.
However, liquid crystal display devices in recent years have been improved in performance, and there is a demand for the development of liquid crystal materials having a large Δn, which can be manufactured at a lower temperature, a wider range of temperatures showing a liquid crystal phase, chemically stable and inexpensive. is the current situation.

JP-A-10-147562

  The present invention has been made in view of the above-described prior art, and has a wider temperature range showing a liquid crystal phase, is chemically stable, can be manufactured at low cost, and has a selective reflection wavelength band Δλ. Wide, that is, a polymerizable liquid crystal compound having a large Δn, a polymerizable liquid crystal composition containing the compound, a liquid crystalline polymer obtained by polymerizing these compounds, and an optical anisotropic body comprising the liquid crystalline polymer as a constituent material It is an issue to provide.

  As a result of diligent research to solve the above-mentioned problems, the present inventor generally has a conjugated linear atom called a mesogenic group that imparts liquid crystal alignment properties that exists at the center of a chain of a polymerizable liquid crystal compound having a chain structure. As a group, a specific compound having an azine skeleton is chemically stable to heat, light, etc., has excellent liquid crystallinity, can be easily manufactured industrially, and has a selective reflection wavelength band Δλ. It has been found that it is wide, that is, Δn is large and is particularly suitable as a material for forming a cholesteric liquid crystal layer, and the present invention has been completed.

Thus, according to the first aspect of the present invention, the following polymerizable liquid crystal compounds (1) to (5) are provided.
(1) The following formula (I)

[In formula, M represents the C1-C30 bivalent organic group which may have a substituent.
Y _{1 to} Y ₈ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C ( ═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (═O ) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O—. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G ₁ and G ₂ each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent. The aliphatic group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ^2. -C (= O) -, - C (= O) -NR 2 -, - NR 2 -, or, -C (= O) - may be interposed (but, -O- and S- are Except when two or more adjacent to each other.) Here, R < ² > represents a hydrogen atom or a C1-C6 alkyl group.
Z ₁ and Z ₂ each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
A ₁ and A ₂ each independently represent a divalent organic group A having 1 to 30 carbon atoms.
X _{1 to} X ₁₆ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ³ , —O—C ( ═O) —R ³ , —C (═O) —OR ³ , —O—C (═O) —OR ³ , —NR ⁴ —C (═O) —R ³ , —C (═O) —N (R ³ ) R ⁴ or —O—C (═O) —N (R ³ ) R ⁴ is represented. Here, R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, the alkyl group includes —O—, — S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ⁵ —C (═O) —, —C (= O) —NR ⁵ —, —NR ⁵ —, or —C (═O) — may be present (except when two or more of —O— and —S— are present adjacent to each other). .) Wherein, ^{R 4} and ^{R 5} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
a, b, c and d are each independently 0 or 1; ]
A polymerizable liquid crystal compound represented by:

(2) The M has a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a naphthylene group which may have a substituent, or a substituent. The polymerizable liquid crystal compound according to (1), which may be a triphenylene group.
(3) Z ₁ and Z ₂ are each independently CH ₂ = CH-, CH ₂ = C (CH ₃ )-, CH ₂ = C (Cl)-, CH ₂ = CH-CH _2- , _{CH 2 = C (CH 3)} -CH 2 -, CH 2 = C (CH 3) -CH 2 -CH 2 -, (CH 3) 2 C = CH-CH 2 -, CH 3 -CH = CH-, Alternatively, the polymerizable liquid crystal compound according to (1) or (2), wherein CH ₃ —CH═CH—CH ₂ —.

(4) M is a phenylene group which may have a substituent,
a = d = 1, b = c = 0,
Y ₁ , Y _{3 to} Y ₆ , Y ₈ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G _{1 to} G ₂ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —, and these groups include —O—, —C (═O) —O. -, -OC (= O)-, or -C (= O)-may be interposed,
The polymerizable liquid crystal compound according to (1), wherein Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —.

(5) The M is a phenylene group which may be substituted with a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group includes —O—, —C (═O) —O—, — O—C (═O) — or —C (═O) — may be interposed,
The polymerizable liquid crystal compound according to (4), wherein Z ₁ and Z ₂ are both CH ₂ ═CH—.
(6) The polymerizable liquid crystal compound according to (4), wherein M is a phenylene group which may be substituted with —C (═O) —OR ³ (R ³ represents the same meaning as described above).

According to the second aspect of the present invention, the following polymerizable liquid crystal composition (6) is provided.
(7) A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of (1) to (6) and a polymerizable chiral compound.

According to the third aspect of the present invention, the following liquid crystalline polymer (8) is provided.
(8) A liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound according to any one of (1) to (6) or the polymerizable liquid crystal composition according to (7).
According to the fourth aspect of the present invention, the following optical anisotropic body (9) is provided.
(9) An optical anisotropic body comprising the liquid crystalline polymer according to (8) as a constituent material.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a polymerizable liquid crystal compound, 2) a polymerizable liquid crystal composition, 3) a liquid crystal polymer, and 4) an optical anisotropic body.

1) Polymerizable liquid crystal compound The polymerizable liquid crystal compound of the present invention is a compound represented by the formula (I).

In said formula (I), in formula, M represents the C1-C30 bivalent organic group which may have a substituent. As carbon number of the organic group M, 6-20 are preferable. Although it does not restrict | limit especially as an organic group of M, What has an aromatic ring is preferable.
Specific examples of M include the following.

The organic group mentioned as a specific example of M may have a substituent at an arbitrary position. Examples of the substituent include a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, —C (═O) —OR ³ (R ³ is , Which represents the same meaning as R ³ described later).

Among these, M is a phenylene group which may have a substituent, a biphenylene group which may have a substituent, or a substituent from the viewpoint of better expressing the desired effect of the present invention. A naphthylene group which may have, or a triphenylene group which may have a substituent is preferable, and a p-phenylene group represented by the following formula (M ₁ ) which may have a substituent, and A 1,4′-biphenylene group represented by (M ₂ ) is more preferred, and a p-phenylene group represented by the following formula (M ₁ ) is particularly preferred.

As the substituent of the above-mentioned substituent (phenylene group, biphenylene group, naphthylene group, or triphenylene group), a hydrocarbon group having 1 to 10 carbon atoms, or —C (═O) —OR ³ (R ³ represents the same meaning as R ³ described later) is preferable.

  Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms. Further, these hydrocarbon groups may contain —O—, —C (═O) —O—, —O—C (═O) —, —C (═O) — or the like. Good.

Y _{1 to} Y ₈ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C ( ═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (═O ) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O—.

Here, R ¹ is a hydrogen atom; or methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n -An alkyl group having 1 to 6 carbon atoms such as a hexyl group. Among these, R ¹ is preferably a hydrogen atom or a methyl group.

Among these, Y _{1 to} Y ₈ are preferably —C (═O) —O—, —O—C (═O) —, or —O—.
As a preferable combination of Y, Y ₁ , Y ₃ , Y ₄ and Y ₇ are —C (═O) —O— from the viewpoint of easy synthesis and better expression of the desired effect of the present invention. Yes, Y ₂ , Y ₅ , Y ₆ and Y ₈ are combinations in which —O—C (═O) —.

G ₁ and G ₂ each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent, and preferably a divalent aliphatic group having 1 to 12 carbon atoms. .

Examples of the divalent aliphatic group having 1 to 20 carbon atoms of G ₁ and G ₂ include chain aliphatic groups such as an alkylene group having 1 to 20 carbon atoms and an alkenylene group having 2 to 20 carbon atoms. Of these, an alkylene group having 2 to 20 carbon atoms such as an ethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group is preferable from the viewpoint of better expressing the desired effect of the present invention.

Examples of the substituent of the aliphatic group of G ₁ and G ₂ include a halogen atom and an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a fluorine atom, and the alkoxy group is preferably a methoxy group or an ethoxy group.

The aliphatic group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, — NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or C (═O) — may be present (however, —O— and —S—) may be present. Except for two or more adjacent to each other.)

Here, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms similar to the alkyl group having 1 to 6 carbon atoms of R ¹ , and is preferably a hydrogen atom or a methyl group.

Among these, G _{1 to} G ₂ are each independently —O—, —C (═O) —O—, —O—C (═O) —, or —C (═O) —. There may be _{interposed, - (CH 2) 6 -} , or, - _{(CH 2) 4} - a is preferably.

Z ₁ and Z ₂ each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.

The number of carbon atoms of the alkenyl group of Z ₁ and Z _2, from the viewpoint of better express the desired effects of the present invention, 2 to 6 are preferred. As the halogen atom is a substituent of alkenyl groups Z ₁ and Z _2, a chlorine atom is preferable.

