JPWO2008026482A1 - Unsaturated fatty acid ester, polymerizable liquid crystal composition, optically anisotropic material, and optical element using the same - Google Patents

Abstract

A novel unsaturated fatty acid ester capable of preparing a heat-resistant polymer, which suppresses unevenness of film thickness and disorder of alignment at the same time, hardly precipitates crystals even when left at room temperature, polymerizable liquid crystal composition using the same, optical Anisotropic materials and optical elements are provided. The unsaturated fatty acid ester is represented by the following formula (1), and a polymerizable liquid crystal composition containing the unsaturated fatty acid ester is prepared and polymerized to provide an optically anisotropic material and an optical element. In the formula, RF: a polyfluoroalkylene group having 2 to 12 carbon atoms, or a group represented by —CF 2 — (OCF 2 CF 2) x —OCF 2 — (x is an integer of 1 to 6). R1: a hydrogen atom or a methyl group. R2: an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group. E1: 1,4-phenylene group. E2, E3, E4: each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group. m: An integer of 1 to 3. n: An integer of 1 to 3. k: 0 or 1. h: 0 or 1. CH2 = CR1-COO- (CH2) m-RF- (CH2) n-O-E1- (E2) k- (E3) h-E4-R2 (1)

Description

  The present invention relates to a novel unsaturated fatty acid ester useful as a component of a polymerizable liquid crystal composition used in the production of optical elements and the like, a polymerizable liquid crystal composition using the same, and the polymerizable liquid crystal composition. The present invention relates to an optically anisotropic material and an optical element.

  As a method for producing a retardation film, a method is known in which a polymerizable liquid crystal composition is applied to a substrate and then polymerized. In this production method, it is effective to add a surfactant or a leveling agent to the polymerizable liquid crystal composition for the purpose of eliminating the film thickness unevenness that occurs when the polymerizable liquid crystal composition is applied (patent) Reference 1 and 2).

JP-A-8-231958 JP-A-11-148080

  However, conventional surfactants and leveling agents have a problem that they have low compatibility with the liquid crystal composition and cause alignment disorder.

  Further, in the method for producing a retardation film by coating, there is a problem that when a polymerizable liquid crystal composition is coated on a substrate and left at room temperature, crystals are precipitated and a transparent film cannot be obtained. Furthermore, in order to overcome the problem of precipitation of the crystals, the heat resistance of the film at a high temperature is often sacrificed as a result.

  The present invention has been made in view of the above circumstances, the film thickness unevenness and the alignment disorder are suppressed, the crystals are hardly precipitated even when left at room temperature, and the polymerizability is suitable for application to a substrate having a large area. It is an object of the present invention to provide a liquid crystal composition and a novel unsaturated fatty acid ester suitable for preparing the liquid crystal composition.

  Moreover, this invention makes it a subject to provide the polymeric liquid crystal composition from which the polymer excellent in heat resistance is obtained, the optically anisotropic material manufactured using this, and an optical element.

  According to one aspect of the present invention, the unsaturated fatty acid ester is represented by the following formula (1).

CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -OE ^1- (E ² ) _k- (E ³ ) _h -E ⁴ -R ² (1)

However, the symbol in Formula (1) is as follows.
R ^F : a polyfluoroalkylene group having 2 to 12 carbon atoms or a group represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ — (x is an integer of 1 to 6).
R ¹ : a hydrogen atom or a methyl group.
R ² : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group.
E ^{1 is a} 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.
E ² , E ³ , E ⁴ : each independently a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and a hydrogen atom bonded to a carbon atom in the group is a fluorine atom or a chlorine atom Alternatively, it may be substituted with a methyl group.
m: An integer of 1 to 3.
n: An integer of 1 to 3.
k: 0 or 1.
h: 0 or 1.

  Moreover, according to one aspect of the present invention, the polymerizable liquid crystal composition contains an unsaturated fatty acid ester represented by the following formula (1) and a polymerizable liquid crystal compound not corresponding to the following formula (1). The gist.

CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -OE ^1- (E ² ) _k- (E ³ ) _h -E ⁴ -R ² (1)

However, the symbol in Formula (1) is as follows.
R ^F : a polyfluoroalkylene group having 2 to 12 carbon atoms or a group represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ — (x is an integer of 1 to 6).
R ¹ : a hydrogen atom or a methyl group.
R ² : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group.
E ^{1 is a} 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.
E ² , E ³ , E ⁴ : each independently a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and a hydrogen atom bonded to a carbon atom in the group is a fluorine atom or a chlorine atom Alternatively, it may be substituted with a methyl group.
m: An integer of 1 to 3.
n: An integer of 1 to 3.
k: 0 or 1.
h: 0 or 1.

  The unsaturated fatty acid ester represented by the formula (1) is preferably a polymerizable liquid crystal compound having liquid crystallinity.

  It is preferable that at least a part of the polymerizable liquid crystal compound not corresponding to the formula (1) is a compound represented by the following formula (2).

CH ₂ = CR ³ -COO- (CH ₂ ) _t- (O) _p -E ⁵ -wE ^6- (E ⁷ ) _q- (E ⁸ ) _s -R ⁴ (2)

However, the symbol in Formula (2) is as follows.
R ³ : a hydrogen atom or a methyl group.
R ⁴ : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group.
E ⁵ , E ⁶ , E ⁷ , E ⁸ : each independently 1,4-phenylene group or trans-1,4-cyclohexylene group, and a hydrogen atom bonded to a carbon atom in the group is a fluorine atom, chlorine It may be substituted with an atom or a methyl group.
w: -OCO- or a single bond.
t: An integer from 0 to 8.
p: 0 when t is 0, 1 when t is 1-8.
q: 0 or 1.
s: 0 when q is 0, 0 or 1 when q is 1.

  The total amount of the unsaturated fatty acid ester represented by the formula (1) and the polymerizable liquid crystal compound not corresponding to the formula (1) is preferably 70% by mass or more based on the polymerizable liquid crystal composition.

  The amount of the unsaturated fatty acid ester represented by the formula (1) is 5 with respect to the total amount of the unsaturated fatty acid ester represented by the formula (1) and the polymerizable liquid crystal compound not corresponding to the formula (1). It is preferable in it being -50 mol%.

  The gist of the optically anisotropic material of the present invention is that it is obtained by polymerizing the above polymerizable liquid crystal composition in a state where the polymerizable liquid crystal compound in the composition exhibits a liquid crystal phase and is aligned.

  The optical element of the present invention supports a polymer obtained by polymerizing the above polymerizable liquid crystal composition in a state where the polymerizable liquid crystal compound in the composition exhibits a liquid crystal phase and is aligned, and the polymer. The gist is to have a support.

  In addition, said optical element is used suitably as a phase plate.

  According to the present invention, by using a novel unsaturated fatty acid ester, the prepared polymerizable liquid crystal composition has reduced film thickness unevenness and alignment disorder when applied to a substrate, and is crystallized even when left at room temperature. Can hardly be deposited, and can be suitably applied to a substrate having a large area. An optically anisotropic material obtained by polymerizing the polymerizable liquid crystal composition is excellent in heat resistance and useful for constituting an optical element such as a phase plate.

  Hereinafter, the present invention will be described in detail. Terms used in the description of the present application shall be interpreted in accordance with the following. In addition, the compound represented by the formula is also expressed as a compound given the number of the formula, for example, the compound represented by the formula (1) is also expressed as the compound (1).

  “Liquid crystal compound” means “a compound capable of exhibiting a liquid crystal phase alone”, and “polymerizable liquid crystal compound” means “a compound capable of exhibiting polymerizability and capable of exhibiting a liquid crystal phase alone”. “Polymerizable liquid crystal composition” means “a composition having polymerizability and capable of exhibiting a liquid crystal phase”.

  “(Meth) acryloyl group” means “acryloyl group or methacryloyl group”, and “(meth) acryloyloxy group” means “acryloyloxy group or methacryloyloxy group”. “Ph” represents a 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may include a hydrogen atom substituted by a fluorine atom, a chlorine atom or a methyl group. “Cy” refers to a trans-1,4-cyclohexylene group, and the hydrogen atom bonded to the carbon atom in the group may include those substituted with a fluorine atom, a chlorine atom or a methyl group.

  “Δn” is an abbreviation for “refractive index anisotropy”. In addition, the wavelength value in the following description shall include the range of description value +/- 2nm.

<New compound (1) and polymerizable liquid crystal compound>
The compound used for the preparation of the polymerizable liquid crystal composition of the present invention is a compound represented by the following formula (1). However, symbols R ¹ , R ² , E ^{1 to} E ⁴ , m, n, x, k, and h in the formula (1) are the same as defined above. This compound (1) is an unsaturated fatty acid ester containing a liquid crystalline skeleton composed of a plurality of 6-membered rings, and has both polymerizability and liquid crystallinity. The compound (1) may or may not exhibit a liquid crystal phase alone, but can be in a liquid crystal state when mixed with other components and used as a constituent component of a polymerizable liquid crystal composition exhibiting a liquid crystal phase. Is possible.

CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -OE ^1- (E ² ) _k- (E ³ ) _h -E ⁴ -R ² (1)

The compound (1) has a structure having a polyfluoroalkylene group or a polyfluoroalkylene oxide group in the spacer portion of the molecule, and the compound contained in the polymerizable liquid crystal composition (details will be described later) by the action of this group ( 1) moves to the surface of the composition film during polymerization and cures on the outermost surface. For this reason, the leveling property of the polymerizable liquid crystal composition is improved, and the film thickness unevenness is eliminated. In order to prevent the compatibility with the component not containing a fluorine atom in the polymerizable liquid crystal composition, the carbon number of the polyfluoroalkylene group is 2 to 12, and the number x of the polyfluoroalkylene oxide group is 1 to 6. . In terms of leveling properties and compatibility, the polyfluoroalkylene group preferably has 2 to 8 carbon atoms, and the polyfluoroalkylene oxide group x has preferably 1 to 4 carbon atoms. In addition, the polyfluoroalkylene group preferably has 2, 4, or 6 carbon atoms because of non-crystallinity. The polyfluoroalkylene group preferably has one or more fluorine atoms bonded to the terminal carbon atom, more preferably a perfluoroalkylene group. The polyfluoroalkylene group has better liquid crystallinity than the polyfluoroalkylene oxide group.
Specific examples of the polyfluoroalkylene group include the following groups.
_{- (CF 2) 2 -,} - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -, - (CF 2) 10 -, - (CF 2) 12 -, - CF _{2 CHF -, - CF 2 CHF} (CF 2) 2 -, - CF 2 CHF (CF 2) 4 -, - CF 2 CHF (CF 2) 2 CHFCF 2 -, - CF 2 CHF (CF 2) 4 CHF- _{, -CF 2 CH 2 (CF 2} ) 4 CH 2 CF 2 -, - CF 2 CHF (CF 2) 4 CHFCF 2 -, - CHF (CF 2) 6 CHF -, - CF 2 CH (CF 2 CF 3) _{(CF 2) 2 CH 2 -} .

R ¹ of the compound (1) is a hydrogen atom or a methyl group. When R ¹ is a hydrogen atom (that is, the compound (1) is an acrylate ester), a polymerizable liquid crystal composition containing the compound (1) is photopolymerized to obtain an optically anisotropic material and an optical element. This is preferable because the polymerization reaction proceeds rapidly. In addition, the characteristics of the optically anisotropic material and the optical element obtained by the photopolymerization reaction are not easily affected by the external environment (temperature, etc.), and there is an advantage that the in-plane distribution of retardation is small.

The compound (1) has an alkyl group, an alkoxy group, a fluorine atom or a cyano group as R ² , and this widens the temperature range showing the liquid crystallinity of the polymerizable liquid crystal composition containing the compound (1). When R ² is an alkyl group or an alkoxy group, the number of carbon atoms is preferably 2 to 6, more preferably 3 to 5, and the linear structure is particularly preferable because the temperature range in which the compound (1) exhibits liquid crystallinity can be widened. It is.

m and n are each an integer of 1 to 3, and 1 or 2 is preferable. Moreover, it is preferable from the point of the manufacture ease of a compound (1) that m and n are the same value.
Preferable specific examples of compound (1) include the following compounds (1A) to (1C).

CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -O-Ph-Ph-R ² (1A)
CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -O-Ph-Cy-Ph-R ² (1B)
CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -O-Ph-Cy-Ph-Ph-R ² (1C)

However, the symbols R ^F , R ¹ , R ² , m, and n in the formulas (1A) to (1C) are independent for each formula, and are the same as those described above. In addition, Ph and Cy are each independently the same as defined above for each formula, and a plurality of Ph in one molecule can also independently represent a substituted or unsubstituted phenylene group.

  As more specific examples, the following compound (1A0a) to compound (1A0aa), the following compound (1B0a) to compound (1B0aa), the following compound (1C0a) to compound (1C0aa), the following compound (1A5a) to compound (1A5r) The following compounds (1B5a) to (1B5r) and the following compounds (1C5a) to (1C5r) can be mentioned. However, the symbols Ph and Cy in the following formula are the same as defined above independently for each formula, and a plurality of Ph in one molecule also independently represent a substituted or unsubstituted phenylene group. To get. The symbol r represents an integer of 1 to 8 independently for each formula.

CH ₂ = CH-COO-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Ph-CN (1A0a)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Ph-CN (1A0b)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Ph-CN (1A0c)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₈ -CH ₂ -O-Ph-Ph-CN (1A0d)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₁₀ -CH ₂ -O-Ph-Ph-CN (1A0e)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₁₂ -CH ₂ -O-Ph-Ph-CN (1A0f)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A0g)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A0h)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 4 - (CH 2) 2 -O-Ph-Ph-CN (1A0i)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Ph-CN (1A0j)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A0k)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A0l)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 8 - (CH 2) 2 -O-Ph-Ph-CN (1A0m)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 8 - (CH 2) 3 -O-Ph-Ph-CN (1A0n)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _10- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A0o)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _10- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A0p)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 12 - (CH 2) 2 -O-Ph-Ph-CN (1A0q)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 12 - (CH 2) 3 -O-Ph-Ph-CN (1A0r)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF-CH ₂ -O-Ph-Ph-CN (1A0s)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ -CH ₂ -O-Ph-Ph-CN (1A0t)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ -CH ₂ -O-Ph-Ph-CN (1A0u)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ CHFCF ₂ -CH ₂ -O-Ph-Ph-CN (1A0v)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHF-CH ₂ -O-Ph-Ph-CN (1A0w)
CH ₂ = CH-COO-CH ₂ -CF ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CF ₂ -CH ₂ -O-Ph-Ph-CN (1A0x)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHFCF ₂ -CH ₂ -O-Ph-Ph-CN (1A0y)
CH ₂ = CH-COO-CH ₂ -CHF (CF ₂ ) ₆ CHF-CH ₂ -O-Ph-Ph-CN (1A0z)
CH ₂ = CH-COO-CH ₂ -CF ₂ CH (CF ₂ CF ₃ ) (CF ₂ ) ₂ -CH ₂ -O-Ph-Ph-CN (1A0aa)

CH ₂ = CH-COO-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0a)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0b)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0c)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₈ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0d)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₁₀ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0e)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₁₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0f)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0g)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0h)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 4 - (CH 2) 2 -O-Ph-Cy-Ph- (CH 2) r H (1B0i)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Cy-Ph- (CH 2) r H (1B0j)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0k)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0l)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 8 - (CH 2) 2 -O-Ph-Cy-Ph- (CH 2) r H (1B0m)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 8 - (CH 2) 3 -O-Ph-Cy-Ph- (CH 2) r H (1B0n)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _10- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0o)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _10- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0p)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 12 - (CH 2) 2 -O-Ph-Cy-Ph- (CH 2) r H (1B0q)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 12 - (CH 2) 3 -O-Ph-Cy-Ph- (CH 2) r H (1B0r)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF-CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0s)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0t)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0u)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ CHFCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0v)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHF-CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0w)
CH ₂ = CH-COO-CH ₂ -CF ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0x)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHFCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0y)
CH ₂ = CH-COO-CH ₂ -CHF (CF ₂ ) ₆ CHF-CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0z)
CH ₂ = CH-COO-CH ₂ -CF ₂ CH (CF ₂ CF ₃ ) (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B0aa)

CH ₂ = CH-COO-CH _2- (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0a)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0b)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₆ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0c)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₈ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0d)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₁₀ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0e)
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₁₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0f)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0g)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0h)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 4 - (CH 2) 2 -O-Ph-Cy-Ph-Ph- (CH 2) r H (1C0i)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 4 - (CH 2) 3 -O-Ph-Cy-Ph-Ph- (CH 2) r H (1C0j)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0k)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0l)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 8 - (CH 2) 2 -O-Ph-Cy-Ph-Ph- (CH 2) r H (1C0m)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 8 - (CH 2) 3 -O-Ph-Cy-Ph-Ph- (CH 2) r H (1C0n)
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) _10- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0o)
CH ₂ = CH-COO- (CH ₂ ) _3- (CF ₂ ) _10- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0p)
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 12 - (CH 2) 2 -O-Ph-Cy-Ph-Ph- (CH 2) r H (1C0q)
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 12 - (CH 2) 3 -O-Ph-Cy-Ph-Ph- (CH 2) r H (1C0r)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF-CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0s)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0t)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0u)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ CHFCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0v)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHF-CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0w)
CH ₂ = CH-COO-CH ₂ -CF ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0x)
CH ₂ = CH-COO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHFCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0y)
CH ₂ = CH-COO-CH ₂ -CHF (CF ₂ ) ₆ CHF-CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0z)
CH ₂ = CH-COO-CH ₂ -CF ₂ CH (CF ₂ CF ₃ ) (CF ₂ ) ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C0aa)

CH ₂ = CH-COO-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5a)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5b)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5c)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5d)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5e)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF ₂ -CH ₂ -O-Ph-Ph-CN (1A5f)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5g)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5h)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5i)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5j)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5k)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5l)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5m)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5n)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5o)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5p)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₂ -O-Ph-Ph-CN (1A5q)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₃ -O-Ph-Ph-CN (1A5r)

CH ₂ = CH-COO-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5a)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5b)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5c)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5d)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5e)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5f)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5g)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5h)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5i)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5j)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5k)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5l)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5m)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5n)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5o)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5p)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5q)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph- (CH ₂ ) _r H (1B5r)

CH ₂ = CH-COO-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5a)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5b)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5c)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5d)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5e)
CH ₂ = CH-COO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF ₂ -CH ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5f)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5g)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (1C5h)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5i)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5j)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5k)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5l)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5m)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5n)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5o)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5p)
CH ₂ = CH-COO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₂ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5q)
CH ₂ = CH-COO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₃ -O-Ph-Cy-Ph-Ph- (CH ₂ ) _r H ( 1C5r)

  In the above compound, r is preferably an integer of 2 to 6, and more preferably 3 to 5. Further, it is preferable that Ph is an unsubstituted 1,4-phenylene group or a methyl-substituted 1,4-phenylene group, and Cy is an unsubstituted trans-1,4-cyclohexylene group. Among the above compounds, compounds (1A0a) to (1A0c), compounds (1A0j) to (1A0l), compounds (1B0a) to (1B0c), compounds (1B0j) to (1B0l), compounds (1C0a) to (1C0c) ), Compounds (1C0j) to (1C01), compounds (1A5a) to (1A5c), compounds (1A5g) to (1A5j), compounds (1B5a) to (1B5c), compounds (1B5g) to (1B5j), compounds (1C5a) ) To (1C5c) and compounds (1C5g) to (1C5j) are preferred.

  A method for synthesizing the compound (1) of the present invention will be described with specific examples. Examples of the method for synthesizing the compound (1A0b) include the method shown in the following reaction formula. However, the symbols in the formula have the same meaning as described above.

  First, the following compound (01b) and 3,4-dihydropyran are reacted in dichloromethane in the presence of p-toluenesulfonic acid to obtain the following compound (02b). Next, this compound (02b) is reacted with perfluorobutanesulfonyl fluoride in the presence of triethylamine, and this is reacted with the following compound (13A) in DMF in the presence of cesium carbonate to obtain the following compound (14A0b) Get. Further, this compound (14A0b) is reacted with p-toluenesulfonic acid to obtain the following compound (15A0b). This compound (15A0b) is reacted with acrylic acid chloride in the presence of triethylamine to obtain compound (1A0b).

  The compound (1A0a) can be synthesized by replacing the compound (01b) in the synthesis method of the compound (1A0b) with the following compound (01a). (1A0c) to (1A0aa) can be synthesized by replacing the compound (01b) in the above synthesis method with the following compounds (01c) to (01aa), respectively.

HO-CH _2- (CF ₂ ) ₂ -CH ₂ -OH (01a)
HO-CH _2- (CF ₂ ) ₄ -CH ₂ -OH (01b)
HO-CH _2- (CF ₂ ) ₆ -CH ₂ -OH (01c)
HO-CH _2- (CF ₂ ) ₈ -CH ₂ -OH (01d)
HO-CH _2- (CF ₂ ) ₁₀ -CH ₂ -OH (01e)
HO-CH _2- (CF ₂ ) ₁₂ -CH ₂ -OH (01f)
HO- (CH ₂ ) _2- (CF ₂ ) _2- (CH ₂ ) ₂ -OH (01g)
HO- (CH ₂ ) _3- (CF ₂ ) _2- (CH ₂ ) ₃ -OH (01h)
_{HO- (CH 2) 2 - (} CF 2) 4 - (CH 2) 2 -OH (01i)
_{HO- (CH 2) 3 - (} CF 2) 4 - (CH 2) 3 -OH (01j)
HO- (CH ₂ ) _2- (CF ₂ ) _6- (CH ₂ ) ₂ -OH (01k)
HO- (CH ₂ ) _3- (CF ₂ ) _6- (CH ₂ ) ₃ -OH (01l)
_{HO- (CH 2) 2 - (} CF 2) 8 - (CH 2) 2 -OH (01m)
_{HO- (CH 2) 3 - (} CF 2) 8 - (CH 2) 3 -OH (01n)
HO- (CH ₂ ) _2- (CF ₂ ) _10- (CH ₂ ) ₂ -OH (01o)
HO- (CH ₂ ) _3- (CF ₂ ) _10- (CH ₂ ) ₃ -OH (01p)
_{HO- (CH 2) 2 - (} CF 2) 12 - (CH 2) 2 -OH (01q)
_{HO- (CH 2) 3 - (} CF 2) 12 - (CH 2) 3 -OH (01r)
HO-CH ₂ -CF ₂ CHF-CH ₂ -OH (01s)
HO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ -CH ₂ -OH (01t)
HO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ -CH ₂ -OH (01u)
HO-CH ₂ -CF ₂ CHF (CF ₂ ) ₂ CHFCF ₂ -CH ₂ -OH (01v)
HO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHF-CH ₂ -OH (01w)
HO-CH ₂ -CF ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CF ₂ -CH ₂ -OH (01x)
HO-CH ₂ -CF ₂ CHF (CF ₂ ) ₄ CHFCF ₂ -CH ₂ -OH (01y)
HO-CH ₂ -CHF (CF ₂ ) ₆ CHF-CH ₂ -OH (01z)
HO-CH ₂ -CF ₂ CH (CF ₂ CF ₃ ) (CF ₂ ) ₂ -CH ₂ -OH (01aa)

The compound (1B0b) can be similarly synthesized by replacing the compound (13A) in the method for synthesizing the compound (1A0b) with the following compound (13B). (1B0a) and (1B0c) to (1B0aa) are obtained by changing the compound (13A) to the compound (13B) and further changing the compound (01b) to (01a) and (01c) to (01aa), respectively. Can be synthesized in the same way.
The compound (1C0b) can be synthesized in the same manner by replacing the compound (13A) in the synthesis method of the compound (1A0b) with the following compound (13C). (1C0a) and (1C0c) to (1C0aa) are obtained by changing the compound (13A) to the compound (13C) and further changing the compound (01b) to (01a) and (01c) to (01aa), respectively. Can be synthesized in the same way.
The symbols in the formulas are the same as defined above independently for each formula.

HO-Ph-Ph-CN (13A)
HO-Ph-Cy-Ph- (CH ₂ ) _r H (13B)
HO-Ph-Cy-Ph-Ph- (CH ₂ ) _r H (13C)
Examples of a method for synthesizing the compound (1A5a) include a method for synthesizing according to the following reaction formula. The definition of the symbols in the formula is the same as described above.

