JP4576928B2 - Optically active liquid crystalline compounds, compositions and polymers thereof - Google Patents

Description

  The present invention relates to an optically active liquid crystalline compound having a fluorene ring, a liquid crystal composition containing the compound, a polymer thereof, and a liquid crystal display device containing the polymer having optical anisotropy.

  In recent years, polymerizable liquid crystalline compounds have been used for molded articles having optical anisotropy such as polarizing plates and retardation plates. This is because this compound has optical anisotropy in a liquid crystal state, and the orientation of this compound is fixed by polymerization. Since the optical characteristics required for the molded article having optical anisotropy vary depending on the purpose, a compound having the characteristics suitable for the purpose is required. In general, this compound is polymerized to obtain a polymer, which is then molded and used. In addition to the above-mentioned anisotropy, the compound used for such a purpose is also important for the polymer-related characteristics. This property includes compound polymerization rate, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, Such as chemical resistance.

Moreover, when manufacturing an optical compensation film, in order to induce a helical structure, a polymerizable optically active compound having liquid crystallinity is added to fix the helical structure. Properties important as a compound used for such a purpose include helical induction (HTP), liquid crystallinity, compatibility with liquid crystals, temperature dependence of the induced helical structure, and the like.
In recent years, a circularly polarized light separating functional element using a polymerizable cholesteric liquid crystal has been used as a brightness enhancement film (Non-Patent Document 1). A cholesteric liquid crystal can be usually prepared by adding an optically active compound to a nematic liquid crystal. In order to obtain a circularly polarized light separating function from the ultraviolet region to the visible light region, a very short pitch helical structure (280 to 800 nm) is required. When an optically active compound having a small HTP is used, the amount added must be increased, and it becomes difficult to adjust other physical properties, particularly the CN point and optical anisotropy. If the amount of the optically active compound not exhibiting liquid crystallinity is increased, the liquid crystallinity of the composition is lost, and the intended cholesteric liquid crystal phase cannot be obtained.

  The optically active compound used for the above-mentioned purpose is required to have a large helical induction force (HTP), liquid crystallinity, and compatibility with other liquid crystal compounds. A liquid crystal composition containing an optically active compound is required to have cholesteric liquid crystallinity, orientation, and coatability on a substrate. The polymer film is required to have mechanical strength, shrinkage, water absorption, gas permeability, melting point, glass transition point, clearing point, chemical resistance and the like.

Y. Hisatake et al, Asia Display / IDW '01 LCT8-2

  The first object of the present invention is a polymerizable liquid crystal compound having a fluorene skeleton having a large helical induction force, excellent compatibility with other compounds, and further having necessary characteristics such as liquid crystallinity, and It is to provide a liquid crystal composition containing a compound. The second purpose is a polymer excellent in properties such as transparency, mechanical strength, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, chemical resistance, and It is providing the molded object which has the optical anisotropy manufactured from the union. A third object is to provide a liquid crystal display element containing this polymer.

As a result of intensive studies to fundamentally solve the above problems, the present inventor has found that the fluorene derivative of the present invention exhibits liquid crystallinity, has a large helical induction force, and has excellent compatibility with other compounds. ing. In addition, the liquid crystal composition containing the compound of the present invention has a helical structure with a very short pitch, and is excellent in coatability, orientation, and polymerizability, and the polymer is an optically anisotropic film exhibiting a circularly polarized light separation function. As a result, the present invention was completed. The present invention is as described in the following items [1] to [37].

[1] An optically active compound represented by the formula (1).

In the formula (1), R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl is —O—, —S. -, -COO-, -OCO-, -CO-, -CH = CH- or -C≡C- may be replaced, and any hydrogen in the alkyl may be replaced by a halogen; A ¹ And A ² are independently 1,4-cyclohexylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-cyclohexenylene, 1,4-phenylene, at least 1 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2 in which two hydrogens are replaced by halogen, methyl or trifluoromethyl 6-diyl, is a tetrahydronaphthalene-2,6-diyl or 1,3-dioxane-2,5-diyl,; ^{X 1} and ^{X 4} independently represent a single bond, -O -, - S -, - COO -Or -OCO-; X ² and X ³ are independently -COO-, -OCO-, -CH ₂ CH ₂ -or -C≡C-; Y ¹ and Y ² are independently It is an optically active group represented by the formula (C1), (C2), (C3), (C4), (C5), (C6) or (C7). P is independently present; P is independently of the formula (P1), (P2), (P3), (P4), (P5), (P6), (P7), (P8), (P9), (P10) or ( P11) is a polymerizable group.

[2] In the formula (1), R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 15 carbons, and in this alkyl, any —CH ₂ — is —O—. , -S-, -COO-, -OCO-, -CO-, -CH = CH- or -C≡C-, and any hydrogen in the alkyl may be replaced by halogen. Well, A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-cyclohexenylene, 1,4- Phenylene, 1,4-phenylene in which one hydrogen in the group is replaced by fluorine, chlorine, methyl or trifluoromethyl, 1,4-phenylene in which two hydrogens in the group are replaced by fluorine or trifluoromethyl Nylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or 1,3-dioxane-2 , 5-diyl, X ¹ and X ⁴ are independently a single bond or —O—, and X ² and X ³ are independently —COO—, —OCO—, or —C≡C—. , Y ¹ and Y ² are each independently an optically active group represented by the formula (C1), (C2), (C3), (C4), (C5), (C6) or (C7), In these formulas, * indicates the presence of asymmetric carbon; P independently represents formulas (P1), (P2), (P3), (P4), (P5), (P6), (P7), (P8 ), (P9), (P10) or (P11) is a polymerizable group represented by the item [1]. Of the compound.

[3] In Formula (1), R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 10 carbon atoms, and A ¹ and A ² are independently 1,4-cyclo Hexylene, 1,4-phenylene, one hydrogen in the group is replaced by fluorine, chlorine, methyl or trifluoromethyl, two hydrogens in the group are replaced by fluorine or trifluoromethyl 1,4-phenylene, X ¹ and X ⁴ are independently a single bond or —O—, and X ² and X ³ are independently —COO—, —OCO—, or —C≡C—. Y ¹ and Y ² are each independently an optically active group represented by the formula (C2), (C3) or (C4), and in these formulas, * indicates the presence of an asymmetric carbon. P is independently the formulas (P1), (P2), (P ), (P4), (P5), (P6), (P7), (P8), (P9), (P10), or a polymerizable group represented by (P11), Compound.

[4] In the formula (1), R ¹ and R ² are independently hydrogen, fluorine or alkyl having 1 to 2 carbon atoms, and A ¹ and A ² are independently 1,4-cyclohexylene. 1,4-phenylene, 1,4-phenylene in which one hydrogen in the group is replaced by fluorine or chlorine, X ¹ and X ⁴ are independently —O—, and X ² and X ³ are Independently —COO— or —OCO—, Y ¹ and Y ^{2 are each} independently an optically active group represented by the formula (C2), (C3) or (C4). * Indicates the presence of an asymmetric carbon; P is a compound according to item [1], which is independently a polymerizable group represented by formula (P1), (P2) or (P3).

[5] In the formula (1), R ¹ and R ² are independently hydrogen, fluorine, or alkyl having 1 to 2 carbon atoms, and A ¹ and A ² are independently 1,4-cyclohexylene. 1,4-phenylene, 1,4-phenylene in which one hydrogen in the group is replaced by fluorine or chlorine, X ¹ and X ⁴ are independently —O—, and X ² and X ³ are Independently —COO— or —OCO—, Y ¹ and Y ² are each independently an optically active group represented by (C6) or (C7). The compound according to item [1], wherein P is a polymerizable group represented by (P11).

[6] The compound according to item [1], wherein P is independently (P1), (P2), (P3) or (P10).

[7] The compound according to item [1], wherein P is independently (P4), (P5), (P6), (P7), (P8), (P9) or (P11).

[8] Any compound represented by the following formula. However, in these formulas, * indicates the presence of an asymmetric carbon.

[9] A liquid crystal composition comprising at least two compounds, wherein at least one compound is the compound according to any one of items [1] to [8].