Preferable specific examples of the alkenyl group having 2 to 10 carbon atoms that may be substituted with a halogen atom in Z ₁ and Z ₂ include CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, and CH ₂ ═. _{C (Cl) -, CH 2} = CH-CH 2 -, CH 2 = C (CH 3) -CH 2 -, CH 2 = C (CH 3) -CH 2 -CH 2 -, (CH 3) 2 C ═CH—CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH═CH—CH ₂ — and the like.

Among these, as Z ₁ and Z ₂ , each independently preferably CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —. ₂ = CH— is particularly preferred.

X _{1 to} X ₁₆ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ³ , —O—C. (═O) —R ³ , —C (═O) —OR ³ , —O—C (═O) —OR ³ , —NR ⁴ —C (═O) —R ³ , —C (═O) — N (R ³ ) R ⁴ or —O—C (═O) —N (R ³ ) R ⁴ is represented.

Here, R < ³ > represents the C1-C10 alkyl group which may have a hydrogen atom or a substituent.
Examples of the alkyl group having 1 to 10 carbon atoms of the alkyl group having 1 to 10 carbon atoms which may have a substituent for R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group and the like.

  Moreover, as a substituent of the C1-C10 alkyl group which may have the said substituent, C1-C6 alkoxy, such as halogen atoms, such as a fluorine atom and a chlorine atom; A methoxy group, an ethoxy group, etc. Group; phenyl group which may have a substituent such as phenyl group, 4-methylphenyl group; and the like.

In addition, when R ³ is an alkyl group, the alkyl group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C ( ═O) —O—, —NR ⁵ —C (═O) —, —C (═O) —NR ⁵ —, —NR ⁵ —, or —C (═O) — may be present. (However, the case where two or more of -O- and -S- are adjacent to each other is excluded).
Wherein, ^{R 4} and ^{R 5} denotes a hydrogen atom or the same alkyl group having 1 to 6 carbon atoms and the ^{R 1.}

Among them, from the viewpoint of easy availability of raw _materials, X 1 to X ₁₆ is ₍₁₎ or X 1 _{to X 16} are both hydrogen _atoms, (2) _{X 2,} X 4 _{to X 13} and X ₁₅ is a hydrogen atom, and at least one of X ₁ , X ₃ , X ₁₄ and X ₁₆ is —OR ³ or C (═O) —O—R ³ (wherein R ³ has the same meaning as described above). And X ₁ , X ₃ , X ₁₄ and X ₁₆ which are not —OR ³ and C (═O) —O—R ³ are preferably hydrogen atoms,

(3) X _{1 to} X ₁₆ are all hydrogen atoms, (4) X ₂ , X _{4 to} X ₁₃ and X ₁₅ are all hydrogen atoms, and X ₁ , X ₃ , X ₁₄ and X ₁₆ of at least one _{of, -OCH 3, -OC 2 H 5} , -C (= O) -O-CH 3, -C (= O) -O-C 2 H 5, -C (= O) -O- _{CH 2 CH 2 CH 3, -C} (= O) -O-CH 2 CH 2 OCH 3, -C (= O) -O-CH 2 CH 2 OCH 2 CH 3, or, -C (= O) - O—CH ₂ CH ₂ OCH ₂ CH ₂ CH ₃ and, among X ₁ , X ₃ , X ₁₄ and X ₁₆ , —OCH ₃ , —OC ₂ H ₅ , —C (═O) —O—. _{CH 3, -C (= O)} -O-C 2 H 5, -C (= O) -O-CH 2 CH 2 CH 3, -C (= O) -O-CH 2 CH OCH _3, be _{-C (= O) -O-CH} 2 CH 2 OCH 2 CH 3, and _{-C (= O) -O-CH} 2 CH 2 OCH 2 shall not _CH 2 CH ₃ is a hydrogen atom More preferred.

A ₁ and A ₂ each independently represent a divalent organic group having 1 to 30 carbon atoms. Specific examples of the organic group of A ₁ and A ₂ include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc. An alkylene group having -30 carbon atoms; a phenylene group which may have a substituent; a biphenylene group which may have a substituent; a naphthylene group which may have a substituent; Arylene groups; and combinations of alkylene groups and arylene groups as shown below.

Among them, as the A ₁ and A _2, from the viewpoint of better express the desired effects of the present invention, preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms .

a, b, c and d are each independently 0 or 1;
In the formula (I), are respectively coupled to _{A 1} and _{A 2, wherein: -Y 2 - (G 1 -Y} 1) a -Z 1 and the _{formula: -Y 7 - (G 2 -Y} 8) d Specific examples of the group represented by —Z ₂ include the following.

Incidentally, each of the a and _{d, (G} 1 -Y ₁₎ units and _(G 2 -Y ₈₎ represents the number of repeating units, a and d are each independently 0 or 1. As a particularly preferred combination of a and d, a and d are both 1 and b and c are 0 from the viewpoint of ease of synthesis and better expression of the desired effect of the present invention.

  First, a legend in which a or d is 1, that is, a structure represented by the following formula (α) will be described below.

In the formula, Y ₂ or Y ₇ is —C (═O) —O—, G ₁ or G ₂ is a hexamethylene group, Y ₁ or Y ₈ is —O—C (═O) —, Z ₁ or Z ₂ Corresponds to a vinyl group.
Furthermore, the specific example is shown below.

  Next, the legend of a to d = 0, that is, the structure represented by the following formula (β) will be described below.

In the formula, Y ₃ or Y ₆ corresponds to —C (═O) —O—, and Z ₁ or Z ₂ corresponds to a vinyl group.
Furthermore, the specific example is shown below.

  In the polymerizable liquid crystal compound represented by the formula (I) of the present invention, two groups represented by the following formulas may be the same or different.

(Wherein, Z ₁ , Z ₂ , Y _{1 to} Y ₃ , Y _{6 to} Y ₈ , A ₁ , A ₂ , G ₁ , G ₂ , a, and d represent the same meaning as described above.)

  Preferable specific examples of the polymerizable liquid crystal compound of the present invention represented by the formula (I) include the following, but the polymerizable liquid crystal compound of the present invention is not limited to the following compounds.

  All of the polymerizable liquid crystal compounds of the present invention are —O—, —S—, —NH—C (═O) —, —C (═O) —NH—, —NH—C (═O) —NH—. , -O-C (= O)-, -C (= O) -O-, -C (= O) -O-C (= O)-and other known methods for forming various chemical bonds (for example, Sandra, Caro functional group-specific organic compound synthesis method [I], [II] Yodogawa Shoten, published in 1976)).

  The polymerizable liquid crystal compound of the present invention typically includes an ether bond (—O—), an ester bond (—C (═O) —O—), an amide bond (—C (═O) NH—), an acid. A plurality of known compounds having a desired structure by arbitrarily combining the formation reaction of chloride (—C (═O) —Cl) and acid anhydride (—C (═O) —O—C (═O) —) It can be produced by appropriately binding and modifying the compound.

The ether bond can be formed, for example, as follows.
1) A compound represented by the formula: Q1-X (X represents a halogen atom; the same applies hereinafter) and a formula: Q2-OMa (Ma represents an alkali metal (mainly sodium). The same applies hereinafter. .) Is mixed and condensed. In the formula, Q1 and Q2 represent arbitrary organic groups (the same applies hereinafter). This reaction is generally called Williamson synthesis.
2) A compound represented by the formula: Q1-X and a compound represented by the formula: Q2-OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
3) A compound represented by the formula: Q1-E (E represents an epoxy group) and a compound represented by the formula: Q2-OH were mixed in the presence of a base such as sodium hydroxide or potassium hydroxide. To condense.
4) A compound represented by the formula: Q1-OFN (OFN represents a group having an unsaturated bond) and a compound represented by the formula: Q2-OMa are present in the presence of a base such as sodium hydroxide or potassium hydroxide. Under mixing, the addition reaction is carried out.
5) A compound represented by the formula: Q1-X and a compound represented by the formula: Q2-OMa are mixed and condensed in the presence of copper or cuprous chloride. This reaction is generally called Ullmann condensation.

Formation of an ester bond and an amide bond can be performed as follows, for example.
6): a compound represented by Q1-COOH, wherein: Q2-OH or a compound represented by Q2-NH _2, dehydrated in the presence of a dehydrating condensing agent (N, N-dicyclohexylcarbodiimide, etc.) condensation Let
7) A chlorinating agent is allowed to act on the compound represented by the formula: Q1-COOH to obtain an acid chloride represented by the formula: Q1-C (═O) Cl. Alternatively, the compound represented by Q2-NH ₂ is reacted in the presence of a base.
8): by the action of an acid anhydride to a compound represented by Q1-COOH, after obtaining a mixed acid anhydride, in this one, the formula: Q2-OH or a compound represented by Q2-NH ₂ React.
9): with a compound represented by Q1-COOH, wherein: the Q2-OH or the compound represented by Q2-NH _2, dehydration condensation in the presence of an acid catalyst or base catalyst.