  First, the following compound (51a) and 3,4-dihydropyran are reacted in dichloromethane in the presence of p-toluenesulfonic acid to obtain the following compound (52a). Next, this compound (52a) is reacted with perfluorobutanesulfonyl fluoride in the presence of triethylamine, and this is reacted with the following compound (13A) in DMF in the presence of cesium carbonate, whereby the following compound (14A5a) Get. Furthermore, this compound (14A5a) and p-toluenesulfonic acid are reacted to obtain the following compound (15A5a). This compound (15A5a) is reacted with acrylic acid chloride in the presence of triethylamine to obtain compound (1A5a).

  The compounds (1A5b) to (1A5r) can be synthesized by replacing the compound (51a) in the synthesis method with the following compounds (51b) to (51r), respectively.

HO-CH ₂ -CF ₂ -OCF ₂ CF ₂ -OCF ₂ -CH ₂ -OH (51a)
HO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF ₂ -CH ₂ -OH (51b)
HO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF ₂ -CH ₂ -OH (51c)
HO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF ₂ -CH ₂ -OH (51d)
HO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF ₂ -CH ₂ -OH (51e)
HO-CH ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF ₂ -CH ₂ -OH (51f)
HO- (CH ₂ ) ₂ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₂ -OH (51g)
HO- (CH ₂ ) ₃ -CF ₂ -OCF ₂ CF ₂ -OCF _2- (CH ₂ ) ₃ -OH (51h)
HO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₂ -OH (51i)
HO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₂ -OCF _2- (CH ₂ ) ₃ -OH (51j)
HO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₂ -OH (51k)
HO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₃ -OCF _2- (CH ₂ ) ₃ -OH (51l)
HO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₂ -OH (51m)
HO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₄ -OCF _2- (CH ₂ ) ₃ -OH (51n)
HO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₂ -OH (51o)
HO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₅ -OCF _2- (CH ₂ ) ₃ -OH (51p)
HO- (CH ₂ ) ₂ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₂ -OH (51q)
HO- (CH ₂ ) ₃ -CF _2- (OCF ₂ CF ₂ ) ₆ -OCF _2- (CH ₂ ) ₃ -OH (51r)

  Moreover, the said compound (1B5a) is compoundable similarly by changing the compound (13A) in the synthesis | combining method of the said compound (1A5a) with the compound (13B). Compounds (1B5b) to (1B5r) are similarly obtained by changing compound (13A) to compound (13B) in the above synthesis method and further changing compound (51a) to compounds (51b) to (51r), respectively. Can be synthesized.

The compound (1C5a) can be synthesized in the same manner by replacing the compound (13A) in the method for synthesizing the compound (1A5a) with the compound (13C). Compounds (1C5b) to (1C5r) can be synthesized in the same manner by changing compound (13A) to compound (13C) and further changing compound (51a) to compounds (51b) to (51r), respectively.
The symbols in the formulas are the same as defined above independently for each formula.

In addition, a compound in which R ¹ is a methyl group in formula (1) can be synthesized in the same manner by changing acrylic acid chloride to methacrylic acid chloride.

<Polymerizable liquid crystal composition>
The compound (1) of the present invention contains a polymerizable group by an unsaturated bond and a liquid crystalline skeleton by a plurality of 6-membered rings, and constitutes a liquid crystal component constituting a polymerizable liquid crystal composition for obtaining a polymer liquid crystal, that is, It can be used as a polymerizable liquid crystal compound. However, in the preparation of the polymerizable liquid crystal composition, the compound (1) is not necessarily required to exhibit a liquid crystal phase alone, exhibits good compatibility with the polymerizable liquid crystal composition, and exhibits a supercooled state. That's fine. That is, a polymerizable liquid crystal composition can be constituted by combining the compound (1) and a polymerizable liquid crystal compound not corresponding to the formula (1) (hereinafter, the compound (1) alone which exhibits a liquid crystal phase is polymerized. A polymerizable liquid crystal compound that is referred to as a polymerizable liquid crystal compound (A) and does not correspond to the formula (1) is referred to as a polymerizable liquid crystal compound (B)).

When compound (1) is prepared into a polymerizable liquid crystal composition in combination with polymerizable liquid crystal compound (B), the temperature range showing the liquid crystal phase can be broadened. Moreover, since melting | fusing point ( _Tm ) fall arises, the handling of a composition becomes easy. Therefore, when a polymerizable liquid crystal composition containing the compound (1) and the polymerizable liquid crystal compound (B) is prepared, the polymerizable liquid crystal composition for obtaining a polymer liquid crystal exhibits liquid crystallinity even in a low temperature range. It becomes possible. The polymerizable liquid crystal component constituting the liquid crystal phase of the polymerizable liquid crystal composition is preferably composed of one or more compounds (1) and one or more polymerizable liquid crystal compounds (B).

Since the compound (1) of the present invention has a structure containing a polyfluoroalkylene group or a polyfluoroalkylene oxide group in the spacer portion, when a polymerizable liquid crystal composition is prepared using this, the compound (1) It moves toward the surface of the polymerizable liquid crystal composition and cures at the outermost surface, and the composition can exhibit excellent leveling properties. In particular, it exhibits excellent leveling properties in a composition prepared by combining with a polymerizable liquid crystal compound containing no fluorine atom. This is presumably because the fluorine atom-containing monomer and the monomer not containing a fluorine atom have different polymerization rates, and the fluorine atom-containing monomer whose compatibility is relatively lowered as the polymerization proceeds progresses to the film surface. That is, the fluorine atom causes a difference in the polymerization reactivity of the monomer. Therefore, the greater the difference in fluorine atom content among the plural types of monomers combined, the greater the difference in reactivity and the higher leveling can be expressed. However, the compound (1) has a relatively small number of fluorine atoms in one molecule of 28 or less, and in particular, since a polyfluoroalkylene group or a polyfluoroalkylene oxide group exists in the molecule, the polymerizable liquid crystal composition Good compatibility with other components that do not contain fluorine atoms. In addition, when compound (1) is added to a polymerizable liquid crystal composition using another liquid crystal compound, the crystalline liquid crystal composition undergoes crystal precipitation when left at room temperature due to a decrease in the melting point of the polymerizable liquid crystal composition. Can be prevented. Furthermore, since — (CH ₂ ) _m R ^F (CH ₂ ) _n — is linked to the (meth) acryloyloxy group, it is possible to suppress a decrease in Δn value often observed before and after the polymerization reaction of the polymerizable liquid crystal. The polymer exhibits a high Δn value. This property is remarkable when R ^F is a polyfluoroalkylene group. Therefore, by preparing a polymer from the polymerizable liquid crystal composition using the compound (1), it is possible to provide an optically anisotropic material and an optical element that are low in scattering and excellent in in-plane distribution uniformity of retardation.

  The polymerizable liquid crystal composition of the present invention may contain a non-liquid crystalline component or a non-polymerizable liquid crystal compound, but the unsaturated fatty acid ester represented by the formula (1), that is, the compound (1) and The total amount of the polymerizable liquid crystal compound (B) is preferably 70% by mass or more, more preferably 80% by mass, and more preferably 90% by mass or more based on the total amount of the polymerizable liquid crystal composition. Particularly preferred. When the ratio is such, the polymerizable liquid crystal composition can ensure liquid crystallinity in a wide temperature range, and a polymer obtained by polymerizing the polymerizable liquid crystal composition expresses the necessary Δn, depending on the temperature of Δn. This is because there is little change.

The polymerizable liquid crystal compound (B) is preferably a compound having a (meth) acryloyl group, and more preferably a compound having an acryloyl group. Specifically, the polymerizable liquid crystal compound (B) is preferably a compound represented by the following formula (2). However, the definitions of symbols R ³ , R ⁴ , E ^{5 to} E ⁸ , t, p, q, s, and w in the formula (2) are the same as described above.

CH ₂ = CR ³ -COO- (CH ₂ ) _t- (O) _p -E ⁵ -wE ^6- (E ⁷ ) _q- (E ⁸ ) _s -R ⁴ (2)

R ³ of the compound (2) is a hydrogen atom or a methyl group, but when R ³ is a hydrogen atom, a polymerization reaction occurs when the polymerizable liquid crystal composition is photopolymerized to obtain an optically anisotropic material and an optical element. Is preferable because it proceeds rapidly.

When the compound (2) has an alkyl group, an alkoxy group, a fluorine atom or a cyano group as R ⁴ , the temperature range showing the liquid crystallinity of the polymerizable liquid crystal composition can be widened. When R ⁴ is an alkyl group or an alkoxy group, the number of carbon atoms is preferably 2-6, more preferably 3-5, and when R ⁴ is a linear alkyl group or alkoxy group, the compound (2) is liquid crystalline. This is preferable because the temperature range showing can be increased.

Specific preferred examples of the compound (2) include compounds represented by the following formulas (2A) to (2G). However, in formulas (2A) to (2G), Z ^{1 to} Z ¹⁴ are each independently Ph or Cy for each formula, but at least one of Z ^{9 to} Z ¹¹ is Cy, and Z ⁹ And Z ¹⁰ do not become Ph at the same time. When Z ¹⁴ is Ph, Z ¹³ is Cy, and when Z ¹² is Cy, Z ¹³ is Ph. The symbols R ³ , R ⁴ , t, Ph and Cy in the formulas (2A) to (2G) are independent for each formula and are the same as defined above.

CH ₂ = CR ³ -COO-Ph-OCO-Cy-Z ¹ -R ⁴ (2A)
CH ₂ = CR ³ -COO-Ph-OCO-Z ² -R ⁴ (2B)
CH ₂ = CR ³ -COO-Z ³ -Z ⁴ -R ⁴ (2C)
CH ₂ = CR ³ -COO- (CH ₂ ) _t -O-Ph-Z ⁵ -R ⁴ (2D)
CH ₂ = CR ³ -COO-Z ⁶ -Z ⁷ -Z ⁸ -R ⁴ (2E)
CH ₂ = CR ³ -COO- (CH ₂ ) _t -OZ ⁹ -Z ¹⁰ -Z ¹¹ -R ⁴ (2F)
CH ₂ = CR ³ -COO- (CH ₂ ) _t -O-Ph-Z ¹² -Z ¹³ -Z ¹⁴ -R ⁴ (2G)

More specifically, preferred examples of the compound (2) include the following formulas (2Aa), (2Ab), (2Ba), (2Bb), (2Ca), (2Cb), (2Da), (2Db), ( 2Ea), (2Eb), (2Fa), (2Ga) compounds. However, the symbols R ⁴ , Ph and Cy in formulas (2Aa) to (2Ga) are the same as defined above independently for each formula, and a plurality of Ph and a plurality of Cy in one molecule are each Independently different substituted or unsubstituted phenylene groups, different substituted or unsubstituted cyclohexylene groups may be represented. The symbol t in the formula is an integer of 1 to 8, and preferably an integer of 2 to 6.

CH ₂ = CH-COO-Ph-OCO-Cy-Ph-R ⁴ (2Aa)
CH ₂ = CH-COO-Ph-OCO-Cy-Cy-R ⁴ (2Ab)
CH ₂ = CH-COO-Ph-OCO-Cy-R ⁴ (2Ba)
CH ₂ = CH-COO-Ph-OCO-Ph-R ⁴ (2Bb)
CH ₂ = CH-COO-Cy-Cy-R ⁴ (2Ca)
CH ₂ = CH-COO-Ph-Cy-R ⁴ (2Cb)
CH ₂ = CH-COO-Ph-Ph-R ⁴ (2Cc)
CH ₂ = CH-COO- (CH ₂ ) _t -O-Ph-Ph-R ⁴ (2Da)
CH ₂ = CH-COO- (CH ₂ ) _t -O-Ph-Cy-R ⁴ (2Db)
CH ₂ = CH-COO-Ph-Ph-Cy-R ⁴ (2Ea)
CH ₂ = CH-COO-Ph-Cy-Ph-R ⁴ (2Eb)
CH ₂ = CH-COO- (CH ₂ ) _t -O-Ph-Cy-Ph-R ⁴ (2Fa)
CH ₂ = CH-COO- (CH ₂ ) _t -O-Ph-Cy-Ph-Ph-R ⁴ (2Ga)

  When preparing the polymerizable liquid crystal composition of the present invention using the compound (1) and the compound (2), depending on the type of the compound (1), for example, the compatibility, the liquid crystal temperature range, etc. are taken into consideration as appropriate. A preferred combination may be determined by selecting the compound (2). Preferred examples based on the above selection criteria include a polymerizable liquid crystal composition containing the compound (1A) or compound (1B) and the compound (2Bb) or the compound (2Da), and the compound (1C) Examples thereof include a polymerizable liquid crystal composition containing the compound (2Eb).