[10] The liquid crystal composition according to item [9], wherein all of the compounds are polymerizable compounds.

[11] At least one of the compounds according to any one of [1] to [8], and the formulas (M1), (M2), (M3), (M4), (M5), (M6), A liquid crystal composition containing at least one polymerizable compound selected from the compounds represented by (M7), (M8) and (M9).

In the above formula, R ³ is independently hydrogen, fluorine, chlorine, cyano, or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — represents —O—, —S—, — COO—, —OCO—, or —CO— may be replaced, and any hydrogen may be replaced with a halogen; R ⁴ is independently hydrogen or alkyl of 1 to 5 carbons; A ³ , A ⁴ and A ⁵ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by halogen, pyridine-2,5-diyl, Pyrimidine-2,5-diyl, naphthalene-2,6-diyl or fluorene-2,7-diyl; B is independently a single bond, 1,4-phenylene, at least one hydrogen is halogen, methyl Shi It was replaced with trifluoromethyl 1,4-phenylene, naphthalene-2,6-diyl, biphenyl-4,4'-diyl, fluorene-2,7-diyl, 9-methyl-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene-2,7-diyl or 9,9-difluorofluorene-2,7-diyl ; X ⁶ is independently a single bond or —O—; Z ¹ and Z ² are independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, or —C≡C—. in it; m is independently 1 or 0, n and p is independently an integer from 1 to 20.

[12] R ³ is hydrogen, fluorine, chlorine or alkyl or alkoxy having 1 to 20 carbon atoms, R ⁴ is independently methyl or ethyl, and A ³ , A ⁴ and A ⁵ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which 1 or 2 hydrogens are replaced with fluorine, or 1,4-phenylene in which 1 or 2 hydrogens are replaced with chlorine , B is 1,4-phenylene, 1,4-phenylene in which 1 or 2 hydrogens are replaced by fluorine, 1,4-phenylene in which 1 or 2 hydrogens are replaced by methyl, 1 or 2 1,4-phenylene substituted with trifluoromethyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl or 9-ethylfluorene-2,7-diyl , Z ¹ and Z ² are each independently a single bond, —COO— or —OOC—, [11].

[13] The total content of the compounds represented by the formula (1) in the item [1] is 3 to 90% by weight, and the compounds represented by any one of the formulas (M1) to (M9) The liquid crystal composition according to item [11] or [12], wherein the total content is 10 to 97% by weight.

[14] In the formula (1) of the item [1], P is represented by formulas (M1) and (M2), a compound in which P is at least one of (P1), (P2) and (P3) The liquid crystal composition according to item [11] or [12], comprising at least one compound selected from each compound.

[15] In the formula (1) of the item [1], P contains (P1) and at least one compound selected from the compounds represented by formulas (M1) and (M2) The liquid crystal composition according to item [11] or [12].

[16] In the formula (1) of the item [1], the total content of each compound represented by P is (P1), (P2) and (P3) is 3 to 90% by weight, and the formula (M1 ) And (M2) The liquid crystal composition according to item [14] or [15], wherein the total content of each compound is 10 to 97% by weight.

[17] In the formula (1) of the item [1], at least one of the compounds in which P is (P4) and (P5), and at least one of the compounds represented by the formula (M5); The liquid crystal composition according to item [11] or [12], comprising at least one compound selected from the compounds represented by formulas (M3) and (M4).

[18] In the formula (1) of the item [1], the total content of each compound in which P is (P4) and (P5) and the compound represented by the formula (M5) is 10 to 90% by weight. The liquid crystal composition according to item [17], wherein the total content of the compounds represented by formulas (M3) and (M4) is 10 to 90% by weight.

[19] In the formula (1) of the item [1], at least one of the compounds in which P is (P6), (P7), (P8), (P9) and (P11), and the formula (M3) Or [M4), (M6), (M7), (M8), or at least one compound selected from the group of compounds represented by (M9). Composition.

[20] In the formula (1) of the item [1], P contains (P11) and at least one compound selected from the compounds represented by formulas (M8) and (M9) The liquid crystal composition according to item [11] or [12].

[21] In the formula (1) of the item [1], any two selected from the compound in which P is (P11) and the compounds represented by the formulas (M6), (M7), and (M9) The liquid crystal composition according to [11] or [12], comprising a compound.

[22] In the formula (1) of the item [1], the total content of each compound in which P is (P6), (P7), (P8), (P9) and (P11) is 10 to 90% by weight. And the total content of the compounds represented by formulas (M3), (M4), (M6), (M7), (M8) and (M9) is 10 to 90% by weight [19] to The liquid crystal composition according to item [21].

[23] In the formula (1) of the item [1], P contains (P10) and at least one compound selected from the compounds represented by formulas (M1) and (M2) The liquid crystal composition according to item [11] or [12].

[24] In the formula (1) of the item [1], the content of the compound in which P is (P10) is 10 to 90% by weight, and the content of each compound represented by the formulas (M1) and (M2) The liquid crystal composition according to item [23], wherein the total amount is 10 to 90% by weight.

[25] In the formula (1) of the item [1], P contains (P10) and at least one compound selected from the compounds represented by formulas (M3) and (M4) [11] The composition according to item [12].

[26] The content of each compound represented by the formulas (M3) and (M4), in which the content of the compound in which P is (P10) in the formula (1) in the item [1] is 10 to 90% by weight. The liquid crystal composition according to item [25], in which the total amount is 10 to 90% by weight.

[27] A polymer obtained by polymerizing the liquid crystal composition according to any one of items [9] to [26].

[28] A polymer obtained by polymerizing at least one compound according to item [1].

[29] The polymer according to the item [27] or [28], which has a weight average molecular weight of 500 to 1,000,000.

[30] The polymer according to item [27] or [28], which has a weight average molecular weight of 1,000 to 500,000.

[31] In the item [29] or [30], the liquid crystal composition described in any one of items [9] to [26] or the compound represented by formula (1) is polymerized by irradiating with electromagnetic waves. An optically anisotropic film comprising the polymer as described.

[32] An optical anisotropy obtained by aligning the liquid crystal composition according to any one of items [9] to [26] or the compound of formula (1) and then fixing the alignment of the liquid crystal phase by irradiation with electromagnetic waves. Sex film.

[33] The optically anisotropic film according to item [31] or [32], wherein the irradiated electromagnetic wave is an electron beam or an ultraviolet ray.

[34] The optically anisotropic film according to any one of [31] to [33], wherein the alignment of the liquid crystal fixed by electromagnetic waves is planar alignment.

[35] An optical element comprising the optically anisotropic film according to any one of items [31] to [34].

[36] The optical element according to item [35], wherein the optically anisotropic film has circular dichroism.

[37] The optical element according to item [35] or [36], which exhibits circular dichroism in a visible light region that selectively reflects light in a part or all of a wavelength of 350 to 750 nm.

[38] In a helical structure induced by a chiral nematic phase or a cholesteric phase, the pitch is continuously changed in the thickness direction of the molded article having optical anisotropy, so that light in all regions having a wavelength of 350 to 750 nm can be obtained. The optical element according to the item [35], which selectively reflects.

[39] The optical element according to the item [37], which is made of a polymer having two or more layers having different wavelength regions exhibiting circular dichroism and selectively reflects light in all regions having a wavelength of 350 to 750 nm.

[40] An optical element in which a layer functioning as a quarter-wave function plate is provided on the optical element according to any one of items [35] to [39].

[41] The optical element according to any one of [35] to [39], which functions as a brightness enhancement film.

[42] The optical element according to [35] or [36], which exhibits circular dichroism in an ultraviolet light region having a wavelength of 100 to 350 nm.

[43] A liquid crystal display element comprising the optical element according to any one of items [35] to [39].