  The acid chloride can be produced by a known method. For example, (α) a method in which a chlorinating agent such as phosphorus trichloride, phosphorus pentachloride, thionyl chloride, oxalyl chloride is allowed to act on a carboxylic acid represented by the formula: Q1-COOH; (β) a formula: Q1-COOAg A method in which chlorine is allowed to act on the silver salt of the carboxylic acid represented; (γ) a method in which a carbon tetrachloride solution of red mercuric oxide is allowed to act on the compound represented by the formula: Q1-COOH;

In the synthesis of the polymerizable liquid crystal compound of the present invention, the yield can be improved by protecting the hydroxyl group present in the intermediate.
As a method for protecting a hydroxyl group, it can be produced using a known method (for example, see Green's Protective Groups in Organic Synthesis 3rd edition published by Wiley-Interscience, published in 1999).

More specifically, the protection of the hydroxyl group can be performed as follows.
a) A compound represented by the formula: Q1Q2Q3-Si-X and a compound represented by the formula: Q4-OH are mixed and reacted in the presence of a base such as imidazole or pyridine. In the formula, Q3 and Q4 represent an arbitrary organic group B (the same applies hereinafter).
b) Reaction by mixing a vinyl ether compound such as 3,4-dihydro-2H-pyran and a compound represented by Q2-OH in the presence of an acid such as p-toluenesulfonic acid, p-toluenesulfonic acid pyridine salt and hydrogen chloride. Let
c) A compound represented by the formula: Q1-C (= O) -X and a compound represented by the formula: Q4-OH are mixed and reacted in the presence of a base such as triethylamine or pyridine.
d) The acid anhydride compound represented by the formula: Q1-C (= O) -OC (= O) -Q2 and the compound represented by the formula: Q3-OH are mixed and reacted, or water In the presence of a base such as sodium oxide or triethylamine, they are mixed and reacted.
e) A compound represented by Q1-X and a compound represented by the formula: Q2-OH are mixed and reacted in the presence of a base such as sodium hydroxide or triethylamine.
f) formula: and _Q1-O-CH compound represented by 2 -X, wherein: the Q2-OH are represented by compounds, sodium hydride, sodium hydroxide, triethylamine, presence of a base such as pyridine, mixed And react.
g) A compound represented by Q1-O—CH ₂ —C (═O) —X and a compound represented by the formula: Q4-OH were mixed in the presence of a base such as potassium carbonate or sodium hydroxide. To react.
h) A compound represented by the formula: Q1-OC (= O) -X and a compound represented by the formula: Q2-OH are mixed and reacted in the presence of a base such as triethylamine or pyridine.

The deprotection of the protecting group for the hydroxyl group can be deprotected by utilizing a known method depending on the structure and type of the protecting group.
(I) Fluoride such as tetrabutylammonium fluoride is mixed to be deprotected.
(Ii) Deprotection by mixing in the presence of an acid such as paratoluenesulfonic acid, pyridine salt of paratoluenesulfonic acid, hydrogen chloride, acetic acid or the like.
(Iii) Deprotection by mixing in the presence of a base such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine.
(Iv) Deprotection is carried out by hydrogenation in the presence of a catalyst such as Pd-C.

  More specifically, the compound of the present invention can be synthesized as follows.

(In the formula, M, Y _{1 to} Y ₈ , G ₁ , G ₂ , Z ₁ , Z ₂ , A ₁ , A ₂ , X _{1 to} X ₁₆ , a, b, c and d represent the same meaning as described above. L ₁ and L ₂ represent a leaving group, Y ₃ ′ represents a group that reacts with L ₁ to generate Y ₃ , and Y ₆ ′ represents a group that reacts with L ₂ to generate Y ₆ . , L ₁ is COCl and Y ₃ is —C (═O) —O—, Y ₃ ′ is an OH group, L ₁ is an OH group, and Y ₃ is —O—C (═O). - in the case of the, _{Y 3} 'is a COOH group, ₂ group _{L 1} is NH, _{Y 3} is -NHC (= O) - in the case of the, _{Y 3'} is COOH group .Y ₆ The same applies to '.)

  That is, an aldehyde compound represented by formula (10) (aldehyde compound (10)) and a hydrazide compound represented by formula (11a) and formula (11b) (hydrazide compound (11a), hydrazide compound (11b)) To obtain a compound represented by formula (12) (compound (12)) (step 1), and this compound and a compound represented by formula (13a) and formula (13b) (compound (13a) ) And the compound (13b)), the target compound of the present invention represented by the formula (I) (the present compound (I)) can be obtained (step 2).

The reaction of Step 1 can be performed by mixing and stirring the aldehyde compound (10) and the hydrazide compound (11a) (and the hydrazide compound (11b)) in an appropriate solvent.
In this case, when the hydrazide compound (11a) and the hydrazide compound (11b) are different compounds, they may be reacted sequentially. In addition, when the hydrazide compound (11a) and the hydrazide compound (11b) are the same, they may be used in a double amount or more.

  In Step 1, the amount of the hydrazide compounds (11a) and (11b) used is usually 0.5 to 5 times the mol of the aldehyde compound (10).

  Examples of the solvent used in Step 1 include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ether solvents such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; Ester solvents such as ethyl acetate, propyl acetate and methyl propionate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; N Amide solvents such as N, dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; and mixed solvents composed of two or more of these solvents.

The reaction in Step 1 proceeds smoothly in a temperature range from −10 ° C. to the boiling point of the solvent used.
The reaction time is usually from several minutes to several hours, although depending on the reaction scale.
As described above, a reaction solution containing the compound (12) is obtained.

  In the present invention, the compound (12) is isolated from the obtained reaction solution, and the isolated compound (12) may be subjected to the next step 2, or the compound (12) may be isolated without isolation. You may use the reaction liquid containing (12) for the process 2 as it is.

Many of the aldehyde compounds (10) are known compounds and can be produced and obtained by known methods.
The hydrazide compounds (11a) and (11b) can be obtained by reacting hydrazine and benzaldehyde derivatives (14a and 14b), respectively, as shown below.

In addition, as a benzaldehyde derivative to be used, a compound in which a protecting group is bonded to Y ₃ ′ and Y ₆ ′ is used. Before the reaction in Step 2, the protecting group is deprotected to obtain a hydrazide compound (11a), ( After step 11b), the reaction of step 2 may be performed. For example, when Y ₃ ′ and Y ₆ ′ are hydroxyl groups, the reaction in Step 1 is performed after the reaction of Step 1 using a benzaldehyde derivative in which the hydroxyl groups are protected with a protecting group such as t-butyldimethylsilyl group. The hydrazide compounds (11a) and (11b) can be obtained by performing deprotection according to the method.

  Next, the compound (12) obtained in the step 1 is reacted with the compounds (13a) and (13b) to obtain the target compound (I) of the present invention (step 2).

The reaction of step 2 can be performed by mixing and stirring the compound (12) and the compound (13a) (and the compound (13b)) in a suitable solvent.
In this case, when the compound (13a) and the compound (13b) are different compounds, they may be reacted sequentially. In addition, when the compound (13a) and the compound (13b) are the same, they may be used in a double amount or more.

  In Step 2, the amount of compounds (13a) and (13b) used is usually 0.5 to 5 moles compared to compound (12).

  Examples of the solvent used in Step 2 include ether solvents such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; ester solvents such as ethyl acetate, propyl acetate, and methyl propionate; benzene, toluene, Aromatic hydrocarbon solvents such as xylene; Aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; Amides such as N, N-dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide System solvents; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; and mixed solvents composed of two or more of these solvents.

  When the compounds (13a) and (13b) are acid chlorides or anhydrides, the reaction may be able to proceed more smoothly by adding a base to the reaction system.

  Examples of the base to be used include organic bases such as pyridine, triethylamine and diisopropylethylamine; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. The amount of the base used is usually 1 to 3 moles compared to the compounds (13a) and (13b).

The reaction in Step 2 proceeds smoothly in a temperature range from −10 ° C. to the boiling point of the solvent used.
The reaction time is usually from several minutes to several hours, although depending on the reaction scale.

Many of the compounds (13a) and (13b) are known compounds, and can be produced and obtained by known methods.
Preferable specific examples of the compounds (13a) and (13b) include the following compounds. Of course, the present invention is not limited to these compounds.

(In the formula, r and s each independently represent an integer of 1 to 6, L represents a chlorine atom or a hydroxyl group, and R ₁₀ represents a hydrogen atom or a methyl group.)

In any reaction, after the completion of the reaction, the usual post-treatment operation in organic synthetic chemistry is performed, and if desired, by applying known separation / purification means such as column chromatography, recrystallization method, distillation method, etc. Product can be isolated.
The structure of the target product can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.