Further, as the compound (2) blended in the polymerizable liquid crystal composition of the present invention, the following compounds (2Ha), (2Hb), (2Ia), (2Ib), (2Ja), (2Jb), (2Ka) , (2 Kb) may be used. However, the symbols R ⁴ , Ph and Cy in the formula are each independently the same as defined above for each formula, and a plurality of Ph and Cy in one molecule are each independently substituted or non-substituted. A substituted phenylene group and different substituted or unsubstituted cyclohexylene groups may be represented.

CH ₂ = CH-COO-Ph-Cy-COO-Cy-Ph-R ⁴ (2Ha)
CH ₂ = CH-COO-Ph-Cy-OCO-Cy-Ph-R ⁴ (2Hb)
CH ₂ = CH-COO-Cy-COO-Cy-Ph-R ⁴ (2Ia)
CH ₂ = CH-COO-Cy-OCO-Cy-Ph-R ⁴ (2Ib)
CH ₂ = CH-COO-Ph-Ph-C≡C-Ph-Cy-R ⁴ (2Ja)
CH ₂ = CH-COO-Cy-Ph-C≡C-Ph-Cy-R ⁴ (2Jb)
CH ₂ = CH-COO-Ph-C≡C-Ph-Ph-Cy-R ⁴ (2Ka)
CH ₂ = CH-COO-Ph-C≡C-Ph-Cy-Ph-R ⁴ (2Kb)

  The content of the compound (1) is preferably 5 to 50 mol%, more preferably 8 to 30 mol%, based on the total amount of the compound (1) and the polymerizable liquid crystal compound (B). If it is less than 5 mol%, the film thickness unevenness tends to be difficult to control, and if it exceeds 50 mol%, domains due to phase separation are formed and a uniform film tends to be difficult to obtain.

  Non-liquid crystalline components (hereinafter referred to as other components) that may be contained in the polymerizable liquid crystal composition of the present invention include a polymerization initiator, a chiral agent, an ultraviolet absorber, an antioxidant, and light stability. Agents, dichroic dyes and the like.

As described above, the preferred ratio of the compound (1) and the polymerizable liquid crystal compound (B) (hereinafter referred to as liquid crystal components) contained in the polymerizable liquid crystal composition is 70% by mass or more. Since the blending ratio of the non-liquid crystalline component as described above varies greatly depending on the application, the ratio of the liquid crystalline component and other components in the polymerizable liquid crystal composition is appropriately adjusted depending on the application.
For example, when a chiral agent is used as the other component, the content of the chiral agent is preferably 5 to 29% by mass, particularly preferably 5 to 20% by mass with respect to the total amount of the polymerizable liquid crystal composition. Therefore, the amount of the liquid crystal component is preferably 71 to 95% by mass, and particularly preferably 80 to 95% by mass with respect to the total amount of the polymerizable liquid crystal composition.

  When using a dichroic dye as another component, 1-20 mass% is preferable with respect to the whole quantity of a polymeric liquid crystal composition, and, as for the quantity of a dichroic dye, 3-18 mass% is especially preferable. Therefore, the amount of the liquid crystal component is preferably 80 to 99% by mass, particularly preferably 82 to 97% by mass, based on the total amount of the polymerizable liquid crystal composition.

  When using an ultraviolet absorber, an antioxidant, a light stabilizer, etc. as other components, the amount of these components is preferably 5% by mass or less based on the total amount of the polymerizable liquid crystal composition, and 2% by mass. The following are particularly preferred: Accordingly, the amount of the liquid crystal component in this case is preferably 95 to 100% by mass, particularly preferably 98 to 100% by mass, based on the total amount of the polymerizable liquid crystal composition. The ratio of the polymerization initiator will be described later.

  When a plurality of functional components are used in combination as the non-liquid crystalline component described above, it is preferable to set each amount to be small within a preferable range of the content of each functional component so that the polymerizable liquid crystal compound is not insufficient. . When each functional component is a combination of a plurality of compounds, the total amount is preferably within the above range.

<Optically anisotropic material and optical element>
Polymer obtained by polymerizing compound (1) or polymerizable liquid crystal composition in a state where the liquid crystal is aligned in an environment in which compound (1) of the present invention or a polymerizable liquid crystal composition using the same exhibits a liquid crystal phase Can be used as an optically anisotropic material and can be applied to components of optical elements. In particular, it is preferable to obtain a polymer using a polymerizable liquid crystal composition.
Hereinafter, preparation of a polymer using the polymerizable liquid crystal composition will be described.

In general, the environment that affects the presentation of the liquid crystal phase includes temperature, pressure, electric field, magnetic field, composition mixing state, composition interface state, etc. In the present invention, the polymerizable liquid crystal composition is a liquid crystal. In order to maintain the state showing the phase, the atmospheric temperature may be adjusted to be equal to or lower than the nematic phase-isotropic phase transition temperature (T _c ). However, since the Δn value of the polymerizable liquid crystal composition is extremely small at a temperature close to T _c , the upper limit of the ambient temperature is preferably (T _c −10) ° C. or lower.

  Examples of the polymerization reaction include a photopolymerization reaction and a thermal polymerization reaction, and a photopolymerization reaction is preferred. The light used for the photopolymerization reaction is preferably ultraviolet light or visible light. When carrying out the photopolymerization reaction, it is preferable to use a photopolymerization initiator, and the photopolymerization initiators are acetophenones, benzophenones, benzoins, benzyls, Michler's ketones, benzoin alkyl ethers, benzyldimethylketals and thioxanthones. It can select suitably from etc., and can be used 1 type or in combination of 2 or more types. The amount of the photopolymerization initiator is preferably from 0.1 to 5% by mass, particularly preferably from 0.3 to 2% by mass, based on the total amount of the polymerizable liquid crystal composition. When using a plurality of types of photopolymerization initiators, the total amount is preferably in the above range.

  The polymer of the present invention is obtained by polymerizing a polymerizable liquid crystal composition in a state where liquid crystal components are aligned. Specifically, a polymerizable liquid crystal composition is applied to a substrate that has been subjected to an alignment treatment, the liquid crystal is aligned, and a polymerization component is polymerized to obtain a polymer supported on the substrate. It can also be used as an element.

As the substrate, for example, a substrate rubbed with fibers such as cotton, wool, nylon, polyester, or the like, a substrate formed with an organic thin film on the surface and rubbed with cloth, or SiO ₂ was obliquely deposited. A substrate having an alignment film can be used. By preparing and applying a substrate subjected to such an alignment treatment, the coating film on the substrate is in a state where the liquid crystal component is aligned.

As the alignment treatment using means other than the rubbing treatment and the oblique deposition of SiO ₂ , a flow alignment of the polymerizable liquid crystal composition, a method using an electric field or a magnetic field, and the like can be used. These orientation means may be used alone or in combination. Further, a photo-alignment method can be used as an alignment treatment method instead of the rubbing treatment. In this method, for example, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that isomerizes with light, and an organic thin film such as a polyimide thin film are formed. The alignment film is formed by irradiating polarized light, preferably polarized ultraviolet rays. By applying an optical mask in this photo-alignment method, alignment patterning can be easily achieved, so that the molecular orientation inside the polymer can be precisely controlled.

  As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

  If appropriate orientation cannot be obtained by rubbing the substrate with fibers such as cotton, wool, nylon, polyester, etc., an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method. This may be rubbed with a cloth or the like. In addition, the polyimide thin film that gives a pretilt angle used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element can control the molecular orientation structure inside the polymer more precisely. preferable.

  Examples of the method for applying the polymerizable liquid crystal composition of the present invention on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. it can. At the time of coating, an organic solvent may be added to the polymerizable liquid crystal composition as a diluent for improving the coating property. In this case, the organic solvent is volatilized and removed after coating on the substrate. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolves and the like. The solvent may be used alone or in combination of a plurality of types, and may be appropriately selected in consideration of the vapor pressure and the solubility of the compound (1) and the polymerizable liquid crystal composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used.

  In order to further improve the applicability of the polymerizable liquid crystal composition, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate. An intermediate layer such as a polyimide thin film is also effective as a means for improving the adhesion when the adhesion between the polymer and the substrate is not good.

As a method of polymerizing the polymerizable liquid crystal composition of the present invention, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is particularly preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when polymerization is performed in a state where the polymerizable liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency with respect to active energy rays. . Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, a polymerization method may be used. The temperature at the time of light irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention is maintained. Intensity of the active energy ray is preferably ^{0.1~2W / cm 2, 0.5~1.5W / cm} 2 is more preferable. When the strength is 0.1 mW / cm ² or less, a great amount of time is required to complete the photopolymerization, which may reduce productivity. When the strength is 2 W / cm ² or more, the polymerizable liquid crystal composition may be deteriorated.

The polymer prepared by the polymerization reaction can be further subjected to heat treatment for the purpose of reducing the initial characteristic change of the polymer and achieving stable characteristic expression. The temperature of the heat treatment is in the range of 50 to 250 ° C, preferably 80 to 180 ° C, and the heat treatment time is preferably in the range of 30 seconds to 12 hours.
The thickness of the polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention is preferably 0.5 to 8 μm, more preferably 0.7 to 6 μm. If it is too thin, uneven coating may occur, and the uniformity of retardation in the surface may be reduced. If it is too thick, the orientation may be disturbed and the transmittance may be reduced.
In the present invention, the polymer obtained by the polymerization reaction may be used while being held on the support using the substrate as a support, or may be used after being peeled off from the substrate. Further, the obtained polymer may be laminated or bonded to another substrate for use. Since the polymer of the present invention is optically transparent and has anisotropy, it is useful for applications utilizing the function of modulating polarized light. Specifically, it is useful as an optically anisotropic material used for the purpose of modulating the phase state and / or wavefront state of polarized light, and can be suitably applied to an optical element having a member made of an optically anisotropic material. For example, the polymer of the present invention can be used as a phase plate or the like mounted on a liquid crystal display or an optical pickup device. As a specific form used as the phase plate, for example, a form in which a quarter wave plate is installed on the front surface of the Lcos panel to improve light leakage at the time of black display can be cited.

[Synthesis of Hydroxyl Compound (13B-1)]
The hydroxyl compound (13B-1) was synthesized from the compound (21) through the compound (22), the compound (24), the compound (25) and the compound (26) according to the following procedure.
(1) Synthesis of compound (22)

Compound (21) (13.00 g) was added to a 500 mL four-necked flask equipped with a reflux apparatus, a stirrer, and a dropping apparatus, and a 2 mol / L sodium hydroxide aqueous solution (250 mL) was added thereto. To this, dimethyl sulfate (34.48 g) was added dropwise over 1 hour while taking care that the temperature of the reaction vessel did not exceed 60 ° C. under a nitrogen stream. After completion of dropping, the temperature in the reaction vessel was raised to 70 ° C. over 30 minutes, and the mixture was stirred and refluxed for 12 hours. After completion of the reaction, water and diethyl ether were added for liquid separation, and the organic layer was recovered. The collected organic layer was washed with a saturated aqueous sodium chloride solution (40 mL), then washed with water, and the organic layer was collected again.
The organic layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration under reduced pressure, and the filtrate was concentrated.

  The filtrate was purified by silica gel column chromatography using dichloromethane / hexane (5: 5, volume ratio) as a developing solution, and then the fraction containing the target product was concentrated to obtain powder crystals. A mixed solvent (200 mL) of dichloromethane and hexane was added to the powder crystals and recrystallization was performed to obtain Compound (22) (11.8 g). The yield was 85%.

  (2) Synthesis of compound (24)

  To a 500 mL four-necked flask equipped with a reflux apparatus, a stirrer, and a dropping apparatus, magnesium (1.53 g) was added and compound (23) (19.3 g) was dissolved in dehydrated tetrahydrofuran (50 mL). It was added dropwise over 30 minutes under a nitrogen stream. After completion of dropping, the mixture was stirred and refluxed at 70 ° C. for 3 hours to prepare a Grignard reagent. Next, this four-necked flask was cooled to 0 ° C., and compound (22) (18.4 g) dissolved in dehydrated tetrahydrofuran (100 mL) was added dropwise over 30 minutes under a nitrogen stream. . After completion of the dropwise addition, the mixture was stirred and refluxed at 70 ° C. for 3 hours, and then a 1 mol / L aqueous ammonium chloride solution (100 mL) was added to stop the reaction.