  The compound (1) of the present invention exhibits large HTP, orientation and compatibility. Since the polymerizable liquid crystal composition containing the compound (1) exhibits a liquid crystal phase, the compound (1) itself exhibits a liquid crystal phase, so even if it is added in a large amount to the composition composed of the compounds (M1) to (M9). Can be prepared. By adjusting the addition amount of the compound of the present invention, a cholesteric liquid crystal composition having a pitch capable of reflecting light in an arbitrary region from an ultraviolet ray to a visible ray region (wavelength 280 to 750 nm) can be prepared. Since it is composed of a liquid crystalline compound having a polymerizable group having high polymerization reactivity, it can be cured quickly by an electron beam such as ultraviolet rays by adding an appropriate polymerization initiator. An optically anisotropic film obtained by orientation-curing these compositions can be used for an optically anisotropic film such as a brightness enhancement film.

  The term liquid crystalline compound is used as a general term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be referred to as a compound, a composition, and an element, respectively. Formula (1), Formula (M1), Formula (M2), Formula (M3), Formula (M4), Formula (M5), Formula (M6), Formula (M7), Formula (M8), and Formula (M9) The compounds represented are compound (1), compound (M1), compound (M2), compound (M3), compound (M4), compound (M5), compound (M6), compound (M7), compound (M8) and It may be described as a compound (M9). Acrylate and methacrylate may be referred to as (meth) acrylate.

The meaning of the phrase “any —CH ₂ — in alkyl may be replaced by —O—, —CH═CH—, etc.” is shown by way of example. A part of the group in which any —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— is C ₃ H ₇ O—, CH ₃ —O— (CH ₂ ) ₂ —, _{CH 3 -O-CH 2 -O-,} H 2 C = CH- (CH 2) 3 -, CH 3 -CH = CH- (CH 2) 2 -, and _{CH 3 -CH = CH-CH 2} -O -. Thus, the term “arbitrary” means “at least one selected without distinction”. In consideration of the stability of the compound, oxygen and oxygen adjacent _CH 3 -O-O-CH2- than towards oxygen and oxygen of _CH 3 _-O-CH 2 -O- nonadjacent is preferable.

Compound (1) has the following characteristics.
(1) The compound (1) is a liquid crystal compound having a fluorene ring and having two optically active alkylenes.
(2) The compound (1) exhibits a large helical induction force when dissolved in a liquid crystal compound.
(3) The compound (1) is physically and chemically very stable under the conditions usually used, and has good compatibility with other compounds.
(4) By appropriately selecting a ring, a linking group or a side chain constituting the compound (1), a large dielectric anisotropy, a small dielectric anisotropy, a large optical anisotropy, a small optical anisotropy, A physical property value such as a small viscosity can be adjusted.

First, the optically active fluorene derivative of the present invention will be described.
The optically active fluorene derivative of the present invention is represented by the formula (1).

R ¹ and R ^{2 in} this formula are independently hydrogen, fluorine, chlorine or alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —S—, — COO—, —OCO—, —CO—, —CH═CH— or —C≡C— may be replaced, and any hydrogen in the alkyl may be replaced with a halogen.

Preferred examples of R ¹ and R ² are hydrogen, fluorine, chlorine, or alkyl having 1 to 15 carbons. In this alkyl, any —CH ₂ — may be replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH— or —C≡C—. A plurality of —CH ₂ — in the alkyl may be replaced with a different group of —O—, —S—, —COO—, —OCO—, and CO—. An example is —O—CH ₂ CH ₂ —COO—. However, two consecutive —CH ₂ — are not replaced like —O—O—, —O—S— or —S—S—. Any hydrogen in the alkyl may be replaced with halogen. Halogen is preferably chlorine or fluorine.

More preferred examples of R ¹ and R ² are hydrogen, fluorine, and alkyl having 1 to 10 carbons. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl are preferable, and hydrogen, fluorine, and alkyl having 1 to 2 carbon atoms are more preferable. The temperature range of the liquid crystal phase can be adjusted by the difference in R ¹ and R ² between hydrogen, methyl, and ethyl. In the case of fluorine, an effect of lowering the melting point of the compound (1) can be expected.

A ¹ and A ² in the formula (1) are divalent groups having a ring structure. These are independently 1,4-cyclohexylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen Is replaced by fluorine, chlorine, methyl or trifluoromethyl, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2,6- Diyl, tetrahydronaphthalene-2,6-diyl or 1,3-dioxane-2,5-diyl. Preferred examples of A ¹ and A ² are shown below.

Ａ１及びＡ２のさらに好ましい例は、１，４−シクロへキシレン、１，４−フェニレン、基中の１つの水素がフッ素、塩素、メチルまたはトリフルオロメチルで置き換えられた１，４−フェニレンまたは基中の２つの水素がフッ素またはトリフルオロメチルで置き換えられた１，４−フェニレンである。

More preferred examples of A1 and A2 are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene or a group in which one hydrogen in the group is replaced by fluorine, chlorine, methyl or trifluoromethyl. 1,2-phenylene in which two hydrogens are replaced by fluorine or trifluoromethyl.

These ring structures may be bonded in the opposite directions in Formula (1). When the compound (1) has 1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, the steric configuration is preferably a trans type rather than a cis type. Compound (1) may contain an isotope element such as ² H (deuterium) or ¹³ C in an amount higher than the naturally existing ratio, and even in this case, there is no significant difference in the physical properties of the compound.

X ¹ , X ² , X ³ and X ⁴ in the formula (1) are linking groups. X ¹ and X ⁴ are each independently a single bond, —O—, —S—, —COO— or —OCO—. Among them, more preferred examples are a single bond and O-. X ² and X ³ are independently —COO—, —OCO—, —CH ₂ CH ₂ — or —C≡C—. It is particularly preferable that at least one of X ² and X ³ is —COO— or —OCO— because liquid crystallinity tends to be improved.

Y ¹ and Y ² are optically active alkylenes, and are specifically represented by formulas (C1) to (C7).

  The optical purity of the optically active ω-chloroalkanol used as a raw material is 1 to 99% ee (enantiomeric excess) and should not be racemic, but 90% ee or more is required to obtain a large HTP compound (1). Optical purity is preferred.

  P is a polymerizable group, and its specific structure is shown below.

  The polymerizable groups (P1) to (P3) and (P10) are suitable for radical polymerization, and the polymerizable groups (P4) to (P9) and (P11) are suitable for cationic polymerization. Although the compound (1) having these polymerization groups has a high polymerization reactivity, it can be polymerized more quickly by adding an appropriate polymerization initiator.

  A compound (1) having the desired physical properties can be obtained by appropriately selecting a ring, a side chain, a linking group and a polymerizable group.

Next, a method for producing compound (1) will be described. In the formula (1), a method for producing a compound in which X ¹ and X ⁴ are —O—, X ² is —COO—, X ³ is —OOC—, and Y ¹ = Y ² is shown. Furthermore, optically active ω-chloroalkanol [a] can be produced by the method described in Liquid Crystals, Vol 18, No 2, 319 to 326, 1995. [B] is obtained by etherifying [a] and a hydroxybenzoic acid ester derivative in the presence of an appropriate base. Examples of bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium hydride and the like. [C] is produced by hydrolyzing [b]. When the polymerizable group is acrylic, methacrylic or trifluoromethacrylic acid, the benzoic acid derivative [d1] having a polymerizable group is produced by esterification reaction of the corresponding acid or acid chloride with [c]. When the polymerizable group is vinyl ether, it can be produced by converting [b] into vinyl ether using n-butyl vinyl ether and a palladium catalyst, followed by hydrolysis. When the polymerizable group is glycidyl ether, it is etherified with toluene-4-sulfonic acid glycidyl ester [G1] and then hydrolyzed, and in the case of oxetane, toluene-4-sulfonic acid 3-methyl-oxetane-3 -Benzyl acid derivative having a corresponding polymerizable group by etherification with ylmethyl ester [G2], toluene-4-sulfonic acid 3-ethyl-oxetane-3-ylmethyl ester [G3] [ d2] can be manufactured. Compound (1) is produced by esterification reaction of 2,7-dihydroxyfluorene derivative [e] with a benzoic acid derivative of [d1] or [d2].