2) Polymerizable liquid crystal composition The second aspect of the present invention is a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention and a polymerizable chiral compound (hereinafter referred to as “polymerizable chiral compound”). .

  The composition of the present invention contains one or more of the polymerizable liquid crystal compounds of the present invention described above as essential components. The composition of the present invention includes, in addition to the polymerizable liquid crystal compound of the present invention, JP-A-11-130729, JP-A-8-104870, JP-A-2005-309255, JP-A-2005-263789, Other polymerizations such as those described in JP-T-2002-533742, JP-A-2002-308832, JP-A-2002-265421, JP-A-62-070406, JP-A-11-10055, etc. One kind or two or more kinds of conductive liquid crystal compounds may be used.

  The content of the other polymerizable liquid crystal compound added to the polymerizable liquid crystal compound used in the present invention is preferably 50% by weight or less and more preferably 30% by weight or less in the total amount of the polymerizable liquid crystal compound used in the present invention.

The polymerizable chiral compound used in the composition of the present invention is a compound having a chiral carbon atom in the molecule and polymerizable with the polymerizable liquid crystal compound of the present invention, and the orientation of the polymerizable liquid crystal compound of the present invention. If it does not disturb, there is no particular limitation.
Here, “polymerization” means a chemical reaction in a broad sense including a crosslinking reaction in addition to a normal polymerization reaction.

In the composition of the present invention, the polymerizable chiral compound can be used alone or in combination of two or more.
The polymerizable liquid crystal compound of the present invention constituting the polymerizable liquid crystal composition of the present invention can develop a cholesteric phase by mixing with the polymerizable chiral compound.

  As the polymerizable chiral compound, for example, a known compound as described in JP-A No. 11-193287 can be used. Examples of such chiral compounds include, but are not limited to, compounds represented by the following three general formulas.

In the above formula, examples of R ⁶ and R ⁷ include a hydrogen atom, a methyl group, and a methoxy group. Examples of Y ⁹ and Y ¹⁰ include —O—, —O—C (═O) —, —O—C (═O) —O—, and the like. M ¹ and m ² are each independently ² , 4 or 6. Specific examples of the compounds represented by these general formulas include the compounds shown below.

  In the polymerizable liquid crystal composition of the present invention, the mixing ratio of the polymerizable chiral compound is usually 0.1 to 100 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound. .

  In general, a polymerization initiator, particularly a photopolymerization initiator, is preferably added to the polymerizable liquid crystal composition of the present invention from the viewpoint of performing a polymerization reaction more efficiently. Examples of the polymerization initiator include polymerization initiators described in the section “3) Liquid crystalline polymer” described later.

  In the polymerizable liquid crystal composition of the present invention, the blending ratio of the polymerization initiator is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound. It is.

  The polymerizable liquid crystal composition of the present invention preferably contains a surfactant in order to adjust the surface tension. The surfactant is not particularly limited, but a nonionic surfactant is usually preferable. As the nonionic surfactant, a commercially available product may be used, for example, a nonionic surfactant that is an oligomer having a molecular weight of about several thousand, and specific examples include KH-40 manufactured by Seimi Chemical Co., Ltd. It is done. In the polymerizable liquid crystal composition of the present invention, the blending ratio of the surfactant is usually 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound.

  When the polymerizable liquid crystal composition of the present invention is used for applications such as a polarizing film or a raw material for an alignment film, printing ink, paint, protective film, etc., in addition to the above components, other components described below are used depending on the purpose. Copolymerizable monomers, metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange You may mix | blend other additives, such as resin, metal oxides, such as a titanium oxide. In the polymerizable liquid crystal composition of the present invention, the blending ratio of other additives is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable liquid crystal compound.

  The polymerizable liquid crystal composition of the present invention usually contains a predetermined amount of the polymerizable liquid crystal compound of the present invention, a polymerizable chiral compound, a photopolymerization initiator, a nonionic surfactant, and other additives as appropriate. It can be prepared by dissolving in a solvent.

  Organic solvents to be used include ketones such as cyclopentanone, cyclohexanone and methyl ethyl ketone; acetate esters such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; 1,4-dioxane and cyclopentylmethyl And ethers such as ether, tetrahydrofuran and tetrahydropyran;

  The polymerizable liquid crystal composition obtained as described above is useful as a raw material for producing a cholesteric liquid crystal layer or a cholesteric liquid crystal polymer as described later.

3) Liquid crystalline polymer The third of the present invention is a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention or the polymerizable liquid crystal composition of the present invention.
Here, “polymerization” means a chemical reaction in a broad sense including a crosslinking reaction in addition to a normal polymerization reaction.

  Specifically, the liquid crystalline polymer of the present invention is obtained by polymerizing (1) a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention, or (2) polymerizing the polymerizable liquid crystal composition of the present invention. It is a liquid crystalline polymer obtained as described above.

(1) Liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention The liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention includes a single weight of the polymerizable liquid crystal compound of the present invention. A copolymer composed of two or more of the polymerizable liquid crystal compounds of the present invention, a copolymer of the polymerizable liquid crystal compound of the present invention and other polymerizable liquid crystal compounds, and the polymerizable liquid crystal compound of the present invention and other copolymers. Examples thereof include a copolymer with a polymerizable monomer.

  Examples of the other polymerizable liquid crystal compounds include JP-A-11-130729, JP-A-8-104870, JP-A-2005-309255, JP-A-2005-263789, JP-T-2002-533742, Examples thereof include polymerizable liquid crystal compounds such as those described in JP-A No. 2002-308832, JP-A No. 2002-265421, JP-A No. 62-070406, JP-A No. 11-10055 and the like.

  The other copolymerizable monomer is not particularly limited, and examples thereof include 4- (2-methacryloyloxyethyloxy) benzoic acid-4′-methoxyphenyl, 4- (6-methacryloyloxyhexyl). Oxy) benzoic acid biphenyl, 4- (2-acryloyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2-methacrylolyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2 -Methacryloyloxyethyloxy) benzoic acid-3 ', 4'-difluorophenyl, 4- (2-methacryloyloxyethyloxy) benzoic acid naphthyl, 4-acryloyloxy-4'-decylbiphenyl, 4-acryloyloxy- 4′-cyanobiphenyl, 4- (2-acryloyloxyethyloxy) -4′-si Nobiphenyl, 4- (2-methacryloyloxyethyloxy) -4'-methoxybiphenyl, 4- (2-methacryloyloxyethyloxy) -4 '-(4 "-fluorobenzyloxy) -biphenyl, 4-acryloyloxy- 4′-propylcyclohexylphenyl, 4-methacryloyl-4′-butylbicyclohexyl, 4-acryloyl-4′-amyltran, 4-acryloyl-4 ′-(3,4-difluorophenyl) bicyclohexyl, 4- (2- And acryloyloxyethyl) benzoic acid (4-amylphenyl), 4- (2-acryloyloxyethyl) benzoic acid (4- (4′-propylcyclohexyl) phenyl), and the like.

  The liquid crystalline polymer of the present invention comprises the polymerizable liquid crystal compound of the present invention and the other polymerizable liquid crystal compound or other copolymerizable monomer (hereinafter referred to as “other polymerizable liquid crystal compounds, etc. The content of the polymerizable liquid crystal compound unit of the present invention is not particularly limited, but is preferably 50% by weight or more based on the total structural units. 70% by weight or more is more preferable. If it exists in this range, since the glass transition temperature (Tg) of liquid crystalline polymer is high and high film | membrane hardness is obtained, it is preferable.

  The (co) polymerization of the polymerizable liquid crystal compound of the present invention and other polymerizable liquid crystal compounds used as necessary can be carried out in the presence of a suitable polymerization initiator. The proportion of the polymerization initiator used may be the same as the proportion of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition.

  As the polymerization initiator to be used, an appropriate one may be selected and used depending on the type of polymerizable group present in the polymerizable liquid crystal compound to be used. For example, a radical polymerization initiator is used if the polymerizable group is radically polymerizable, an anionic polymerization initiator is used if it is an anionic polymerizable group, and a cationic polymerization initiator is used if it is a cationically polymerizable group. That's fine. As the radical polymerization initiator, either a thermal radical generator or a photo radical generator can be used, but it is preferable to use a photo radical generator.

  Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenones, such as acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, Anthraquinones such as 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthate Such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4,4-dichlorobenzophenone, 4,4-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4-methyldiphenyl sulfide; Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Specific examples of the photo radical polymerization initiator include trade name Irgacure 907, trade name Irgacure 184, trade name Irgacure 369, trade name Irgacure 651 and the like manufactured by Ciba Specialty Chemicals.

  Specific examples of the anionic polymerization initiator include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene and pyrene; polyfunctional initiators such as dilithium salts and trilithium salts; and the like.