  The filtrate obtained by carrying out the same post-treatment as in the synthesis of compound (22) was purified by silica gel column chromatography using ethyl acetate / hexane (7: 3, volume ratio) as a developing solution, and compound (24 ) 21.5 g was obtained. The yield was 68%.

  (3) Synthesis of compound (25)

  Compound (24) (21.1 g), paratoluenesulfonic acid monohydrate (0.65 g), and toluene (400 mL) were added to a 500 mL eggplant-shaped flask equipped with a reflux apparatus and a stirrer, and molecular sieve was added thereto. An isobaric dropping funnel containing 4A (50 g) was attached, and the mixture was stirred and refluxed at 110 ° C. for 4 hours. After completion of the reaction, the same post-treatment as in the synthesis of compound (22) was performed to obtain 15.5 g of compound (25). The yield was 71%.

  (4) Synthesis of compound (26)

Compound (25) (12.9 g), tetrahydrofuran (200 mL), 10% palladium activated carbon (2.5 g) were added to a 5000 mL pressure-resistant reactor, and a cis-trans mixture of compound (26) (12.2 g) Got. The yield was 95%.
Hexane (100 mL) was added thereto and recrystallization was performed to obtain a trans isomer (2.00 g) of the compound represented by the formula (26). The filtrate was concentrated, transferred to a 500 mL eggplant-shaped flask, t-butoxypotassium (28.0 g) and N, N-dimethylformamide (300 mL) were added, and the mixture was stirred and refluxed at 100 ° C. for 6 hours. The cis isomer of the compound represented by 26) was converted to a trans isomer. After completion of the reaction, water (500 mL) was added to stop the reaction, and after the same post-treatment as in the synthesis of compound (22), hexane (100 mL) was added and recrystallization was performed. A trans isomer of the compound represented by (2.07 g) was obtained. The total yield of the compound (26) which was a trans isomer was 4.27 g, and the yield was 32%.

  (5) Synthesis of hydroxyl compound (13B-1)

  Compound (26) (4.07 g) and dichloromethane (200 mL) were added to a 500 mL four-necked flask equipped with a reflux apparatus, a stirrer, and a dropping apparatus. Under a nitrogen stream, boron tribromide (12.74 g) was added dropwise over 30 minutes. The dropping operation was performed while cooling with ice so that the internal temperature did not exceed 10 ° C. After stirring for 3 hours at room temperature, the reaction was stopped by adding water, and after the same post-treatment as in the synthesis of compound (22), a mixed solvent (100 mL) of dichloromethane and hexane was used. Recrystallization gave hydroxyl compound (13B-1) (3.68 g). The yield was 95%.

[Synthesis of Hydroxyl Compound (13C-1)]
The hydroxyl compound (13C-1) was synthesized from the compound (31) through the compound (33), the compound (34), the compound (35) and the compound (36) according to the following procedure.

  (1) Synthesis of compound (33)

  In a 1000 mL four-necked flask equipped with a reflux apparatus, a stirrer, and a dropping apparatus, compound (31) (23.57 g), compound (32) (14.25 g), palladium acetate (0.90 g), triphenylphosphine ( 2.07 g) was added. Acetone (200 mL) and 2 mol / L sodium hydrogen carbonate aqueous solution (250 mL) were added thereto under a nitrogen stream, and the mixture was stirred and refluxed at 65 ° C. for 18 hours. After completion of the reaction, the same post-treatment as in the synthesis of compound (22) of Synthesis Example 1 and silica gel column chromatography purification were performed to obtain compound (33) (16.0 g). The yield was 70%.

  (2) Synthesis of compound (34)

  To a 500 mL four-necked flask equipped with a reflux apparatus, a stirrer, and a dropping apparatus, magnesium (1.53 g) was added and compound (33) (16.5 g) was dissolved in dehydrated tetrahydrofuran (50 mL). It was added dropwise over 30 minutes under a nitrogen stream. After completion of dropping, the mixture was stirred and refluxed at 70 ° C. for 3 hours to prepare a Grignard reagent. Next, this four-necked flask was cooled to 0 ° C., and a solution obtained by dissolving the compound (22) (11.7 g) obtained in Synthesis Example 1 in dehydrated tetrahydrofuran (100 mL) was added for 30 minutes under a nitrogen stream. Was added dropwise. After completion of the dropwise addition, the mixture was stirred and refluxed at 70 ° C. for 3 hours, and then a 1 mol / L aqueous ammonium chloride solution (100 mL) was added to stop the reaction.

  The filtrate obtained by carrying out the same post-treatment as in the synthesis of the above-mentioned compound (22) was purified by silica gel column chromatography using ethyl acetate / hexane (7: 3, volume ratio) as a developing solution. (34) 13.6 g was obtained. The yield was 60%.

  (3) Synthesis of compound (35)

  Compound (34) (13.6 g), paratoluenesulfonic acid monohydrate (0.32 g), and toluene (200 mL) were added to a 500 mL eggplant-shaped flask equipped with a reflux apparatus and a stirrer, and molecular sieve was added thereto. An isobaric dropping funnel containing 4A (20 g) was attached, and the mixture was stirred and refluxed at 110 ° C. for 4 hours. After completion of the reaction, the same post treatment as in the synthesis of compound (22) of Synthesis Example 1 was performed to obtain 12.8 g of compound (35). The yield was 95%.

  (4) Synthesis of compound (36)

  Compound (35) (12.80 g), tetrahydrofuran (200 mL), 10% palladium activated carbon (2.5 g) were added to a 5000 mL pressure-resistant reactor, and the same as in the synthesis of compound (22) of Synthesis Example 1 Thus, a cis-trans mixture (12.1 g) of the compound represented by the formula (36) was obtained. The yield was 95%.

  Hexane (100 mL) was added thereto and recrystallization was performed to obtain a trans isomer (2.00 g) of compound (36). The filtrate was concentrated, transferred to a 500 mL eggplant-shaped flask, t-butoxypotassium (28.0 g) and N, N-dimethylformamide (300 mL) were added, and the mixture was stirred and refluxed at 100 ° C. for 6 hours. The cis form of 28d) was converted to the trans form. After completion of the reaction, water (500 mL) was added to stop the reaction, and after the same post-treatment as in the synthesis of compound (22) of Synthesis Example 1, hexane (100 mL) was added to perform recrystallization, A trans isomer (1.88 g) of the compound represented by the formula (36) was obtained. The total yield of the compound (36) which was a trans isomer was 3.88 g, and the yield was 30%.

  (5) Synthesis of hydroxyl compound (13C-1)

  Compound (36) (3.70 g) and dichloromethane (200 mL) were added to a 500 mL four-necked flask equipped with a reflux apparatus, a stirrer, and a dropping apparatus. Under a nitrogen stream, boron tribromide (12.74 g) was added dropwise over 30 minutes. The dropping operation was performed while cooling with ice so that the internal temperature did not exceed 10 ° C. After stirring for 3 hours at room temperature, the reaction was stopped by adding water, and after the same post-treatment as in the synthesis of compound (22) of Synthesis Example 1, a mixed solvent of dichloromethane and hexane ( 100 mL) was used for recrystallization to obtain hydroxyl compound (13C-1) (3.40 g). The yield was 95%.

[Synthesis of Diol Compound (51a)]
In Example 4 described on page 39 of WO 02/004397 pamphlet, HO (CH ₂ ) ₂ O (CH ₂ ) ₂ OH is converted to HO (CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ ) FCOCF ₂ O (CF ₂ ) ₂ OCF ₂ COF was obtained in the same manner except that it was changed to ₂ OH.
In the same manner as in Example 1-4a described on page 22 of JP-A-2006-45159, except that compound (E1) is changed to FCOCF ₂ O (CF ₂ ) ₂ OCF ₂ COF, CH ₃ OCOCF ₂ O (CF ₂ ) ₂ OCF ₂ CO ₂ CH ₃ was obtained. Furthermore, in Example 1-5 described on page 23, HOCH ₂ CF was similarly obtained except that compound (G1-1) was changed to CH ₃ OCOCF ₂ O (CF ₂ ) ₂ OCF ₂ CO ₂ CH _{3. 2} O (CF ₂ ) ₂ OCF ₂ CH ₂ OH (diol compound (51a)) was obtained.

Example 1 Synthesis of Unsaturated Fatty Acid Ester (1A0b-1) An unsaturated fatty acid ester (1A0b-1) was synthesized according to the synthesis route shown below. Details are described below.

(1) Synthesis of Compound (02b) Compound (01b) (2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, manufactured by Tokyo Chemical Industry Co., Ltd., 17.3 g) and 3,4-Dihydro-2H-pyran (3.10 g) was dissolved in dichloromethane (500 mL), p-toluenesulfonic acid monohydrate (180 mg) was added, and the mixture was stirred at room temperature for 15 hr. Triethylamine (101 mg) was added and the solvent was distilled off under reduced pressure to obtain a crude product (25.1 g). The title compound (10.7 g, 47% yield) was obtained by silica gel column chromatography (silica gel: MS GEL D-75-120A, manufactured by Asahi Glass Stech Co., Ltd., 500 g, eluent: hexane / ethyl acetate = 3/1). )

Spectral data of the compound (02b);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.57-1.84 (m, 6H, CH ₂ ), 3.57 (m, 1H), 3. 79-4.21 (m, 5H), 4.75 (m, 1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -120.6 (m, 2F), -123.1 (m, 2F), -124.2 (m , 2F), -124.5 (m, 2F).

(2) Synthesis of Compound (14A0b-1) Compound (02b) (5.30 g) was dissolved in ether (80 mL), and triethylamine (3.88 mL) was added. After cooling to 0 ° C., 1,1,2,2,3,3,4,4,4-nonafluorobutanesulfonyl fluoride (5.55 g) was added, gradually warmed to room temperature and stirred for 40 hours. . Water (100 mL) and t-butyl methyl ether (100 mL) were added, and the organic layer was washed with saturated brine, dried and then the solvent was removed to remove 1,1,2,2,3,3,4,4,4. A crude product (9.33 g) of 4-nonafluorobutanesulfonic acid 2,2,3,3,4,4,5,5-octafluoro-6- (tetrahydro-2H-pyran-2-yloxy) hexyl was obtained. Obtained. This crude product and compound (13A-1) (4-cyano-4′-hydroxy-biphenyl, manufactured by SYNTHON, 3.59 g) were dissolved in N, N-dimethylformamide (80 mL), and cesium carbonate (17. 96 g) was added and stirred at 80 ° C. for 1 hour. Water (100 mL) was added, and the mixture was extracted with t-butyl methyl ether (80 mL × 3 times). The obtained organic layer was washed with saturated brine (100 mL), and then the solvent was removed to obtain a crude product (9.42 g) of compound (14A0b-1). Purification by silica gel column chromatography (silica gel: 300 g MS-GEL D50-60-A (N) manufactured by Asahi Glass Stech Co., eluent: hexane / ethyl acetate = 4/1) gave the title compound (6.42 g, yield). 62%) was obtained.

Spectral data of the compound (14A0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.53-1.92 (m, 6H, CH ₂ ), 3.58 (m, 1H), 3. 83 (m, 1H), 3.96 (q, J = 13.5 Hz, 1H), 4.16 (q, J = 14.0 Hz, 1H), 4.52 (t, J = 13.0 Hz, 2H) ), 4.75 (t, J = 3.0 Hz, 1H), 7.06 (m, 2H), 7.56 (m, 2H), 7.66 (m, 2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −120.1 (m, 2F), −120.4 (m, 2F), −124.0 (m , 4F).

(3) Synthesis of Compound (15A0b-1) Compound (14A0b-1) (6.11 g) was dissolved in methanol (300 mL), and p-toluenesulfonic acid monohydrate (266 mg) was added for 3 hours at room temperature. Stir. Triethylamine (0.195 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product.
Purification by silica gel column chromatography (silica gel: MS-GEL D75-120-A 400 g, manufactured by Asahi Glass Co., Ltd., eluent: hexane / ethyl acetate = 3/1) gave the title compound (4.83 g, yield 94%). Got.

Spectral data of the compound (15A0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.11 (m, 2H), 4.52 (t, J = 13.0 Hz, 2H), 7.06 (M, 2H), 7.56 (m, 2H), 7.68 (m, 4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.1 (m, 2F), −123.0 (m, 2F), −124.1 (m , 2F), -124.3 (m, 2F).