In order to produce a compound in which X ¹ and X ⁴ are —O—, X ² is —COO—, X ³ is —OOC— and Y ¹ ≠ Y ² in Formula (1), ^one hydroxyl group Was prepared by esterification of a fluorene derivative [f] protected with a tetrahydropyranyl group and a benzoic acid derivative of [d1] or [d2], followed by deprotection and further selected by the first esterification An asymmetric (Y ¹ ≠ Y ² ) compound (1) is produced by an esterification reaction with a benzoic acid derivative [d1] or [d2] other than the above.

In Formula (1), X ¹ and X ⁴ are —O—, X ² is —COO—, X ³ is —OOC—, Y ¹ is (C6), and Y ² is (C7). The manufacturing method of the compound whose P is (P11) is shown. First, (S) -citronellol is brominated to give (S) -citronellyl bromide [g], and [g] and a hydroxybenzoic acid ester derivative are etherified in the presence of a suitable base [h] ] Is obtained. Examples of bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium hydride and the like. After hydrolyzing [h], [i] is obtained by an esterification reaction with a 2,7-dihydroxyfluorene derivative [e]. (1) is produced by oxidizing [i] with a peroxide such as m-chloroperbenzoic acid.

  Compound No. which can be synthesized 1-No. 94 is shown below.

The composition has the following characteristics.
1) Since the compound (1) itself exhibits a liquid crystal phase, the liquid crystallinity of the composition can be maintained even when it is added in a large amount to the composition composed of the compounds (M1) to (M9). Therefore, the addition amount of the compound (1) can be added in the range of 3 to 90% by weight, and the pitch of the cholesteric phase can be adjusted to the required wavelength in the range of 100 to 750 nm depending on the addition amount.
2) Since it is composed of a liquid crystalline compound having a polymerizable group having high polymerization reactivity, it can be cured quickly by an electron beam such as ultraviolet rays by adding an appropriate polymerization initiator. 3) Excellent in planar orientation.

The present invention is a liquid crystal composition containing at least two compounds, wherein at least one compound is a compound represented by the formula (1). More specifically, at least one of the compounds represented by formula (1) and the formula (M1), formula (M2), formula (M3), formula (M4), formula (M5), formula (M6), formula A liquid crystal composition containing (M7), at least one polymerizable compound selected from the compounds represented by formula (M8) and formula (M9).

  Among the compounds (M1), particularly preferable compounds are monofunctional liquid crystal acrylate compounds represented by the formulas (M1a) to (M1f).

  Particularly preferred compounds among the compounds (M2) are compounds represented by the formulas (M2a) to (M2e), which are bifunctional liquid crystal acrylates.

  Among the compounds (M3), particularly preferable compounds are monofunctional liquid crystalline vinyl ethers represented by formulas (M3a) to (M3f).

  Among the compounds (M4), particularly preferred compounds are those represented by the formulas (M4a) to (M4b) are bifunctional liquid crystalline vinyl ethers.

  Among the compounds (M5), particularly preferred compounds are monofunctional liquid crystalline maleimides represented by the formulas (M5a) to (M5f).

  Among the compounds (M6), particularly preferred compounds are monofunctional liquid crystalline epoxides represented by the formulas (M6a) to (M6f).

  Among the compounds (M7), a particularly preferable compound is a bifunctional liquid crystalline epoxide represented by the formula (M7a) to the formula (M7b).

  Among the compounds (M8), particularly preferable compounds are monofunctional liquid crystalline oxetanes represented by the formulas (M8a) to (M8f).

  Among the compound (M9), a particularly preferable compound is a bifunctional liquid crystalline oxetane represented by the formula (M9a) to the formula (M9b).

In these formulas: R ³ is hydrogen, fluorine, chlorine, cyano or alkyl or alkoxy having 1 to 20 carbon atoms, R ⁴ is methyl or ethyl, and W ¹ and W ² are each independently hydrogen, chlorine or Fluorine, W ³ and W ⁴ are each independently hydrogen, fluorine, methyl or trifluoromethyl, X ⁶ is a single bond or —O—, and n and p are each independently an integer of 1 to 20 expressed.

  The basic composition of the composition of the present invention is composed of at least one compound represented by the formula (1) and at least one compound selected from the compounds represented by the formulas (M1) to (M9). In the compositions (MIX1) to (MIX20), the wavelength of light selectively reflected by the content of the compound (1) in the compositions (MIX1) to (MIX20) can be adjusted from the visible light region to the ultraviolet region (100 nm to 700 nm). The content of the compound (1) can be arbitrarily set, but is preferably 1 to 90% by weight, preferably 10 to 50% by weight for obtaining visible light reflection of 380 nm to 780 nm, and ultraviolet light having a wavelength of 380 nm or less. For reflection, it is preferably 50 to 90% by weight.

The content of the compound selected from Formula (M1) to Formula (M9) is preferably 10 to 99% by weight.

Furthermore, a first basic configuration of the preferred composition is a compound in which the polymerizable group P is selected from (P1), (P2), (P3) and (P10) in the formula (1), the formula (M1) and the formula It consists of compositions (MIX1), (MIX2) and (MIX3) in which a compound selected from (M2) is mixed. Each compound (1), compound (M1) and compound (M2) may be a single compound or two or more compounds.
(MIX1): Compound (1) + Compound (M1)
(MIX2): Compound (1) + Compound (M2)
(MIX3): Compound (1) + Compound (M1) + Compound (M2)
These compositions can be rapidly cured by fixing a liquid crystal phase by adding a radical photopolymerization initiator and irradiating an electron beam such as ultraviolet rays.

  The film obtained by photopolymerization of the composition (MIX1) is flexible. In the film obtained from the composition (MIX1), since the compound (M2) plays a role as a crosslinking component, a tough and high heat resistant film can be obtained. The film obtained from the composition (MIX3) is suitable for producing a film having a good balance between flexibility and heat resistance as a film.

A second basic structure of the preferred composition is a compound selected from the formula (1) in which the polymerizable group P is selected from (P4), (P5) and (P10), a compound selected from the formula (M5), and the formula (M3). And a composition (MIX4), (MIX5) and (MIX6) in which a compound selected from the formula (M4) is mixed. Each compound (1), compound (M5), compound (M3) and compound (M4) may be a single compound or two or more compounds.
(MIX4): Compound (1) + Compound (M5) + Compound (M3)
(MIX5): Compound (1) + Compound (M5) + Compound (M4)
(MIX6): Compound (1) + Compound (M5) + Compound (M3) + Compound (M4)

  In the compositions (MIX4), (MIX5) and (MIX6), the compound (M5) also serves as a polymerization initiator. Although content of the compound (M5) in the composition of this invention can be set arbitrarily, 3 to 50 weight% is preferable. When the compound (M5) is 3% by weight or more, the sensitivity of the composition to light is improved, and photopolymerization tends to proceed. However, since most of the compound (M5) does not have a liquid crystal phase and has only a melting point, when added in an amount of 50% by weight or less, the temperature range of the liquid crystal phase of the composition is widened, and photopolymerization at an optimum temperature is easily performed. On the other hand, the addition amount of the compound (M3) and the compound (M4) can be arbitrarily set, but a suitable amount for maintaining the liquid crystal temperature range of the composition is the sum of the compound (M3) and the compound (M4). The content of is preferably 50 to 10% by weight. These compositions can be quickly cured and fixed in a liquid crystal phase by irradiating with an electron beam such as ultraviolet rays without adding a radical photopolymerization initiator.

A third basic structure of the preferred composition is a compound in which the polymerizable group P in the formula (1) is selected from (P6), (P7), (P8), (P9) and (P11), and the formula (M3) , Formula (M4), Formula (M6), Formula (M7), Formula (M8) and Composition (MIX7) to (MIX20) in which compounds selected from Formula (M9) are mixed. Each compound may be a single compound or two or more compounds.
(MIX7): Compound (1) + Compound (M3)
(MIX8): Compound (1) + Compound (M4)
(MIX9): Compound (1) + Compound (M6)
(MIX10): Compound (1) + Compound (M7)
(MIX11): Compound (1) + Compound (M8)
(MIX12): Compound (1) + Compound (M9)
(MIX13): Compound (1) + Compound (M6) + Compound (M7)
(MIX14): Compound (1) + Compound (M8) + Compound (M9)
(MIX15): Compound (1) + Compound (M6) + Compound (M9)
(MIX16): Compound (1) + Compound (M7) + Compound (M9)
(MIX17): Compound (1) + Compound (M3) + Compound (M7) + Compound (M9)
(MIX18): Compound (1) + Compound (M4) + Compound (M7) + Compound (M9)
(MIX19): Compound (1) + Compound (M3) + Compound (M7)
(MIX20): Compound (1) + Compound (M4) + Compound (M7)
These compositions can be quickly cured by fixing a liquid crystal phase by adding a cationic photopolymerization initiator and irradiating an electron beam such as ultraviolet rays. Further, the polymerization product is obtained at a good curing rate without being subjected to polymerization inhibition even under air.