Specific examples of the cationic polymerization initiator include proton acids such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; Lewis such as boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. Acid; an aromatic onium salt or a combination system of an aromatic onium salt and a reducing agent.
These polymerization initiators can be used singly or in combination of two or more.

  In performing (co) polymerization with the polymerizable liquid crystal compound and other polymerizable liquid crystal compounds used as necessary, an ultraviolet absorber, an infrared absorber, an antioxidant, etc., if necessary. The functional compound may be present.

  More specifically, the liquid crystalline polymer of the present invention comprises (A) the above-mentioned polymerizable liquid crystal compound and other polymerizable liquid crystal compound used as necessary in the presence of a suitable polymerization initiator ( Co) polymerization in a suitable organic solvent, (B) a solution prepared by dissolving the polymerizable liquid crystal compound and other polymerizable liquid crystal compound used if necessary in an organic solvent together with a polymerization initiator. After coating on a support by the coating method, the solvent can be removed in the oriented state, and then heated or irradiated with active energy rays.

  The organic solvent used in the method (A) is not particularly limited as long as it is inert, and examples thereof include aromatic hydrocarbons such as toluene, xylene, mesitylene, etc .; ketones such as cyclohexanone, cyclopentanone, and methyl ethyl ketone. Acetic esters such as butyl acetate and amyl acetate; Halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; Ethers such as cyclopentyl methyl ether, tetrahydrofuran and tetrahydropyran; Among these, from the viewpoint of excellent handleability, those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 150 ° C are more preferable.

  In the case of the method (A), for example, after reacting according to the polymerization reaction conditions described later, the target liquid crystalline polymer is isolated from the obtained polymerization reaction liquid, and the isolated liquid crystalline polymer is removed. A solution is prepared by dissolving in an appropriate organic solvent, and after drying the coating film obtained by coating this solution on an appropriate support, it is heated to a temperature that exhibits liquid crystallinity or higher, and then slowly cooled. Thus, the liquid crystal state can be fixed.

  Organic solvents for dissolving the liquid crystalline polymer include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; dichloromethane, chloroform, dichloroethane, and the like And halogenated hydrocarbon solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl methyl ether, and the like.

  As the support, a substrate made of a commonly used material can be used regardless of organic or inorganic. Examples of the material of the substrate include polycycloolefins (for example, ZEONEX, ZEONOR (registered trademark; manufactured by ZEON CORPORATION), ARTON (registered trademark; manufactured by JSR), and APPEL (registered trademark; manufactured by Mitsui Chemicals)). Polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose, cellulose triacetate, polyethersulfone, silicon, glass, calcite and the like. As a shape of a board | substrate, it may have a curved surface other than a flat plate. These substrates may have an electrode layer, an antireflection function, and a reflection function as necessary.

  As a method of applying the liquid crystalline polymer solution to the support, a known method can be used. For example, a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a dip coating method, a bar coating method, Examples thereof include a spray coating method, a slide coating method, and a printing coating method.

  Examples of the organic solvent used in the method (B) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; dichloromethane, chloroform, dichloroethane, and the like. Halogenated hydrocarbon solvents; ether solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl methyl ether;

  Although it does not specifically limit as a support body to be used, For example, the thing similar to what was listed as what can be used for coating the solution of the liquid crystalline polymer mentioned above is mentioned.

  Moreover, it does not specifically limit as a method of apply | coating the solution for polymerization reaction to a support body in the method of said (B), A well-known method can be used. Examples thereof include the same ones listed as methods for applying the above-mentioned liquid crystalline polymer solution on the support.

  In the method (B), it is preferable to align the polymerizable liquid crystal compound coated on the support. Examples of the method for aligning the polymerizable liquid crystal compound include a method in which an alignment treatment is performed on the above-described support in advance.

Preferred methods of applying an orientation treatment to the support, various polyimide alignment film, a liquid crystal alignment layer comprising a polyvinyl alcohol alignment film provided on the support, the method performs the process such as rubbing; SiO the support ₂ A method of irradiating polarized or non-polarized light to an organic thin film having a functional group that undergoes photodimerization reaction in the molecule or an organic thin film having a functional group that is isomerized by light; There are known methods. Polymerization of the polymerizable liquid crystal compound may be performed according to polymerization reaction conditions as described later.

(2) Liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention By polymerizing the polymerizable liquid crystal composition of the present invention in the presence of a polymerization initiator, the liquid crystalline polymer of the present invention is obtained. Can be easily obtained. The obtained liquid crystalline polymer is a cholesteric liquid crystalline polymer. In the present invention, it is preferable to use a polymerizable liquid crystal composition containing a polymerization initiator as described above, particularly a photopolymerization initiator and a polymerizable chiral compound, from the viewpoint of performing a polymerization reaction more efficiently. Hereinafter, an embodiment using such a polymerizable liquid crystal composition will be described.

  Specifically, for example, the polymerizable liquid crystal composition of the present invention is applied on a support having an alignment function obtained according to the method for performing the alignment treatment, and the polymerization in the polymerizable liquid crystal composition of the present invention is performed. The liquid crystalline polymer of the present invention can be obtained by uniformly aligning and polymerizing the liquid crystalline compound while holding the cholesteric layer. As the support, those described above can be used.

  In the above method, in order to form a uniform alignment state, a polyimide thin film that gives a pretilt angle used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element is used. Control of the alignment state of the polymerizable liquid crystal compound can be facilitated.

Generally, when a liquid crystal composition is brought into contact with a support having an alignment function, the liquid crystal compound is aligned along the direction in which the support is aligned on the support surface. Whether the liquid crystal compound is aligned horizontally with respect to the support surface or inclined or perpendicular is greatly influenced by the alignment treatment method on the support surface.
For example, when an alignment film having a very small pretilt angle as used in an in-plane switching (IPS) type liquid crystal display element is provided on a support, a polymerizable liquid crystal layer aligned almost horizontally can be obtained.

  In addition, when an alignment film used for a TN type liquid crystal display element is provided on a support, a polymerizable liquid crystal layer having a slightly inclined alignment is obtained, and an alignment used for an STN type liquid crystal display element is obtained. When a film is used, a polymerizable liquid crystal layer having a large alignment can be obtained.

  In addition, when the polymerizable liquid crystal composition of the present invention is brought into contact with a support having a pre-tilt angle and having a horizontal alignment function, the angle changes uniformly or continuously from the support surface to the vicinity of the air interface. An oriented optical anisotropic body can be obtained.

  In addition, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule or an organic thin film having a functional group that is isomerized by light (hereinafter abbreviated as “photo-alignment film”) is irradiated with polarized light or non-polarized light, etc. If the photo-alignment method is used, a substrate in which regions having different orientation directions are distributed in a pattern can be produced.

  First, a support having a uniform orientation is prepared by irradiating light having a wavelength in the absorption band of the photo-alignment film onto the support on which the photo-alignment film is installed. Thereafter, the support is covered with a mask and irradiated with light having a different state from the first irradiation at the absorption wavelength of the photo-alignment film, for example, light having a different polarization state or light having a different irradiation angle and direction from above the mask. Only the irradiated portion has an orientation function different from that of the portion obtained by the first irradiation.

  If the polymerizable liquid crystal composition is brought into contact with the support in which regions having different alignment functions are distributed in the pattern obtained as described above, regions having different alignment directions are formed in a pattern according to the alignment function of the support. Distributed. If polymerization by light irradiation is performed in this state, a liquid crystalline polymer film having an alignment pattern can be obtained.

  In particular, when a support having a substantially horizontal alignment function in which regions having different alignment directions are distributed in a pattern is used as the support, a liquid crystalline polymer film particularly useful as a retardation film can be obtained. .

  In addition, as a method for obtaining an alignment pattern, a method that does not use a photo-alignment film, such as a method of rubbing the alignment film with an AFM (atomic force microscope) stylus or a method of edging an optical anisotropic body, can be employed. A method using a photo-alignment film is simple and preferable.

  Examples of a method for applying the polymerizable liquid crystal composition of the present invention on a support include known and usual coating methods such as bar coating, spin coating, roll coating, gravure coating, spray coating, die coating, cap coating, and dipping. Can be mentioned. At this time, in order to improve coatability, a known and commonly used organic solvent may be added to the polymerizable liquid crystal composition of the present invention. In this case, it is preferable to remove the organic solvent by natural drying, heat drying, reduced pressure drying, reduced pressure heat drying or the like after coating the polymerizable liquid crystal composition of the present invention on the support.

  After coating, the liquid crystal compound in the polymerizable liquid crystal composition of the present invention is preferably uniformly aligned while holding the cholesteric layer. Specifically, the alignment can be further promoted by performing a heat treatment that promotes the alignment of the liquid crystal.