(4) Synthesis of unsaturated fatty acid ester (1A0b-1) Compound (15A0b-1) (4.83 g) was dissolved in dichloromethane (100 mL), triethylamine (2.30 mL) was added, and the mixture was cooled to 0 ° C. Acrylic acid chloride (1.35 mL) was added, and the mixture was gradually raised to room temperature and stirred for 15 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 400 g, manufactured by Asahi Glass Stech Co., Ltd.), eluent: hexane / ethyl acetate = 4 / Purification by 1) gave the title compound (5.14 g, yield 96%).

Spectral data of the compound (1A0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.52 (t, J = 13.0 Hz, 2H), 4.68 (t, J = 13.5 Hz, 2H), 5.97 (dd, J = 1.0 Hz, 10.0 Hz, 1H), 6.19 (dd, J = 10.5 Hz, 17.0 Hz, 1H), 6.53 (dd, J = 1) 0.0 Hz, 17.5 Hz, 1H), 7.06 (m, 2H), 7.55-7.72 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -120.1 (m, 4F), -123.9 (m, 2F), -124.2 (m , 2F).

[Example 2] Synthesis of unsaturated fatty acid ester (1B0b-1) Using the hydroxyl compound (13B-1) synthesized above, an unsaturated fatty acid ester (1B0b-1) was synthesized by the synthesis route shown below. Details are described below.

(1) Synthesis of Compound (14B0b-1) Compound (02b) (2.84 g) obtained in the same manner as in Example 1 was dissolved in ether (40 mL), and triethylamine (2.07 mL) was added. . After cooling to 0 ° C., 1,1,2,2,3,3,4,4,4-nonafluorobutanesulfonyl fluoride (1.76 g) was added, and the temperature was gradually raised to room temperature and stirred for 40 hours. . Water (100 mL) and t-butyl methyl ether (50 mL) were added, and the organic layer was washed with saturated brine, dried, and the solvent was removed to remove 1,1,2,2,3,3,4,4,4. A crude product (4.86 g) of 4-nonafluorobutanesulfonic acid 2,2,3,3,4,4,5,5-octafluoro-6- (tetrahydro-2H-pyran-2-yloxy) hexyl was obtained. Obtained.

  This crude product and the aforementioned hydroxyl compound (13B-1) (2.99 g) were dissolved in N, N-dimethylformamide (40 mL), cesium carbonate (9.33 g) was added, and the mixture was heated at 80 ° C. for 1 hour. Stir. Water (50 mL) was added, and the mixture was extracted with t-butyl methyl ether (50 mL × 3 times). The obtained organic layer was washed with saturated brine (50 mL), and then the solvent was removed to obtain a crude product (9.42 g) of compound (14Bb-1). Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 150 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 10/1) gave the title compound (4.77 g, yield). 95%).

Spectral data of the compound (14B0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.88 (m, 3H), 1.31-1.04 (m, 20H), 2.58 (m , 4H), 3.58 (m, 1H), 3.79-4.21 (m, 3H), 4.44 (t, J = 13.0 Hz, 2H), 4.75 (m, 1H), 6.90 (m, 2H), 7.11-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.4 (m, 4F), −124.2 (m, 4F).

(2) Synthesis of Compound (15B0b-1) Compound (14B0b-1) (4.77 g) was dissolved in a mixed solvent of methanol (100 mL) and tetrahydrofuran (100 mL), and p-toluenesulfonic acid monohydrate ( 136 mg) was added and stirred at room temperature for 3 hours. Triethylamine (0.100 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product.
Purification by silica gel column chromatography (silica gel: MS-GEL D75-120-A 400 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 3/1) gave the title compound (3.96 g, yield 95%). Got.

Spectral data of the compound (15B0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (m, 3H), 1.33 (m, 4H), 1.59 (m, 6H), 2.01 (m, 4H), 2.58 (m, 4H), 4.08 (m, 2H), 4.44 (t, J = 13.0 Hz, 2H), 6.90 (m, 2H) , 7.11-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.3 (m, 2F), −123.0 (m, 2F), −124.1 (m , 2F), -124.5 (m, 2F).

(3) Synthesis of unsaturated fatty acid ester (1B0b-1) Compound (15B0b-1) (3.96 g) was dissolved in dichloromethane (80 mL), triethylamine (1.46 mL) was added, and the mixture was cooled to 0 ° C. Acrylic acid chloride (0.852 mL) was added, and the mixture was gradually raised to room temperature and stirred for 14 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 50 g, manufactured by Asahi Glass Stech Co., Ltd.), eluent: hexane / ethyl acetate = 4 / Purification by 1) gave the title compound (3.27 g, 72% yield).

Spectral data of the compound (1B0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (m, 3H), 1.33 (m, 4H), 1.60 (m, 6H), 2.01 (m, 4H), 2.58 (m, 4H), 4.44 (t, J = 13.0 Hz, 2H), 4.67 (t, J = 13.5 Hz, 2H), 5. 97 (dd, J = 1.0 Hz, 10.5 Hz, 1H), 6.19 (dd, J = 10.5 Hz, 17.5 Hz, 1H), 6.53 (m, 1H), 6.90 (m , 2H), 7.14-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.2 (m, 4F), −124.1 (m, 2F).

Example 3 Synthesis of Unsaturated Fatty Acid Ester (1C0b-1) Using the hydroxyl compound (13C-1) synthesized above, the compound (1C0b-1) was synthesized by the synthesis route shown below. Details are described below.

(1) Synthesis of Compound (14C0b-1) Compound (02b) (2.42 g) was dissolved in ether (50 mL), and triethylamine (1.75 mL) was added. After cooling to 0 ° C., 1,1,2,2,3,3,4,4,4-nonafluorobutanesulfonyl fluoride (1.49 mL) was added, and the temperature was gradually raised to room temperature and stirred for 40 hours. . Water (50 mL) and t-butyl methyl ether (30 mL) were added, and the organic layer was washed with saturated brine, dried and then the solvent was removed to remove 1,1,2,2,3,3,4,4,4. A crude product (4.28 g) of 4-nonafluorobutanesulfonic acid 2,2,3,3,4,4,5,5-octafluoro-6- (tetrahydro-2H-pyran-2-yloxy) hexyl was obtained. Obtained.

  This crude product and the above-mentioned hydroxyl compound (13C-1) (2.99 g) were dissolved in N, N-dimethylformamide (30 mL), cesium carbonate (17.96 g) was added, and 0.5 ° C. was added at 80 ° C. Stir for hours. Water (40 mL) was added, and the mixture was extracted with t-butyl methyl ether (40 mL × 3 times). The obtained organic layer was washed with saturated brine (50 mL), and then the solvent was removed to obtain a crude product of compound (14C0b-1). Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 100 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 15/1) gave the title compound (2.29 g, yield). 82%).

Spectral data of the compound (14C0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.99 (t, J = 7.0 Hz, 3H), 1.54-2.07 (m, 16H) 2.29 (s, 3H), 2.63 (m, 4H), 3.59 (m, 1H), 3.78-4.22 (m, 3H), 4.45 (t, J = 13) 0.0 Hz, 2H), 4.76 (m, 1H), 6.91 (m, 2H), 7.11-7.23 (m, 9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.4 (m, 4F), −124.1 (m, 4F).

(2) Synthesis of Compound (15C0b-1) Compound (14C0b-1) (2.29 g) was dissolved in a mixed solvent of methanol (50 mL) and tetrahydrofuran (50 mL), and p-toluenesulfonic acid monohydrate ( 73 mg) was added and stirred at room temperature for 3 hours. Triethylamine (0.054 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product.
Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 100 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 6/1) gave the title compound (1.88 g, yield). 93%).

Spectral data of the compound (15C0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.99 (t, J = 7.0 Hz, 3H), 1.56-2.07 (m, 10H) 2.29 (s, 3H), 2.63 (m, 4H), 4.10 (m, 2H), 4.45 (t, J = 13.0 Hz, 2H), 6.91 (m, 2H) ), 7.11-7.25 (m, 9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -120.3 (m, 2F), -123.1 (m, 2F), -124.1 (m , 2F), -124.4 (m, 2F).

(3) Synthesis of unsaturated fatty acid ester (1C0b-1) Compound (15C0b-1) (1.87 g) was dissolved in dichloromethane (40 mL), triethylamine (0.622 mL) was added, and the mixture was cooled to 0 ° C. Acrylic acid chloride (0.363 mL) was added, and the mixture was gradually raised to room temperature and stirred for 14 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 100 g, manufactured by Asahi Glass Stech Co., Ltd.), eluent: hexane / ethyl acetate = 10 / Purification by 1) gave the title compound (1.46 g, 72% yield).

Spectral data of the compound (1C0b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.99 (t, J = 7.0 Hz, 3H), 1.56-2.07 (m, 10H) 2.29 (s, 3H), 2.63 (m, 4H), 4.45 (t, J = 13.0 Hz, 2H), 4.67 (t, J = 13.5 Hz, 2H), 5 .97 (dd, J = 1.0 Hz, 10.5 Hz, 1H), 6.19 (dd, J = 10.5 Hz, 17.0 Hz, 1H), 6.53 (dd, J = 1.0 Hz, 17 .5Hz, 1H), 6.91 (m, 2H), 7.10-7.23 (m, 9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.2 (m, 4F), −124.0 (m, 2F), −124.2 (m , 2F).

Example 4 Synthesis of Unsaturated Fatty Acid Ester (1C0a-1) Compound (01b) is converted into Compound (01a) (2,2,3,3-tetrafluoro-1,4-butanediol: manufactured by Tokyo Chemical Industry Co., Ltd.) Compound (1C0a-1) was synthesized in the same manner as Example 3 except that the amount was changed to 95 g to obtain the title compound (3.38 g, yield 95%).

Spectral data of the compound (1C0a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (m, 3H), 1.33 (m, 4H), 1.60 (m, 6H), 2.01 (m, 4H), 2.58 (m, 4H), 4.44 (t, J = 13.0 Hz, 2H), 4.67 (t, J = 13.5 Hz, 2H), 5. 97 (dd, J = 1.0 Hz, 10.5 Hz, 1H), 6.19 (dd, J = 10.5 Hz, 17.5 Hz, 1H), 6.53 (m, 1H), 6.90 (m , 2H), 7.14-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.2 (m, 2F), −124.1 (m, 2F).

  The phase transition temperature from the crystal phase of the unsaturated fatty acid ester (1C0a-1) to the nematic phase was 121 ° C. Moreover, (DELTA) n with respect to the laser beam of wavelength 589nm in 60 degreeC of unsaturated fatty acid ester (1C0a-1) was 0.1278 (extrapolated value).

Example 5 Synthesis of unsaturated fatty acid ester (1C0c-1) Compound (01b) was converted to compound (01c) (2,2,3,3,4,4,5,5,6,6,7,7-dodeca Fluoro-1,8-octanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) Compound (1C0c-1) was synthesized in the same manner as in Example 3 except that 6.59 g was used, and the title compound (4.54 g, yield 95%) Got.

Spectral data of the compound (1C0c-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (m, 3H), 1.33 (m, 4H), 1.60 (m, 6H), 2.01 (m, 4H), 2.58 (m, 4H), 4.44 (t, J = 13.0 Hz, 2H), 4.67 (t, J = 13.5 Hz, 2H), 5. 97 (dd, J = 1.0 Hz, 10.5 Hz, 1H), 6.19 (dd, J = 10.5 Hz, 17.5 Hz, 1H), 6.53 (m, 1H), 6.90 (m , 2H), 7.14-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −120.2 (m, 6F), −124.1 (m, 2F).

The phase transition temperature from the crystal phase of the unsaturated fatty acid ester (1C0c-1) to the nematic phase was 147 ° C. Moreover, (DELTA) n with respect to the laser beam of wavelength 589nm in 60 degreeC of unsaturated fatty acid ester (1C0c-1) was 0.1367 (extrapolated value).
[Example 6] Synthesis of unsaturated fatty acid ester (1A5a-1) Using the diol compound (51a) synthesized above, an unsaturated fatty acid ester (1A5a-1) was synthesized according to the synthetic route shown below. Details are described below.

(1) Synthesis of Compound (52a) Compound (51a) (19.85 g) and 3,4-dihydro-2H-pyran (2.53 g) were dissolved in dichloromethane (1400 mL), and p-toluenesulfonic acid monohydrate The Japanese product (1.03 g) was added and stirred at 40 ° C. for 24 hours. Triethylamine (0.853 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product. The title compound (10.8 g, Yield 47%) was obtained.