  For the purpose of improving physical properties, each of the compositions (MIX1) to (MIX20) includes a non-polymerizable liquid crystal compound and a polymerizable compound as components other than the compound (1) and the compounds (M1) to (M9). Alternatively, compounds such as a non-polymerizable optically active compound, a non-liquid crystalline polymerizable compound, a polymerization initiator, a solvent, a surfactant, an antioxidant, a filler, and an ultraviolet absorber may be added. Any structure may be used as long as the object is achieved. These compounds can utilize a well-known thing suitably. The content of each component is preferably such that the composition does not impair the liquid crystallinity. Even if the atoms constituting the components of the composition contain more isotopes than their natural abundance, it is preferable because they have similar characteristics.

Next, the polymer will be described.
Compound (1) has a polymerizable unsaturated bond or cyclic ether. A polymer can be produced by polymerizing the compound (1). The polymer is obtained by a reaction such as radical polymerization or cationic polymerization. When only one of the compounds (1) is polymerized, a homopolymer is obtained. This polymer consists of one structural unit. When a composition containing at least two compounds (1) is polymerized, a copolymer is obtained. This copolymer has at least two structural units. Since the polymerization in the aligned liquid crystal state is desirable for the production of the optically anisotropic film which is the object of the present invention, photoradical polymerization or photocationic polymerization is a particularly preferred polymerization method.

  A non-liquid crystalline polymerizable compound may be added for the purpose of adjusting film forming properties, mechanical strength, and the like. Examples of preferred non-liquid crystal polymerizable compounds are (meth) acrylate compounds, vinyl compounds, styrene compounds, vinyl ether compounds, epoxy compounds, and oxetane compounds.

  Preferred non-liquid crystalline polymerizable compounds that can be added to the liquid crystal compositions (MIX1) to (MIX6) of the present invention are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, phenyl (meth) acrylate, vinyl chloride, vinyl fluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, Vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, styrene, o- , M- or p-chloromethylstyrene, α-methylstyrene, tetrafur Roechiren, and hexafluoropropene.

  In order to further increase the film-forming ability of the polymer, a polyfunctional acrylate can be added to the composition. Preferred polyfunctional acrylates are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glycidyl di Acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name: Biscoat 700), and polyethylene glycol diacri It is over door.

  Preferred non-liquid crystalline polymerizable compounds that can be added to (MIX7) to (MIX20) of the present invention are ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, or viscosity adjustment of the composition or 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, di (3-ethyl-oxeta-3-ylmethyl), 3-ethyl-3- (2-ethyl) for the purpose of reducing cure shrinkage Hexyloxymethyl) oxetane can be added.

  A surfactant may be added within a range that does not impair the effects of the present invention in order to facilitate coating or to control the orientation of the liquid crystal phase. As the surfactant, for example, imidazoline, quaternary ammonium salt, alkylamine oxide, polyamine derivative, polyoxyethylene-polyoxypropylene condensate, polyethylene glycol and its ester, sodium uraryl sulfate, ammonium lauryl sulfate, amine lauryl sulfate, Alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, uralylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, perfluoroalkyl Sulfonate, perfluoroalkylcarboxylate, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoro Alkyl group and a hydrophilic group-containing oligomer, perfluoroalkyl group and lipophilic group-containing oligomer, perfluoroalkyl group-containing urethane and the like. The addition amount of the surfactant varies depending on the kind of the surfactant, the composition ratio of the photopolymerizable liquid crystal composition, and the like, but is 100 ppm to 5%, more preferably 0.8%, based on the weight of the photopolymerizable liquid crystal composition. It is in the range of 1% to 1%.

  The compositions (MIX1) to (MIX6) of the present invention can be used with addition of a normal photoradical polymerization initiator. Examples of radical photopolymerization initiators include Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) and Irgacure 184 (1) from the products of Ciba Specialty Chemicals. -Hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure Cure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, Irgacure 784, and the like.

  Other examples of photo radical polymerization initiators include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine Such as a mixture.

  The compositions (MIX7) to (MIX20) of the present invention are used after adding a normal photocationic polymerization initiator. Examples of the cationic photopolymerization initiator are Dow Chemical's products such as Syracure UVI-6976, Syracure UVI-6992 (both trade names), and Asahi Denka Co., Ltd. products Adekaoptomer SP-150, SP. -152, SP-170, SP-172 (all trade names), Rhodia products to PHOTOINITIATOR 2074 (trade names), Ciba Specialty products to Irgacure 250 (trade names), and the like.

  The optically anisotropic film of the present invention is formed by coating the photopolymerizable composition of the present invention on a support to form a coating film, and the nematic alignment formed by the composition in the coating film in a liquid crystal state It can be produced by a method of fixing by irradiation. For the support substrate, a coating film of the liquid crystal composition can be formed on the surface. For example, triacetyl cellulose, polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, polyethylene terephthalate, polyethylene naphthalate may be used. it can. Other specific product names include “Arton” (trade name) manufactured by JSR Corporation, “ZEONEX” and “ZEONOR” (all trade names) manufactured by Nippon Zeon Co., Ltd., and Mitsui Chemicals Co., Ltd. “Appel” (trade name) is used. These supports may be a uniaxially stretched film or a biaxially stretched film.

  In the production of the optically anisotropic film of the present invention, it is particularly desirable to use a triacetyl cellulose film for the support substrate. The triacetyl cellulose film can be used as it is as a support substrate, but if necessary, the film can be used after being subjected to surface treatment such as saponification treatment, corona discharge treatment, UV-ozone treatment.

  In forming the coating film, the photopolymerizable liquid crystal composition can be dissolved in a suitable solvent and applied. Solvents include benzene, toluene, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate. , Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethylene , Trichlorethylene, tetrachlorethylene, Use lorobenzene, t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, butyl cellosolve, etc. as a single solvent or multiple mixed solvents. Can do.

  The application method of the photopolymerizable liquid crystal composition is spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire barcode, dip coating, spray coating, meniscus coating, casting film forming method, etc. The method can be performed by, for example, a method of developing a thin film by the above method and drying it to remove the solvent.

  A preferred method for orienting the surface of the substrate is, for example, forming a thin film made of commonly used polyimide or polyvinyl alcohol and rubbing it with rayon cloth, or obliquely depositing silicon oxide, stretching This is rubbing-free orientation using a film, a polarizing ultraviolet alignment film, an ion beam, or the like. Alternatively, orientation can be performed by using a metal substrate such as aluminum, iron, or copper having slits on the surface, or a glass substrate such as alkali glass, borosilicate glass, or flint glass etched into a slit.

  The aligned liquid crystal layer fixes the alignment by irradiating electromagnetic waves such as ultraviolet rays or electron beams. The ultraviolet rays to be irradiated preferably have a wavelength longer than 300 nm where the composition does not absorb. In the case of using an electron beam, the copolymer collapses when the irradiation amount is too large, so 1 to 200 Mrad is preferable. The temperature at the time of electromagnetic wave irradiation may be a temperature at which the composition is in a liquid crystal state.

  The compound (1) of the present invention is an optically active compound. Since the composition to which the compound (1) which is an optically active compound is added exhibits a helical structure, a retardation plate having a helical structure can be produced by aligning the polymer and polymerizing it in a liquid crystal state. If the pitch of the helix is about ½ to about the same as the wavelength of light, light having that wavelength can be selectively reflected according to Bragg's law. This can be used, for example, as a circularly polarized light separating functional element. The direction of the helix depends on the configuration of the optically active compound. The desired helical direction can be induced by selecting the configuration of the compound (1) of the present invention as appropriate.