  As the heat treatment method, for example, the polymerizable liquid crystal composition of the present invention is coated on a support, and then the C (solid phase) -N (nematic phase) transition temperature (hereinafter referred to as “CN transition temperature”) of the liquid crystal composition. The aforesaid polymerizable liquid crystal composition is brought into a liquid crystal phase or an isotropic phase liquid state. From there, it is gradually cooled as necessary to develop a cholesteric phase. At this time, it is desirable to maintain the temperature at which the liquid crystal phase is once exhibited, and to sufficiently grow the liquid crystal phase domain into a mono domain.

  In addition, after applying the polymerizable liquid crystal composition of the present invention on a support, a heat treatment may be performed to keep the temperature for a certain time within a temperature range where the cholesteric layer of the polymerizable liquid crystal composition of the present invention is developed. .

If the heating temperature is too high, the polymerizable liquid crystal compound may deteriorate due to an undesirable polymerization reaction. Moreover, when it cools too much, a polymeric liquid crystal composition raise | generates a phase-separation, expresses a high-order liquid crystal phase like crystal precipitation and a smectic phase, and an alignment process may become impossible.
By performing such heat treatment, a homogeneous liquid crystalline polymer film with few alignment defects can be produced as compared with a coating method in which coating is simply performed.

  In addition, after the homogeneous alignment treatment is performed in this manner, the liquid crystal phase is cooled to the lowest temperature at which phase separation does not occur, that is, is brought into a supercooled state, and the liquid crystal phase is aligned at the temperature and polymerized. Thus, a liquid crystalline polymer film having high alignment order and excellent transparency can be obtained.

  Examples of the method for polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method, but the reaction proceeds at room temperature without requiring heating. The method of irradiating active energy rays is preferable. Among these, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

  The temperature at the time of irradiation is set to a temperature at which the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention can maintain a liquid crystal phase, and in order to avoid the induction of thermal polymerization of the polymerizable liquid crystal compound or polymerizable liquid crystal composition, as much as possible. It is preferable to set it at 30 degrees C or less. In addition, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition usually has a N (nematic phase) -I (isotropic liquid phase) transition temperature (hereinafter referred to as “N— Abbreviated as “I transition temperature”).

  On the other hand, in the temperature lowering process, a non-equilibrium state is taken thermodynamically, so that the liquid crystal state may be maintained without being solidified even at a temperature lower than the CN transition temperature. This state is called a supercooled state. In the present invention, a polymerizable liquid crystal compound or a polymerizable liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is maintained.

The ultraviolet irradiation intensity is usually in the range of 1 W / m ^{2 to} 10 kW / m ² , preferably in the range of 5 W / m ^{2 to 2} kW / m ² .

  In addition, after polymerizing only a specific part by ultraviolet irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. A liquid crystalline polymer film having a plurality of regions having different orientation directions can be obtained.

  In addition, when only a specific part is polymerized by ultraviolet irradiation using a mask, the orientation is regulated by applying an electric field, a magnetic field or a temperature to a polymerizable liquid crystal compound or a polymerizable liquid crystal composition in an unpolymerized state in advance. A liquid crystalline polymer film having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it while maintaining this state.

  The liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention can be used alone as it is peeled from the support, or it can be used as it is without being peeled from the support. It can also be used as

  In particular, the liquid crystalline polymer film obtained by polymerizing the polymerizable liquid crystal composition of the present invention is a cholesteric liquid crystal film and has an extremely high reflectance, and thus is suitable as a polarizer in a liquid crystal display element.

  In addition to this, a multilayer that covers all light in the visible spectrum by laminating a plurality of such liquid crystalline polymer films by a laminating method and appropriately selecting the selection wavelength of the selected liquid crystalline polymer film A polarizer can also be obtained (see EP07720041).

  Further, instead of such a multilayer polarizer, it can also be used as a so-called broad-band polarizer in combination with appropriate compounds and processing conditions. As an implementation method for this purpose, for example, the methods described in WO98 / 08135 pamphlet, EP0606940 gazette, GB23125029 gazette, WO96 / 02016 pamphlet and the like can be mentioned.

  Furthermore, a color filter can also be produced using the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention. For this purpose, the required wavelengths can be applied appropriately by the application methods customary for those skilled in the art.

  Furthermore, the thermochromic property of cholesteric liquid crystal can also be used. By adjusting the temperature, the color of the cholesteric layer changes from red to blue via green. A specific zone can be polymerized at a defined temperature using a mask.

  The number average molecular weight of the liquid crystalline polymer of the present invention obtained as described above is preferably 500 to 500,000, more preferably 5,000 to 300,000. If the number average molecular weight is within such a range, a high film hardness can be obtained and handleability is excellent, which is desirable. The number average molecular weight of the liquid crystalline polymer can be measured by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard sample and tetrahydrofuran (THF) as an eluent.

  In the liquid crystalline polymer of the present invention, it is presumed that the crosslinking points are present uniformly in the molecule. Since it is obtained by polymerizing the polymerizable liquid crystal compound of the present invention, the crosslinking efficiency is high and the hardness is excellent.

  The liquid crystalline polymer of the present invention utilizes the orientation and the anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, and the like, a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, It can be used as a constituent material of an optical anisotropic body such as a viewing angle widening plate, a color filter, a low-pass filter, a light polarizing prism, and various optical filters.

4) Optical anisotropic body The fourth aspect of the present invention is an optical anisotropic body comprising the liquid crystalline polymer of the present invention as a constituent material.
Examples of the optical anisotropic body of the present invention include a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, a viewing angle widening plate, a color filter, a low-pass filter, a light polarizing prism, and various optical filters.

  Since the optical anisotropic body of the present invention uses a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention as a constituent material, it has a uniform and high-quality liquid crystal alignment.

  The production method of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. “Parts” and “%” are based on weight unless otherwise specified.

Example 1 Synthesis of Compound 1

(Step 1) Synthesis of Intermediate A

  To a solution of 4.00 g (26.0 mmol) of 2,5-dihydroxybenzoic acid and 9.04 g (77.9 mmol) of 2-hydroxyethyl acrylate in 50 ml of tetrahydrofuran (hereinafter abbreviated as “THF”). A solution of 6.69 g (32.4 mmol) of dicyclohexylcarbodiimide in 70 ml of THF was added at room temperature and stirred for 5 hours. The reaction solution was filtered through Celite, and the filtrate was concentrated with a rotary evaporator to obtain 18.94 g of a crude product as a viscous colorless oil. This was purified by silica gel column chromatography (toluene: ethyl acetate = 80: 20 (volume ratio)) to obtain 2.95 g of Intermediate A as a viscous colorless oil. (Yield 45%)

⁽¹ H-NMR spectral data of the intermediate A)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 9.969 (s, 1H), 7.272 (d, 1H, J = 3.0 Hz), 7.022 (dd, 1H, J = 3) 0.0, 9.2 Hz), 6.877 (d, 1 H, J = 9 Hz), 6.450 (d, 1 H, J = 17.2 Hz), 6.150 (dd, 1 H, J = 10.4, 17.2 Hz), 5.880 (d, 1H, J = 10.4 Hz), 5.316 (br, 1H), 4.599-4.509 (m, 4H)

(Step 2) Synthesis of Intermediate B

  To a solution of Intermediate A 1.50 g (6.0 mmol), 4-formylbenzoic acid 2.68 g (17.9 mmol) and 4-dimethylaminopyridine 733 mg (6.0 mmol) in THF 30 ml, N-dimethylaminopropyl was dissolved. -N'-ethylcarbodiimide hydrochloride 2.88 g (15.0 mmol) was added at room temperature, and the whole volume was stirred for 5 hours. The reaction solution was diluted with 500 ml of ethyl acetate and washed with water and then with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated on a rotary evaporator to obtain 5.86 g of a crude intermediate B product as a viscous colorless oil. Purification by silica gel column chromatography (toluene: ethyl acetate = 90: 10 (volume ratio)) gave 1.44 g of intermediate B as a colorless powder. (Yield 47%)

⁽¹ H-NMR spectral data of the intermediates B)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 10.165 (s, 2H), 8.045 (d, 2H, J = 8.4 Hz), 8.390 (d, 2H, J = 8) .4 Hz), 8.053 (d, 2H, J = 8.4 Hz), 8.051 (d, 2H, J = 8.4 Hz), 8.011 (d, 1H, J = 2.8 Hz), 7 .544 (dd, 1H, J = 2.8, 8.8 Hz), 7.339 (d, 1H, J = 8.8 Hz), 6.376 (d, 1H, J = 17.2 Hz), 6. 040 (dd, 1H, J = 10.4, 17.2 Hz), 5.810 (d, 1H, J = 10.4 Hz), 4.450 (t, 2H, J = 7.0 Hz), 4.288 (T, 2H, J = 7.0Hz)

(Step 3) Synthesis of Intermediate C (Step 3-1) Synthesis of Intermediate D

(In the formula, TBS represents a t-butyldimethylsilyl group. The same applies hereinafter.)
A solution of 2.64 g (11.1 mmol) of 4-t-butyldimethylsilyloxybenzaldehyde in 30 ml of ethanol was added dropwise at room temperature to a solution of 2.80 g (55.9 mmol) of hydrazine monohydrate in 30 ml of ethanol. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours, and then the reaction solution was concentrated with a rotary evaporator to remove ethanol and excess hydrazine monohydrate. Washed with aqueous sodium solution. 3 ml of triethylamine was added to the organic layer, dried over anhydrous magnesium sulfate, and then concentrated on a rotary evaporator to obtain 3.06 g of a crude product of Intermediate D as a viscous brown oil. This composition organism was subjected to the next step 3-2 without purification.