Spectral data of the compound (52a);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.53-1.86 (m, 6H), 2.68 (m, 1H), 3.58 (m , 1H), 3.78-4.05 (m, 5H), 4.77 (m, 1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −78.2 (m, 2F), −81.0 (m, 2F), −89.3 (m , 4F).

(2) Synthesis of Compound (14A5a-1) Compound (52a) (3.00 g) was dissolved in ether (60 mL), and triethylamine (3.93 mL) was added. After cooling to 0 ° C., 1,1,2,2,3,3,4,4,4-nonafluorobutanesulfonyl fluoride (3.30 mL) was added, gradually warmed to room temperature and stirred for 14 hours. . Water (100 mL) and t-butyl methyl ether (60 mL) were added, and the organic layer was washed with saturated brine, dried and then the solvent was removed to remove 1,1,2,2,3,3,4,4,4. 4-nonafluorobutanesulfonic acid 2- (2- (1,1-difluoro-2- (tetrahydro-2H-pyran-2-yloxy) ethoxy) -1,1,2,2-tetrafluoroethoxy) -2, A crude product of 2-difluoroethyl (6.29 g) was obtained. This crude product and compound (13A-1) (4-cyano-4′-hydroxy-biphenyl, manufactured by SYNTHON, 1.86 g) were dissolved in N, N-dimethylformamide (60 mL), and cesium carbonate (9. 30 g) was added and stirred at 80 ° C. for 1 hour. Water (80 mL) was added, and the mixture was extracted with t-butyl methyl ether (60 mL × 3 times). The obtained organic layer was washed with saturated brine, and then the solvent was removed to obtain a crude product (8.70 g) of compound (14A5a-1). Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 200 g, manufactured by Asahi Glass Co., Ltd., eluent: hexane / ethyl acetate = 4/1) gave the title compound (4.27 g, yield). 97%).

Spectral data of the compound (14A5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.57-1.80 (m, 6H, CH ₂ ), 3.56 (m, 1H), 3. 76-4.04 (m, 3H), 4.41 (t, J = 9.0 Hz, 2H), 4.75 (m, 1H), 7.06 (m, 2H), 7.56 (dd, J = 1.5 Hz, 6.5 Hz, 2H), 7.68 (m, 4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −77.8 (m, 2F), −78.2 (m, 2F), −89.2 (m , 4F).

(3) Synthesis of Compound (15A5a-1) Compound (14A5a-1) (4.27 g) was dissolved in methanol (100 mL), and p-toluenesulfonic acid monohydrate (80 mg) was added for 15 hours at room temperature. Stir. Triethylamine (0.129 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product (3.83 g).

  Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 60 g, manufactured by Asahi Glass Co., Ltd., eluent: hexane / ethyl acetate = 3/1) gave the title compound (3.56 g, yield). 98%).

Spectral data of the compound (15A5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.93 (t, J = 9.5 Hz, 2H), 4.42 (t, J = 9.0 Hz, 2H), 7.06 (m, 2H), 7.56 (m, 2H), 7.67 (m, 4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −77.8 (m, 2F), −80.9 (m, 2F), −89.2 (m , 4F).

(4) Synthesis of unsaturated fatty acid ester (1A5a-1) Compound (15A5a-1) (3.55 g) was dissolved in dichloromethane (40 mL), triethylamine (1.57 mL) was added, and the mixture was cooled to 0 ° C. Acrylic acid chloride (0.917 mL) was added, and the mixture was gradually raised to room temperature and stirred for 15 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 100 g, manufactured by Asahi Glass Stech Co., Ltd.), eluent: hexane / ethyl acetate = 5 / 1) to obtain 3.26 g (yield 82%) of unsaturated fatty acid ester (1Aa-1).

Spectral data of unsaturated fatty acid ester (1A5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.42 (t, J = 9.0 Hz, 2H), 4.54 (t, J = 9.5 Hz, 2H), 5.95 (dd, J = 1.0 Hz, 10.5 Hz, 1H), 6.16 (dd, J = 10.5 Hz, 17.0 Hz, 1H), 6.50 (m, 1H), 7.06 (m, 2H), 7.56 (m, 2H), 7.67 (m, 4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −77.8 (m, 4F), −89.2 (m, 4F).

[Example 7] Synthesis of unsaturated fatty acid ester (1B5a-1) Using compound (52a) and hydroxyl compound (13B-1) synthesized above, unsaturated fatty acid ester (1B5a-1) was synthesized according to the synthesis route shown below. Synthesized. Details are described below.

(1) Synthesis of Compound (14B5a-1) Compound (52a) (3.00 g) was dissolved in ether (60 mL), and triethylamine (2.32 mL) was added. After cooling to 0 ° C., 1,1,2,2,3,3,4,4,4-nonafluorobutanesulfonyl fluoride (1.97 mL) was added, and the temperature was gradually raised to room temperature and stirred for 20 hours. . Water (100 mL) and t-butyl methyl ether (60 mL) were added, and the organic layer was washed with saturated brine, dried and then the solvent was removed to remove 1,1,2,2,3,3,4,4,4. 4-nonafluorobutanesulfonic acid 2- (2- (1,1-difluoro-2- (tetrahydro-2H-pyran-2-yloxy) ethoxy) -1,1,2,2-tetrafluoroethoxy) -2, A crude product of 2-difluoroethyl (5.39 g) was obtained.

  This crude product and the aforementioned hydroxyl compound (13B-1) (3.07 g) were dissolved in N, N-dimethylformamide (40 mL), cesium carbonate (9.56 g) was added, and the mixture was heated at 80 ° C. for 1 hour. Stir. Water (50 mL) was added, and the mixture was extracted with t-butyl methyl ether (50 mL × 3 times). The obtained organic layer was washed with saturated brine, and then the solvent was removed to remove 2- (2- (2- (1,1-difluoro-2- (4-((1S, 4S) -4- (4- A crude product of pentylphenyl) cyclohexyl) phenoxy) ethoxy) -1,1,2,2-tetrafluoroethoxy) -2,2-difluoroethoxy) -tetrahydro-2H-pyran was obtained. Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 150 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 20/1) gave the title compound (3.72 g, yield). 69%).

Spectral data of the compound (14B5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (m, 3H), 1.33-2.01 (m, 20H), 2.58 (m , 4H), 3.56 (m, 1H), 3.81-4.01 (m, 3H), 4.33 (m, 2H), 4.76 (m, 1H), 6.89 (m, 2H), 7.11-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −78.0 (m, 2F), −78.2 (m, 2F), −89.2 (m , 4F).

(2) Synthesis of Compound (15B5a-1) Compound (14B5a-1) (3.72 g) was dissolved in a mixed solvent of methanol (50 mL) and tetrahydrofuran (50 mL), and p-toluenesulfonic acid monohydrate (53 mg) ) And stirred at room temperature for 3 hours. Triethylamine (0.093 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product. Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 200 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 5/1) gave the title compound (2.49 g, yield). 75%).

Spectral data of the compound (15B5b-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (m, 3H), 1.33 (m, 4H), 1.59 (m, 6H), 2.01 (m, 4H), 2.58 (m, 4H), 4.08 (m, 2H), 4.44 (t, J = 13.0 Hz, 2H), 6.90 (m, 2H) , 7.11-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.3 (m, 2F), −123.0 (m, 2F), −124.1 (m , 2F), -124.5 (m, 2F).

(3) Synthesis of unsaturated fatty acid ester (1B5a-1) Compound (15B5a-1) (2.48 g) was dissolved in dichloromethane (40 mL), triethylamine (0.868 mL) was added, and the mixture was cooled to 0 ° C. Acrylic acid chloride (0.494 mL) was added, and the mixture was gradually raised to room temperature and stirred for 15 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (silica gel: 300 g MS-GEL D50-60-A (N) manufactured by Asahi Glass Stech Co., Ltd.), eluent: hexane / ethyl acetate = 20 / Purification by 1) gave the title compound (2.55 g, 94% yield).

Spectral data of unsaturated fatty acid ester (1B5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.90 (t, J = 6.5 Hz, 3H), 1.33 (m, 4H), 1.60 (M, 6H), 2.01 (m, 4H), 2.58 (m, 4H), 4.33 (t, J = 9.5 Hz, 2H), 4.53 (t, J = 9.5 Hz) , 2H), 5.94 (m, 1H), 6.16 (dd, J = 10.5 Hz, 17.0 Hz, 1H), 6.51 (m, 1H), 6.89 (m, 2H), 7.11-7.21 (m, 6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −77.8 (m, 2F), −78.0 (m, 2F), −89.2 (m , 4F).

[Example 8] Synthesis of unsaturated fatty acid ester (1C5a-1) Using compound (52a) and hydroxyl compound (13C-1) synthesized above, unsaturated fatty acid ester (1C5a-1) was synthesized according to the synthetic route shown below. Synthesized. Details are described below.

(1) Synthesis of Compound (14C5a-1) Compound (52a) (2.22 g) was dissolved in ether (50 mL), and triethylamine (2.45 mL) was added. After cooling to 0 ° C., 1,1,2,2,3,3,4,4,4-nonafluorobutanesulfonyl fluoride (2.08 mL) was added, and the temperature was gradually raised to room temperature and stirred for 40 hours. . Water (100 mL) and t-butyl methyl ether (80 mL) were added, and the organic layer was washed with saturated brine, dried and then the solvent was removed to remove 1,1,2,2,3,3,4,4,4. 4-Nonafluorobutanesulfonic acid 2- (2- (1,1-difluoro-2- (4-((1S, 4S) -4- (2-methyl-4′-propylbiphenyl-4-yl) cyclohexyl)) A crude product (4.53 g) of phenoxy) ethoxy) -1,1,2,2-tetrafluoroethoxy) -2,2-difluoroethyl was obtained.

  This crude product and the aforementioned hydroxyl compound (13C-1) (1.35 g) were dissolved in N, N-dimethylformamide (50 mL), cesium carbonate (3.44 g) was added, and the mixture was stirred at 80 ° C. for 2 hours. did. Water (40 mL) was added, and the mixture was extracted with t-butyl methyl ether (40 mL × 3 times). The obtained organic layer was washed with saturated brine, and then the solvent was removed to remove 2- (2- (2- (1,1-difluoro-2- (4-((1S, 4S) -4- (2- A crude product of methyl-4′-propylbiphenyl-4-yl) cyclohexyl) phenoxy) ethoxy) -1,1,2,2-tetrafluoroethoxy) -2,2-difluoroethoxy) -tetrahydro-2H-pyran was obtained. Obtained. Purification by silica gel column chromatography (silica gel: 300 g MS-GEL D50-60-A (N) manufactured by Asahi Glass Stech Co., eluent: hexane / ethyl acetate = 40/1 to 20/1) gave the title compound (1. 28 g, yield 47%).

Spectral data of the compound (14C5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.99 (t, J = 7.5 Hz, 3H), 1.52-2.09 (m, 16H) , 2.29 (s, 3H), 2.63 (m, 4H), 3.57 (m, 1H), 3.78-4.05 (m, 3H), 4.34 (t, J = 9 0.0 Hz, 2H), 4.76 (m, 1H), 6.90 (m, 2H), 7.11-7.23 (m, 9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −78.0 (m, 2F), −78.2 (m, 2F), −89.2 (m , 4F).

(2) Synthesis of Compound (15C5a-1) Compound (14C5a-1) (1.28 g) was dissolved in a mixed solvent of methanol (30 mL) and tetrahydrofuran (20 mL), and p-toluenesulfonic acid monohydrate (34 mg) ) And stirred at room temperature for 15 hours. Triethylamine (0.025 mL) was added, and the solvent was distilled off under reduced pressure to obtain a crude product. Purification by silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 60 g, manufactured by Asahi Glass Stech Co., Ltd., eluent: hexane / ethyl acetate = 8/1) gave the title compound (0.862 g, yield). 76%).

Spectral data of the compound (15C5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.99 (t, J = 7.0 Hz, 3H), 1.56-2.13 (m, 10H) 2.29 (s, 3H), 2.63 (m, 4H), 3.92 (m, 2H), 4.35 (t, J = 9.0 Hz, 2H), 6.91 (m, 2H) ), 7.11-7.23 (m, 9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −77.9 (m, 2F), −81.0 (m, 2F), −89.2 (m , 4F).