  The thickness of the optically anisotropic film varies depending on the desired optical function and its characteristics, and the optical anisotropy of the obtained optically anisotropic film. The preferred thickness is 0.05 to 50 μm, more preferably 0.1 to 20 μm, and still more preferably 0.5 to 1 μm. A preferable retardation value is in the range of 0.05 to 50 μm, and a more preferable retardation value is in the range of 0.1 to 20 μm. A more preferable retardation value is in the range of 0.5 to 10 μm. The haze value of the optically anisotropic film is 1.5% or less, more preferably 1.0% or less, and the transmittance is 80% or more, more preferably 85% or more. It is preferable that the transmittance satisfies these ratios in the visible light region. A haze value range of 1.5% or less is a preferable condition in order not to cause a problem in polarization performance. A transmittance range of 80% or more is a preferable condition for maintaining brightness when this optically anisotropic film is used in a liquid crystal display element.

The compound of the present invention is useful as a liquid crystal composition for a liquid crystal display device, and applications of the polymer in the present invention include the following.
Thermoplastic resins can be used for adhesives, synthetic polymers having mechanical anisotropy, cosmetics, decorations, nonlinear optical materials, information storage materials, and the like. This thermoplastic resin is a linear polymer that is not branched, and is obtained by polymerizing the liquid crystal composition of the present invention mainly composed of a monofunctional compound. Their weight average molecular weight is 500 to 1,000,000, preferably 1000 to 500,000, more preferably 5000 to 100,000.
A thermosetting resin can be used for a retardation plate, a polarizing element, a liquid crystal alignment film, an antireflection film, a selective reflection film, a viewing angle compensation film, and the like, which are components of the liquid crystal display element. This thermosetting resin is a polymer having a three-dimensional network structure, and can be obtained as a polymer having a high degree of polymerization by polymerizing the liquid crystal composition of the present invention mainly composed of a bifunctional compound. These polymers become difficult to dissolve in a solvent as the branching proceeds, and the hardness increases. The molecular weight of these polymers is difficult to measure and difficult to define, but is preferably close to infinity.

  Hereinafter, the present invention will be described in detail by way of examples. The phase transition temperature described in the examples was measured by placing a sample on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heating at a rate of 1 ° C./min. C represents a crystal, N represents a nematic phase, Ch represents a cholesteric phase, and I represents an isotropic liquid. The NI point indicates the upper limit temperature of the nematic phase and is the transition temperature from N to I. C 50 N 63 I indicates a transition from C to N at 50 ° C. and a transition from N to I at 63 ° C. The pencil hardness was determined according to the method of JIS standard “JIS-K-5400 8.4 Pencil Scratch Test”. HTP (helical twist power) was calculated using the formula p = 1 / HTP · 1 / c (where p is the pitch and c is the weight concentration of the optically active compound in the host liquid crystal). The pitch was measured by dissolving 1% by weight of a sample in a liquid crystal composition ZLI-1132 (trade name) manufactured by Merck and using a wedge-type cell. In the following, the liter, which is a unit of capacity, is represented by the symbol L.

(Production of Compound No. 10)
(First stage)
Production of (S) -citronellyl chloride 2.5 Kg of triphenylphosphine was added little by little over 8 hours while keeping a solution obtained by mixing 1 Kg of (S) -citronellol and 4 L of carbon tetrachloride at 70 ° C. When the reaction solution was returned to room temperature and poured into 25 L of pentane, a white slurry was obtained. The filtrate obtained by filtering this slurry was concentrated, and the concentrate was purified by distillation under reduced pressure to obtain 848 g of (S) -citronellyl chloride. (Boiling point (20 hPa) 95 ° C.)

(Second stage)
A solution obtained by adding 800 g of (S) -citronellyl chloride to 4 L of methanol was blown with ozone while maintaining the temperature at −15 ° C. After confirming that all the raw materials had reacted with ozone by gas chromatography, 152 g of sodium borohydride was added and stirred for 2 hours. During this time, the temperature of the reaction solution was controlled so as not to exceed 0 ° C. The reaction was stopped by adding 3 kg of ice and 3 L of water and 432 ml of sulfuric acid, and the mixture was extracted with 4 L of chloroform. The chloroform layer was washed with aqueous sodium hydrogen carbonate, dried over anhydrous sodium sulfate, and concentrated. The residue obtained by concentration was purified by distillation under reduced pressure to obtain 350 g of (S) -4-methyl-6-chlorohexanol. (Boiling point (5.3 hPa) 90-92 ° C.)

(3rd stage)
A solution consisting of 128 g of (S) -4-methyl-6-chlorohexanol, 130 g of ethyl 4-hydroxybenzoate, 129 g of potassium carbonate and dimethylformamide was stirred at 90 ° C. for 7 hours. When the reaction solution was poured into 2 L of water, a slurry was obtained. This was filtered to obtain a solid. The solid was dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, concentrated, and recrystallized from cyclohexane to obtain 197 g of ethyl (S) -4- (6-hydroxy-3-methylhexyloxy) benzoate. Melting point 74-75 ° C

(Fourth stage)
A solution consisting of 132 g of ethyl (S) -4- (6-hydroxy-3-methylhexyloxy) benzoate, 500 ml of ethanol, 100 ml of water and 70 g of potassium hydroxide was refluxed for 4 hours. After removing ethanol in the reaction solution as much as possible by distillation under reduced pressure, 400 ml of water and 500 ml of ether were added to the solution for liquid separation. When 12N hydrochloric acid was added to the aqueous layer, a slurry was obtained, which was filtered to obtain crystals. The obtained crystals were dried and recrystallized from diethyl ether to obtain 100 g of (S) -4- (6-hydroxy-3-methylhexyloxy) benzoic acid.

(5th stage)
(S) -4- (6-Hydroxy-3-methylhexyloxy) benzoic acid 22 g, N, N-dimethylaniline 13 ml, 2,6-di-t-butyl-4-methylphenol 0.2 g, dioxane 200 ml To this solution, 8.3 ml of acrylic acid chloride was added dropwise at room temperature and refluxed at 50 ° C. for 2 hours. When the reaction solution was poured into a large amount of water, a slurry was obtained, which was filtered to obtain crystals. The obtained crystals were dried and recrystallized with a mixed solvent of cyclohexane and diethyl ether to obtain 17 g of (S) -4- (6-acryloyloxy-3-methylhexyloxy) benzoic acid.

(6th stage)
(S) -4- (6-acryloyloxy-3-methylhexyloxy) benzoic acid (3 g) and 2,7-dihydroxy-9-methylfluorene (1 g) were dissolved in 80 ml of methylene chloride, cooled to 5 ° C., and then dimethylaminopyridine 0 0.1 g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 2.3 g was added, and the mixture was stirred at room temperature for 12 hours. 50 ml of water was added for liquid separation, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography, recrystallized with a solvent mixed with ethanol and ethyl acetate, and 0.8 g of (S)-(−)-9-methyl-2,7 -Di (4- (6-acryloyloxy-3-methylhexyloxy) benzoyloxy) fluorene was obtained.
Phase transition temperature: C 65 Ch 130 I
This result shows that the compound of the present invention is a liquid crystal compound exhibiting a cholesteric liquid crystal phase in a wide temperature range.

(Comparative Example 1)
As a general chiral agent (CB-15), Compound No. Ten HTPs were compared.

Compound HTP
(CB-15) 5.7 μm ⁻¹ · wt% ⁻¹
(No. 10) 13.4 μm ⁻¹ · wt% ⁻¹
Compound no. 10 showed HTP 2.3 times larger than CB-15. That is, it can be seen from this result that the compound of the present invention has a large helical induction force.