(Step 3-2) Synthesis of Intermediate C

  A solution prepared by dissolving 1.44 g (2.8 mmol) of intermediate D obtained in step 3-1 in 15 ml of ethanol was added dropwise to 3.06 g of intermediate B obtained in step 2 at room temperature, and overnight at the same temperature. Stir. The reaction solution was concentrated with a rotary evaporator, diluted with 500 ml of ethyl acetate, and washed with 50 ml of water and then with 50 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate and then concentrated on a rotary evaporator to obtain 5.06 g of a pale yellow oil. This was purified by silica gel column chromatography (toluene: ethyl acetate = 95: 5 (volume ratio)) to obtain 1.04 g of Intermediate C as a viscous light yellow oil. (Yield 38%)

⁽¹ H-NMR spectral data of the intermediate C)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.717 (s, 2H) 8.658 (s, 2H), 8.288 (d, 4H, J = 8.4 Hz), 8.005 −7.990 (m, 5H), 7.770 (d, 4H, J = 8.4 Hz), 7.551 (d, 1H, J = 8.4 Hz), 7.340 (d, 1H, J = 8.4 Hz), 6.927 (d, 4 H, J = 8.4 Hz), 6.378 (d, 1 H, J = 17.2 Hz), 6.041 (dd, 1 H, J = 10.4, 17) .2 Hz), 5.809 (d, 1 H, J = 10.4 Hz), 4.449 (t, 2 H, J = 7.0 Hz), 4.289 (t, 2 H, J = 7.0 Hz), 1 .026 (s, 18H), 0.256 (s, 12H)

(Step 4) Synthesis of Compound 1 (Step 4-1) Synthesis of Intermediate E

  To a solution obtained by dissolving 0.58 g (2.7 mmol) of mono (2-acryloxyethyl) succinate in 5 ml of toluene, 1.7 g (13.4 mmol) of oxalyl chloride was added dropwise at room temperature, followed by stirring at the same temperature for 3 hours. did. The reaction solution was concentrated under reduced pressure using a rotary evaporator to remove toluene and excess oxalyl chloride to obtain 0.68 g of a crude product of Intermediate E as a viscous colorless oil. This was subjected to the next step 2 without purification.

(Step 4-2) Synthesis of Compound 1

  To a solution of 1.04 g (1.1 mmol) of Intermediate C dissolved in 10 ml of THF, 3.0 ml of a 1 mol / L THF solution of tetra n-butylammonium fluoride was added dropwise at room temperature and stirred at the same temperature for 15 minutes. Next, a solution prepared by dissolving 0.68 g of the intermediate E obtained in Step 4-1 in 10 ml of THF was dropped at room temperature, and the mixture was stirred at the same temperature for 30 minutes. The reaction solution was diluted with 500 ml of ethyl acetate and washed with 50 ml of water and then with 50 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated using a rotary evaporator to obtain 2.21 g of a pale yellow oil. This was purified by silica gel column chromatography (toluene: ethyl acetate = 90: 10 (volume ratio)) to obtain 478.1 mg of Compound 1 as a pale yellow solid. (Yield 54%)

( ¹ H-NMR spectrum data of Compound 1)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.714 (s, 2H), 8.675 (s, 2H), 8.291 (d, 4H, J = 6.8 Hz), 7. 988 (m, 5H), 7.890 (d, 4H, J = 8.0 Hz), 7.548 (d, 1H, J = 8.4 Hz), 7.354 (dd, 1H, J = 8.4) , 13.4 Hz), 7.223 (d, 4H, J = 8.8 Hz), 6.458-6.414 (m, 3H), 6.165-6.009 (m, 3H), 5.866 -5.799 (m, 3H), 4.447-4.278 (m, 12H), 2.925 (t, 4H, J = 6.4 Hz), 2.798 (t, 4H, J = 6. 4Hz)

Example 2 Synthesis of Compound 2

(Step 1) Synthesis of Intermediate F

  In the synthesis of intermediate A in Example 1, intermediate F was synthesized in the same manner as in the synthesis of intermediate A in Example 1, except that 2-hydroxyethyl acrylate was changed to ethylene glycol mono n-propyl ether. did. (Yield 40%)

⁽¹ H-NMR spectral data of the intermediate F)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 10.210 (s, 1H), 7.292 (d, 1H, J = 2.8 Hz), 6.984 (dd, 1H, J = 2) .8, 8.8 Hz), 6.835 (d, 1 H, J = 8.8 Hz), 5.827 (br, 1 H), 4.481 (t, 2 H, J = 4.8 Hz), 3.793 (T, 2H, J = 4.8 Hz), 3.514 (t, 2H, J = 6.8 Hz), 1.673-1.620 (m, 2H), 0.940 (t, 3H, J = 7.4Hz)

(Step 2) Synthesis of Intermediate G

  In the synthesis of Intermediate B of Example 1, Intermediate G was synthesized in the same manner as the synthesis of Intermediate B of Example 1 except that Intermediate A was changed to Intermediate F. (Yield 54%)

⁽¹ H-NMR spectral data of the intermediate G)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 10.166 (s, 1H), 10.160 (s, 1H), 8.047 (d, 2H, J = 8.4 Hz), 8. 385 (d, 2H, J = 8.4 Hz), 8.056 (d, 2H, J = 8.4 Hz), 8.049 (d, 2H, J = 8.4 Hz), 8.005 (d, 1H) , J = 2.8 Hz), 7.545 (dd, 1H, J = 2.8, 8.8 Hz), 7.340 (d, 1H, J = 8.8 Hz), 4.343 (t, 2H, J = 4.8 Hz), 3.559 (t, 2H, J = 4.8 Hz), 3.292 (t, 2H, J = 6.4 Hz), 1.564-1.475 (m, 2H), 0.878 (t, 3H, J = 6.4Hz)

(Step 3) Synthesis of Intermediate H

  In the synthesis of intermediate C in Example 1, intermediate H was synthesized in the same manner as in the synthesis of intermediate C in Example 1, except that intermediate B was changed to intermediate G. (Yield 41%)

( ¹ H-NMR spectrum data of intermediate H)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.716 (s, 2H), 8.659 (s, 2H), 8.320-8.270 (m, 4H), 8.001- 7.981 (m, 5H), 7.769 (d, 4H, J = 8.6 Hz), 7.532 (dd, 1H, J = 2.8, 8.4 Hz), 7.328 (d, 1H) , J = 8.4 Hz), 6.926 (d, 4H, J = 8.6 Hz), 4.344 (t, 2H, J = 4.8 Hz), 3.532 (t, 2H, J = 4. 8 Hz), 3.275 (t, 2H, J = 7.0 Hz), 1.563-1.473 (m, 2H), 1.004 (s, 18H), 0.860 (t, 3H, J = 7.4 Hz), 0.248 (s, 12H)

(Step 4) Synthesis of Compound 2

  In the synthesis of Compound 1 of Example 1, Compound 2 was synthesized in the same manner as the synthesis of Compound 1 of Example 1 except that Intermediate C was changed to Intermediate H. (Yield 64%)

( ¹ H-NMR spectrum data of Compound 2)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.719 (s, 2H), 8.680 (s, 2H), 8.288 (d, 4H, J = 6.8 Hz), 8. 005 (m, 5H), 7.890 (d, 4H, J = 8.0 Hz), 7.528 (d, 1H, J = 8.6 Hz), 7.362 (dd, 1H, J = 8.6) , 13.2 Hz), 7.223 (d, 4H, J = 8.8 Hz), 6.438 (d, 2H, J = 17.2 Hz), 6.131 (dd, 2H, J = 10.4, 17.2 Hz), 5.858 (d, 2 H, J = 10.4 Hz), 4.390 (s, 10 H), 3.536 (t, 2 H, J = 5.0 Hz), 3.278 (t, 2H, J = 6.8 Hz), 2.926 (t, 4H, J = 6.4 Hz), 2.793 (t, 4H, J = 6.4 Hz) , 1.606-1.529 (m, 2H), 0.890 (t, 3H, J = 7.4Hz)

<Evaluation of compound>
(1) Measurement of phase transition temperature 10 mg of each of the compounds 1 and 2 (test compound) was weighed and sandwiched between two glass substrates with a polyimide alignment film that had been subjected to rubbing treatment in a solid state. The substrate was heated from 30 ° C. to 250 ° C. on a hot plate, and then lowered to 30 ° C. again. Changes in the structure of the structure when the temperature was raised or lowered were observed with a deflection optical microscope (ECLIPSE LV100POL type manufactured by Nikon Corporation). The measured phase transition temperatures are shown in Table 1.