(Production of Compound No. 13)
(S) -4- (3-Methyl-6-vinyloxyhexyloxy) benzoic acid (2.6 g) and 2,7-dihydroxy-9-methylfluorene (1 g) were dissolved in methylene chloride (80 ml), and dimethylaminopyridine (0.1 g) was dissolved therein. Then, 2.3 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred at room temperature for 12 hours. 50 ml of water was added for liquid separation, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography, recrystallized with a solvent mixed with ethanol and ethyl acetate, and 0.9 g of (S)-(−)-9-methyl-2,7. -Di (4- (6-vinyloxy-3-methylhexyloxy) benzoyloxy) fluorene was obtained.

(Production of Compound No. 90)
(First stage)
Production of (S) -citronellyl bromide While maintaining a solution of 500 g of (S) -citronellol and 835 g of triphenylphosphine in 1.5 L of methylene chloride at 10 ° C., 1325 g of carbon tetrabromide was dissolved in 1.5 L of methylene chloride. The solution was added dropwise over 2 hours. The reaction solution was returned to room temperature and poured into 10 L of pentane to obtain a white slurry. The filtrate obtained by filtering this slurry was concentrated, and the concentrate was purified by distillation under reduced pressure to obtain 472 g of (S) -citronellyl bromide. (Boiling point (20 hPa) 101-112 ° C.)

(Second stage)
A solution consisting of 100 g of (S) -citronellyl bromide, 71 g of ethyl 4-hydroxybenzoate, 83 g of potassium carbonate and 400 ml of dimethylformamide was stirred at 90 ° C. for 7 hours. The reaction solution was poured into 1 L of water and extracted with toluene. The toluene layer was washed with water and dried over anhydrous magnesium sulfate. To the residue obtained by distilling off the solvent, 10 g of sodium hydroxide, 100 ml of ethanol and 30 ml of water were added and refluxed for 2 hours. After removing ethanol in the reaction solution by distillation under reduced pressure as much as possible, 12N hydrochloric acid was added to the solution to make it acidic, and 500 ml of ether was added for liquid separation. The ether layer was dried over anhydrous magnesium sulfate and recrystallized to obtain 93 g of (S) -4- (3,7-dimethyloctyloxy-6-ene) benzoic acid.
Melting point: 58-60 ° C

(3rd stage)
(S) -4- (3,7-dimethyloctyloxy-6-ene) benzoic acid 10 g and 2,7-dihydroxy-9-methylfluorene 3.8 g were dissolved in 100 ml of methylene chloride and cooled to 5 ° C. 0.1 g of aminopyridine and 7.6 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added and stirred at room temperature for 12 hours. 50 ml of water was added for liquid separation, and the methylene chloride layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography, recrystallized with a solvent mixed with ethanol and ethyl acetate, and 19 g of (S, S) -9-methyl-2,7-di (4 -(3,7-dimethyloctyloxy-6-ene) benzoyloxy) fluorene was obtained.
Phase transition temperature: C 96 Ch 146.9 I

ただし、＊印は不斉炭素の存在を示す。

The * mark indicates the presence of asymmetric carbon.

(Fourth stage)
To a solution of 18 g of (S, S) -9-methyl-2,7-di (4- (3,7-dimethyloctyloxy-6-ene) benzoyloxy) fluorene dissolved in 200 ml of methylene chloride, m-chloroperoxide was added. 15 g of benzoic acid was added and stirred for 8 hours. Water was added to separate the methylene chloride layer, and the solution was washed twice with 30% aqueous sodium bisulfite solution and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography, recrystallized twice with ethanol, and 5 g of (S, S) -9-methyl-2,7-di (4- (3 , 7-dimethyloctyloxy-6,7-epoxy) benzoyloxy) fluorene (No. 90).
Phase transition temperature: C 66 Ch 103.6 I
This result shows that the compound of the present invention is a liquid crystal compound exhibiting a cholesteric liquid crystal phase in a wide temperature range.

(Composition example of (MIX2))
A composition (CL1) containing 50% by weight of compound (No. 10) and 50% by weight of (K1) was prepared. The phase transition temperature of this composition was C 85 Ch 185 I, and the compound (No. 10) exhibited good compatibility without phase separation.

(Example composition showing selective reflection)
The compound (No. 10), the compound (K2) and the compound (K3) were mixed at the following ratios to prepare compositions (CL2) to (CL4).

Compound No. (No. 10) (K2) (K3) Selective Reflective Composition (CL2) 35 wt% 45 wt% 20 wt% Red Composition (CL3) 40 wt% 40 wt% 20 wt% Green Composition (CL4) 45% 35% 20% Blue

  The compound (No. 90), the compound (K4) and the compound (K5) were mixed at the following ratio to prepare a composition (CL5). The clearing point of the composition (CL5) was 100 ° C.

(No. 90) (K4) (K5) Selective reflective composition (CL5) 40% by weight 30% by weight 30% by weight Red

  The compositions (CL2) to (CL5) showed good orientation on a rubbed saponified triacetyl cellulose film. The “selective reflection” indicates the color of reflected light that is visually observed in the alignment state. From this, it can be seen that a composition exhibiting an arbitrary selective reflection wavelength region can be prepared by changing the amount of the compound (1) added.

(Production of optically anisotropic film by ultraviolet irradiation 1)
A microgravure coater was applied to a triacetyl cellulose film having a degree of acetylation of 2.9 having a surface obtained by rubbing the surface of the composition (CL4) 10 g, polymerization initiator Irgacure 907, 0.3 g dissolved in 80 g of toluene with a rayon cloth. Applied. After coating, the solution was heat-treated in an oven set at 70 ° C. for 15 minutes to remove the solvent and align the liquid crystal phase. While maintaining the same temperature, ultraviolet rays were irradiated for 10 seconds with a high-pressure mercury lamp (120 W / cm). After irradiation, the liquid crystal phase was polymerized, and the surface hardness was 2H in pencil hardness. A film with high heat resistance was obtained with no disorder in the orientation of the liquid crystal phase due to temperature change (20 to 100 ° C.). This optically anisotropic film exhibited the same blue selective reflection as when the composition was oriented on the substrate. This indicates that the molecular composition of the oriented composition was maintained and polymerized.

(Production of optically anisotropic film by ultraviolet irradiation 2)
A microgravure coater was used on a triacetylcellulose film having a degree of acetylation of 2.9, in which a solution of 10 g of composition (CL5) and Syracure UVI-6992: 0.3 g dissolved in 80 g of toluene was rubbed with a rayon cloth. And applied. After coating, the solution was heat-treated in an oven set at 70 ° C. for 15 minutes to remove the solvent and align the liquid crystal phase. While maintaining the same temperature, ultraviolet rays were irradiated for 10 seconds with a high-pressure mercury lamp (120 W / cm). After irradiation, the liquid crystal phase was polymerized, and the surface hardness was 2H in pencil hardness. A film with high heat resistance was obtained with no disorder in the orientation of the liquid crystal phase due to temperature change (20 to 100 ° C.). This optically anisotropic film exhibited the same red selective reflection as when the composition was oriented on the substrate. This indicates that the molecular composition of the oriented composition was maintained and polymerized.

An optically anisotropic film was produced by the same method using the compositions (CL1) to (CL3). All the compositions had good orientation and polymerizability by ultraviolet rays. The films of the composition (CL1) all showed about 2H, except that the pencil hardness showed H. All the films produced from the compositions (CL1) to (CL3) were films having high heat resistance without any disturbance in the orientation of the liquid crystal phase due to temperature changes (20 to 100 ° C.). It was visually confirmed that the optically anisotropic films obtained from the compositions (CL2) and (CL3) exhibited the same selective reflection color as when the composition was oriented on the substrate. That is, the optically anisotropic film obtained from the composition (CL2) selectively reflected red light, and the optically anisotropic film obtained from the composition (CL3) selectively reflected green light. In the optically anisotropic film obtained from the composition (CL1), the color of selective reflection could not be confirmed visually. This is thought to be because the pitch of the composition is shortened because the mixing ratio of the compound (1) is large, and the wavelength for selective reflection is shifted to the ultraviolet region instead of the visible region.

Claims (34)

An optically active compound represented by formula (1).