  In Table 1, “C” represents Crystal, “N” represents Nematic, and “I” represents Isotropic. Here, “Crystal” indicates that the test compound is in the solid phase, “Nematic” indicates that the test compound is in the nematic liquid crystal phase, and “Isotropic” indicates that the test compound is in the isotropic liquid phase. .

(2) Measurement of optical anisotropy (Δn value) 100 parts by weight of each of compounds 1 and 2 were dissolved in 233 parts by weight of cyclopentanone to prepare a solution. A solution in which 2.7 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: Irgacure 907) was added to the liquid crystal compound and dissolved therein was prepared. The prepared solution was applied onto a glass substrate having a polyvinyl alcohol film subjected to rubbing treatment using a bar coater (manufactured by Tester Sangyo: Bar coater Rod No. 4, shaft diameter 12.7 mm), and then on a hot plate. And dried at 100 ° C. for 2 minutes. The obtained film was irradiated with ultraviolet rays corresponding to 700 mJ / cm ² with a mercury lamp to obtain a cured polymer film having a thickness of 1.5 μm. The cured film was measured for retardation (Re) at a wavelength of 545.3 nm using an ellipsometer (XLS-100 type, manufactured by JA Woollam). Thereafter, Δn was calculated from the thickness (d) of the liquid crystal layer obtained separately by the calculation formula Δn = Re / d. The calculation results are shown in Table 1.

(3) Formation of Cholesteric Layer 100 parts by weight of each of Compounds 1 and 2 were dissolved in 153 parts by weight of cyclopentanone to obtain a solution. To this, 3.3 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: Irgacure 1919), 6.0 parts by weight of a chiral agent, and a surfactant (used as a 1% by weight cyclopentanone solution) 11 A solution was prepared by adding 6 parts by weight. The compound represented by the formula (X) was used as a chiral agent, and KH-40 (manufactured by Seimi Chemical Co., Ltd.) was used as a surfactant.

Next, the prepared solution was applied on a glass substrate with a polyimide alignment film subjected to a rubbing treatment using a bar coater (manufactured by Tester Sangyo Co., Ltd .: SA-203 bar coater Rod No. 8, shaft diameter 12.7 mm). Then, it was dried on a hot plate at 100 ° C. for 3 minutes. The obtained film was irradiated with ultraviolet rays corresponding to 1000 mJ / cm ² with a mercury lamp to obtain a cured film having a thickness of 4 μm.

The transmission spectrum of the cured film of the test compound obtained above was measured using a spectrophotometer (Otsuka Electronics Co., Ltd., instantaneous multi-photometry system MCPD-3000). A selective reflection region (a region where the transmittance is about 50%) was observed, and it was found that a cholesteric layer was formed. Its bandwidth was about 50-100 nm.
The measurement results are shown in Table 1.

(3) Solubility Solubility of compounds 1 and 2 was evaluated as follows.
That is, a test compound (compounds 1 and 2) in an amount that gives a cyclopentanone solution having a concentration of 40% by weight if completely dissolved is added to cyclopentanone under heating at 60 ° C. The solubility was evaluated by ◯ when it was dissolved in pentanone and x when it could not be dissolved.
The evaluation results are shown in Table 1.

(4) Evaluation of compatibility The compatibility of compounds 1 and 2 was evaluated as follows.
That is, the presence / absence of turbidity in the cured film of the test compound obtained above was visually observed at 23 ° C., and the compatibility was evaluated by ◯ when no turbidity was observed in visual observation and x when turbidity occurred.
The evaluation results are shown in Table 1.

From Table 1, it can be seen that Compounds 1 and 2 not only exhibit high solubility in a solvent, but also have excellent compatibility with additives such as a polymerization initiator and a chiral agent, and excellent handling properties.
Moreover, the cured film of any compound showed favorable liquid crystallinity over a wide temperature range, and formed a cholesteric layer. The obtained cured film was a good liquid crystal film exhibiting high optical anisotropy (Δn).

(Comparative Example 1)
As the liquid crystal compound, the following polymerizable liquid crystal compound (compound 3, manufactured by BASF, trade name: LC242) is used, and the compounds 1 and 2 are evaluated in the same manner as in the methods (1) to (4). And evaluated. The evaluation results are shown in Table 2.

(Comparative Example 2)
Further, the phase transition temperature of a conventional azine liquid crystal compound (Compound 4, the compound described in Example 2 of JP-A-10-147562) is extracted from JP-A-10-147562 and shown in Table 2. It was.

Compound 3
The structure of 4 is shown below.

The polymerizable liquid crystal compound of the present invention is a liquid crystal material that has a wide temperature range showing a liquid crystal phase, is chemically stable, can be produced at low cost, and has a wide selective reflection wavelength band Δλ, that is, a large Δn. .
According to the polymerizable liquid crystal composition of the present invention, a liquid crystal layer having a wide temperature range showing a liquid crystal phase and a wide selective reflection wavelength band Δλ, that is, a large Δn can be formed.
Since the liquid crystalline polymer of the present invention has excellent orientation and high optical anisotropy (Δn), it is a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, a viewing angle widening plate, a color filter, a low pass. It is useful as a raw material for producing optical anisotropic bodies such as filters, light polarizing prisms, and various optical filters. Since the optical anisotropic body of the present invention is produced using the polymerizable liquid crystal compound of the present invention, it has uniform and high-quality liquid crystal alignment.

Claims (7)

Formula (I)

{In the formula, M represents [a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, or -C (= O) -OR ^3]. (R ³ represents the same meaning as R ³ described later .)] Represents a p-phenylene group or a 4,4′-biphenylene group which may be substituted .
Y _{1 to} Y ₈ each independently represent —C (═O) —O—, —O—C (═O) —, or —O— .
G ₁ and G ₂ each independently represent an alkylene group having 2 to 20 carbon atoms .
Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH ₂ ═C (Cl) —, CH ₂ ═CH—CH ₂ —, CH ₂ ═C ( _{CH 3) -CH 2 -, CH} 2 = C (CH 3) -CH 2 -CH 2 -, (CH 3) 2 C = CH-CH 2 -, CH 3 -CH = CH-, or _CH 3 -CH = CH-CH ₂ - represents a.
A ₁ and A ₂ each independently represents an alkylene group having 1 to 10 carbon atoms .
X _{1 to} X ₁₆ are either (1) all hydrogen atoms, or (2) X ₂ , X _{4 to} X ₁₃ and X ₁₅ are all hydrogen atoms, and X ₁ , X ₃ , X ₁₄ and X _At least one of ₁₆ is —OR ³ or C (═O) —O—R ³ , and among X ₁ , X ₃ , X ₁₄ and X ₁₆ , —OR ³ and C (═O) —O What is not -R ³ is a hydrogen atom . Here, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with (a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a 4-methylphenyl group). And R ³ is an alkyl group, the alkyl group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C. Even if (═O) —O—, —NR ⁵ —C (═O) —, —C (═O) —NR ⁵ —, —NR ⁵ —, or —C (═O) — are present. Good (except that -O- and -S- are not less than two adjacent to each other). Here, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
a, b, c and d are each independently 0 or 1; }
A polymerizable liquid crystal compound represented by: Wherein M is [a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, ^{or, -C (= O) -OR 3} (R 3 Represents the same meaning as described above))], and is a phenylene group optionally substituted.
a = d = 1, b = c = 0 ,
G ₁ and G ₂ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ — ,
_2. The polymerizable liquid crystal compound according to claim _1, wherein Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —. The M is a phenylene group which may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group includes —O—, —C (═O) —O—, —O—C. (= O)-or -C (= O)-may be interposed,
The polymerizable liquid crystal compound according to claim ₂ , wherein Z ₁ and Z ₂ are both CH ₂ ═CH—. The polymerizable liquid crystal compound according to claim 2, wherein the M is a phenylene group optionally substituted with —C (═O) —OR ³ (R ³ represents the same meaning as described above). The polymerizable liquid crystal compound according to any one of claims 1-4, and a polymerizable chiral compound containing a polymerizable liquid crystal composition. The polymerizable liquid crystal compound according to any one of claims 1-4, or liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal composition according to claim 5. An optical anisotropic body comprising the liquid crystalline polymer according to claim 6 as a constituent material.