In formula (1), ^{R 1} is hydrogen, ^{R 2} is methyl; A ¹ and ^{A 2} are 1,4-phenylene; ^{X 1} and ^{X 4} is -O-; ^{X 2} and ^{X 3} independently -COO- or a -OCO-; ^{Y 1} and ^{Y 2} has the formula (C3), an optically active group represented by (C6) or (C7), in these formulas * mark It indicates the presence of an asymmetric carbon; P has the formula (P1), (P4) or other is a polymerizable group represented by (P11).

In formula (1), ^{R 1} is hydrogen, ^{R 2} is methyl, ^{A 1} and ^{A 2} are 1,4-phenylene, ^{X 1} and ^{X 4} is -O-, ^{X 2} and ^{X 3} independently -COO- or a -OCO-, ^{Y 1} and ^{Y 2} are the optically active group represented by the formula (C3), in these formulas * mark indicates the presence of an asymmetric carbon; a compound according to claim 1 P is a polymerizable group represented by the formula (P1). In formula (1), ^{R 1} is hydrogen, ^{R 2} is methyl, ^{A 1} and ^{A 2} are 1,4-phenylene, ^{X 1} and ^{X 4} is -O-, ^{X 2} and ^{X 3} Independently —COO— or —OCO—, Y ¹ and Y ² are each independently an optically active group represented by (C6) or (C7). The compound according to claim 1, wherein P is a polymerizable group represented by (P11). Any compound represented by the following formula. However, in these formulas, * indicates the presence of an asymmetric carbon.

A liquid crystal composition comprising at least two compounds, wherein at least one compound is the compound according to any one of claims 1 to 4 . The liquid crystal composition according to claim 5 , wherein all of the compounds are polymerizable compounds. At least one of the compounds according to any one of claims 1 to 4 , and the formula (M1), (M2), (M3), (M4), (M5), (M6), (M7), (M8) And at least one polymerizable compound selected from the compounds represented by (M9).

In the above formula, R ³ is independently hydrogen, fluorine, chlorine, cyano, or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — represents —O—, —S—, — COO—, —OCO—, or —CO— may be replaced, and any hydrogen may be replaced with a halogen; R ⁴ is independently hydrogen or alkyl of 1 to 5 carbons; A ³ , A ⁴ and A ⁵ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by halogen, pyridine-2,5-diyl, Pyrimidine-2,5-diyl, naphthalene-2,6-diyl or fluorene-2,7-diyl; B is independently a single bond, 1,4-phenylene, at least one hydrogen is halogen, methyl Shi Is 1,4-phenylene substituted with trifluoromethyl, naphthalene-2,6-diyl, biphenyl-4,4′-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene-2,7-diyl or 9,9-difluorofluorene-2,7-diyl; X ⁶ is independently a single bond or —O—; Z ¹ and Z ² are independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, or —C≡C—. M is independently 1 or 0, and n and p are each independently an integer of 1-20. R ³ is hydrogen, fluorine, chlorine, or alkyl or alkoxy having 1 to 20 carbon atoms, R ⁴ is independently methyl or ethyl, and A ³ , A ⁴ and A ⁵ are independently 1, 4 -Cyclohexylene, 1,4-phenylene, 1,4-phenylene in which 1 or 2 hydrogens are replaced by fluorine, or 1,4-phenylene in which 1 or 2 hydrogens are replaced by chlorine, and B is 1,4-phenylene, 1,4-phenylene in which 1 or 2 hydrogens are replaced with fluorine, 1,4-phenylene in which 1 or 2 hydrogens are replaced with methyl, 1 or 2 hydrogens in tris 1,4-phenylene, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl or 9-ethylfluorene-2,7-diyl substituted with fluoromethyl, Z ¹ and The liquid crystal composition according to claim 7 , wherein Z ^{2 and} Z ² are each independently a single bond, —COO— or —OOC—. The sum total of content of the compound represented by Formula (1) of Claim 1 is 3 to 90 weight%, and the sum total of content of the compound represented by either of Formula (M1)-(M9) The liquid crystal composition according to claim 7 or 8 , wherein is 10 to 97% by weight. In the formula (1) according to claim 1, the compound P is the (P1) and the formula (M1) and (M2) according to claim 7 or containing at least one compound selected from the compounds represented by 8. A liquid crystal composition according to 8 . In the formula (1) according to claim 1, the sum is 3 to 90 wt% of the content represented by reduction compounds with P is (P1), the compound represented by the formula (M1) and (M2) the liquid crystal composition according to claim 10 total content is 10 to 97 wt%. In the formula (1) according to claim 1, P is the reduction compound is (P4), at least one of compounds represented by the formula (M5), the formula (M3) and (M4) The liquid crystal composition according to claim 7 or 8 , comprising at least one compound selected from each compound. In the formula (1) according to claim 1, the sum is 10 to 90 wt% of the content of P is (P4) at which reduction compound and the compound represented by the formula (M5), formula (M3) and ( The liquid crystal composition according to claim 12 , wherein the total content of each compound represented by M4) is 10 to 90% by weight. In the formula (1) according to claim 1, and of compounds is P is (P11), the formula (M3), represented by (M4), (M6), (M7), (M8) and (M9) The liquid crystal composition according to claim 7 or 8 , comprising at least one compound selected from the group of each compound. In the formula (1) according to claim 1, the compound P is the (P11) and the formula (M8) and (M9) according to claim 7 or containing at least one compound selected from the compounds represented by 8. A liquid crystal composition according to 8 . The compound of formula (1) according to claim 1, wherein P is (P11) and any two compounds selected from the compounds represented by formulas (M6), (M7) and (M9) The liquid crystal composition according to claim 7 or 8 . In the formula (1) according to claim 1, the sum is 10 to 90 wt% of the content of P is (P11) is a reduction compounds of formula (M3), (M4), (M6), (M7) The liquid crystal composition according to any one of claims 14 to 16 , wherein the total content of the compounds represented by (M8) and (M9) is 10 to 90% by weight. A polymer obtained by polymerizing the liquid crystal composition according to any one of claims 5 to 17 .   A polymer obtained by polymerizing at least one compound according to claim 1. The polymer according to claim 18 or 19 , which has a weight average molecular weight of 500 to 1,000,000. The polymer according to claim 18 or 19 , which has a weight average molecular weight of 1,000 to 500,000. The optically anisotropic composition comprising the polymer according to claim 20 or 21, which is obtained by polymerizing the liquid crystal composition according to any one of claims 5 to 17 or the compound of formula (1) by irradiation with electromagnetic waves. Sex film. An optically anisotropic film obtained by aligning the liquid crystal composition according to any one of claims 5 to 17 or the compound of formula (1) and then fixing the alignment of the liquid crystal phase by irradiation with electromagnetic waves. The optically anisotropic film according to claim 22 or 23 , wherein the irradiated electromagnetic wave is an electron beam or an ultraviolet ray. The optically anisotropic film according to any one of claims 22 to 24 , wherein the alignment of the liquid crystal fixed by electromagnetic waves is a planar alignment. An optical element comprising the optically anisotropic film according to any one of claims 22 to 25 . 27. The optical element according to claim 26 , wherein the optically anisotropic film has circular dichroism. 28. The optical element according to claim 26 or 27 , wherein the optical element exhibits circular dichroism in a visible light region that selectively reflects light in a part or all of a wavelength of 350 to 750 nm. In a spiral structure induced by a chiral nematic phase or a cholesteric phase, the pitch is continuously changed in the thickness direction of the molded article having optical anisotropy, so that light in the entire wavelength range of 350 to 750 nm is selectively selected. 27. The optical element according to claim 26, which reflects. 29. The optical element according to claim 28 , wherein the optical element is made of a polymer having two or more layers having different wavelength regions exhibiting circular dichroism, and selectively reflects light in all regions having a wavelength of 350 to 750 nm. The optical element according to any one of claims 26-30, optical element in which a layer that functions as a 1/4-wavelength features plate. The optical element according to any one of claims 26 to 30 , which functions as a brightness enhancement film. 28. The optical element according to claim 26 or 27 , which exhibits circular dichroism in an ultraviolet light region having a wavelength of 100 to 350 nm. The liquid crystal display device comprising the optical element according to any one of claims 26-30.