(3) Synthesis of unsaturated fatty acid ester (1C5a-1) Compound (15C5a-1) (0.862 g) was dissolved in dichloromethane (40 mL), triethylamine (0.289 mL) was added, and the mixture was cooled to 0 ° C. Acrylic acid chloride (0.171 mL) was added, and the mixture was gradually raised to room temperature and stirred for 15 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (silica gel: MS-GEL D50-60-A (N) 100 g, manufactured by Asahi Glass Stech Co., Ltd.), eluent: hexane / ethyl acetate = 20 / Purification by 1) gave the title compound (0.915 g, 98% yield).

Spectral data of unsaturated fatty acid ester (1C5a-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.99 (t, J = 7.0 Hz, 3H), 1.55-2.05 (m, 10H) 2.29 (s, 3H), 2.63 (m, 4H), 4.34 (t, J = 9.5 Hz, 2H), 4.54 (t, J = 9.5 Hz, 2H), 5 .95 (d, J = 10.5 Hz, 1 H), 6.17 (dd, J = 10.5 Hz, 17.0 Hz, 1 H), 6.51 (d, J = 17.5 Hz, 1 H), 6. 90 (m, 2H), 7.10-7.22 (m, 9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −77.8 (m, 2F), −78.0 (m, 2F), −89.2 (m , 4F).

  The phase transition temperature from the crystal phase of the unsaturated fatty acid ester (1C5a-1) to the nematic phase was 130 ° C. Moreover, (DELTA) n with respect to the laser beam of wavelength 589nm in 60 degreeC of unsaturated fatty acid ester (1C5a-1) was 0.1327 (extrapolated value).

[Example 9] Preparation of polymerizable liquid crystal compositions A and A1 Unsaturated fatty acid ester (1A0b-1) obtained in Example 1, the following compound (2Bb-3), the following compound (2Bb-5), the following compound (2Cc- CN) and the following compound (2Da-3-CN) were mixed at 11: 21: 20: 27: 21 (molar ratio) to obtain a polymerizable liquid crystal composition A.

The polymerizable liquid crystal composition A exhibited a nematic phase at 42 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 61 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.
Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition A to obtain a polymerizable liquid crystal composition A1.

[Example 10] Preparation of polymerizable liquid crystal compositions B and B1 Unsaturated fatty acid ester (1B0b-1) obtained in Example 2, the compound (2Bb-3), the compound (2Bb-5), the compound (2Cc- CN) and the above compound (2Da-3-CN) were mixed at 9: 22: 20: 27: 22 (molar ratio) to obtain a polymerizable liquid crystal composition B.
The polymerizable liquid crystal composition B exhibited a nematic phase at 45 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 66 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.
Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition B to obtain a polymerizable liquid crystal composition B1.

[Example 11] Preparation of polymerizable liquid crystal compositions C and C1 The compound (1C0b-1) obtained in Example 3, the compound (2Bb-3), the compound (2Bb-5), the compound (2Cc-CN) and The compound (2Da-3-CN) was mixed at 9: 22: 20: 27: 22 (molar ratio) to obtain a polymerizable liquid crystal composition C.
The polymerizable liquid crystal composition C exhibited a nematic phase at 39 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 68 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.
Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition C to obtain a polymerizable liquid crystal composition C1.

[Example 12] Preparation of polymerizable liquid crystal composition D, D1 2: 1: 1 (mol) of the compound (1C0b-1) obtained in Example 3, the following compound (2Eb-3), and the following compound (2Eb-5). Ratio) to obtain a polymerizable liquid crystal composition D.
The polymerizable liquid crystal composition D exhibited a nematic phase at 68 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 124 ° C. or higher. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.
Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition D to obtain a polymerizable liquid crystal composition D1.

[Example 13] Preparation of polymerizable liquid crystal compositions E and E1 2: 1: 1 (moles) of the compound (1C0a-1) obtained in Example 4, the above compound (2Eb-3), and the above compound (2Eb-5). Ratio) to obtain a polymerizable liquid crystal composition E.
The polymerizable liquid crystal composition E exhibited a nematic phase at 57 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 124 ° C. or higher. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.
Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition E to obtain a polymerizable liquid crystal composition E1.

[Example 14] Preparation of polymerizable liquid crystal compositions F and F1 2: 1: 1 (moles) of the compound (1C0c-1) obtained in Example 5, the compound (2Eb-3), and the compound (2Eb-5) Ratio) to obtain a polymerizable liquid crystal composition F.
The polymerizable liquid crystal composition F exhibited a nematic phase at 81 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 124 ° C. or higher. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.
Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition F to obtain a polymerizable liquid crystal composition F1.

Example 15 Preparation of Polymerizable Liquid Crystal Compositions G and G1 Unsaturated fatty acid ester (1A5a-1) obtained in Example 6, compound (2Bb-3), compound (2Bb-5), compound (2Cc- CN) and the above compound (2Da-3-CN) were mixed at 11: 21: 20: 27: 21 (molar ratio) to obtain a polymerizable liquid crystal composition G.

  The polymerizable liquid crystal composition G exhibited a nematic phase at 32 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 61 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.

  Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition G to obtain a polymerizable liquid crystal composition G1.

[Example 16] Preparation of polymerizable liquid crystal compositions H and H1 Unsaturated fatty acid ester (1B5a-1) obtained in Example 7, the compound (2Bb-3), the compound (2Bb-5), the compound (2Cc- CN) and the compound (2Da-3-CN) were mixed at 5: 23: 21: 28: 23 (molar ratio) to obtain a polymerizable liquid crystal composition H.

  The polymerizable liquid crystal composition H exhibited a nematic phase at 37 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 64 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.

  Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition H to obtain a polymerizable liquid crystal composition H1.

[Example 17] Preparation of polymerizable liquid crystal compositions I and I1 Unsaturated fatty acid ester (1C5a-1) obtained in Example 8, the above compound (2Bb-3), the above compound (2Bb-5), the above compound (2Cc- CN) and the above compound (2Da-3-CN) were mixed at 9: 22: 20: 27: 22 (molar ratio) to obtain a polymerizable liquid crystal composition I.

  The polymerizable liquid crystal composition I exhibited a nematic phase at 34 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 52 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.

  Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition I to obtain a polymerizable liquid crystal composition I1.

[Example 18] Preparation of polymerizable liquid crystal compositions J and J1 2: 1: 1 of unsaturated fatty acid ester (1C5a-1) obtained in Example 8, the above compound (2Eb-3) and the above compound (3Eb-5). A polymerizable liquid crystal composition J was obtained by mixing at a molar ratio.

  The polymerizable liquid crystal composition J exhibited a nematic phase at 28 ° C. The phase transition temperature from the nematic phase to the isotropic phase was 78 ° C. In addition, the nematic phase that appears once after heating to an isotropic liquid and then cooling was maintained at room temperature for 2 hours or more.

  Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition J to obtain a polymerizable liquid crystal composition J1.

[Example 19] Fabrication of optical element A A polyimide substrate was coated on a glass substrate having a length of 20 cm, a width of 20 cm, and a thickness of 0.5 mm using a spin coater, dried, and then rubbed in a certain direction with a nylon cloth to produce a support. did.

Next, on the glass substrate, the polymerizable liquid crystal composition A1 prepared in Example 9 was dissolved in xylene so as to have a concentration of 50% by mass, and this xylene solution was dissolved in a spin coater (3000 rpm, 30 seconds) at room temperature. Applied. Annealed on a hot plate at 80 ° C. for 3 minutes. The coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. In 30 ° C., UV an integrated light quantity of intensity 80 mW / cm ² was obtained an optical element A was photopolymerized by irradiating so as to be 5300mJ / cm ^2. The film thickness of the polymer was about 1 μm. The optical element A was horizontally aligned in the rubbing direction of the substrate. Optical element A was transparent in the visible range, and no scattering was observed. Moreover, (DELTA) n with respect to the laser beam of wavelength 589nm in 25 degreeC was 0.1142. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 20] Production of optical element B An optical element B was obtained in the same manner as in Example 19 except that the polymerizable liquid crystal composition B1 prepared in Example 10 was used instead of the polymerizable liquid crystal composition A1.
Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 1.5 μm. Optical element B was transparent in the visible range, and no scattering was observed. In addition, Δn with respect to laser light having a wavelength of 589 nm at 25 ° C. was 0.1093. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 21] Production of optical element C An optical element C was obtained in the same manner as in Example 19 except that the polymerizable liquid crystal composition C1 prepared in Example 11 was used instead of the polymerizable liquid crystal composition A1.
Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 1 μm. The optical element C was transparent in the visible range, and no scattering was observed. Moreover, (DELTA) n with respect to the laser beam of wavelength 589nm in 25 degreeC was 0.1231. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 22] Production of optical element D Optical element D was obtained in the same manner as in Example 19 except that the polymerizable liquid crystal composition D1 prepared in Example 12 was used instead of the polymerizable liquid crystal composition A1.
Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 0.8 μm. The optical element D was transparent in the visible range, and no scattering was observed. Further, Δn with respect to laser light having a wavelength of 589 nm at 25 ° C. was 0.0982. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 23] Production of optical element E An optical element E was obtained in the same manner as in Example 19 except that the polymerizable liquid crystal composition E1 prepared in Example 13 was used instead of the polymerizable liquid crystal composition A1.
Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 1.5 μm. The optical element E was transparent in the visible range, and no scattering was observed. In addition, Δn with respect to laser light having a wavelength of 589 nm was 0.0989. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 24] Production of optical element F An optical element F was obtained in the same manner as in Example 19 except that the polymerizable liquid crystal composition F1 prepared in Example 14 was used instead of the polymerizable liquid crystal composition A1.
Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 1.5 μm. The optical element F was transparent in the visible range, and no scattering was observed. Further, Δn with respect to laser light having a wavelength of 589 nm at 25 ° C. was 0.1473. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 25] Production of optical element G A polyimide substrate was coated on a glass substrate having a length of 20 cm, a width of 20 cm, and a thickness of 0.5 mm using a spin coater, dried, and then rubbed in a certain direction with nylon cloth to produce a support. did.

Next, on the glass substrate, the polymerizable liquid crystal composition G1 obtained in Example 15 was dissolved in xylene so as to have a concentration of 50% by mass, and this xylene solution was dissolved in a spin coater (3000 rpm, 30 seconds) at room temperature. Applied. Annealed on a hot plate at 80 ° C. for 3 minutes. The coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. In 30 ° C., UV an integrated light quantity of intensity 80 mW / cm ² performs a photopolymerization reaction by irradiation so as to be 5300mJ / cm ^2, to obtain an optical element G. The film thickness of the polymer was about 1 μm. The optical element G was horizontally aligned in the rubbing direction of the substrate. Optical element A was transparent in the visible range, and no scattering was observed. Further, Δn with respect to laser light having a wavelength of 589 nm at 25 ° C. was 0.087.
Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 26] Production of optical element H An optical element H was obtained in the same manner as in Example 25 except that the polymerizable liquid crystal composition H1 obtained in Example 16 was used instead of the polymerizable liquid crystal composition G1.
Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 1.5 μm. The optical element H was transparent in the visible range, and no scattering was observed. In addition, Δn with respect to laser light having a wavelength of 589 nm at 25 ° C. was 0.1093. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 27] Production of optical element I An optical element I was obtained in the same manner as in Example 25 except that the polymerizable liquid crystal composition I1 obtained in Example 17 was used instead of the polymerizable liquid crystal composition G1.

  Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 1 μm. The optical element I was transparent in the visible range, and no scattering was observed. Moreover, (DELTA) n with respect to the laser beam of wavelength 589nm in 25 degreeC was 0.065. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 28] Production of optical element J An optical element J was obtained in the same manner as in Example 25 except that the polymerizable liquid crystal composition J1 obtained in Example 18 was used instead of the polymerizable liquid crystal composition G1.

  Before the ultraviolet irradiation, the coating state was uniform, and when observed with a polarizing microscope, it was confirmed that a uniform alignment state was obtained without generation of domains. The film thickness of the polymer was about 0.8 μm. The optical element J was transparent in the visible range, and no scattering was observed. Further, Δn with respect to laser light having a wavelength of 589 nm at 25 ° C. was 0.047. Moreover, even if it heated at 150 degreeC for 10 hours, the change of (DELTA) n was not seen but it confirmed that it was excellent in heat resistance.

[Example 29] Preparation of polymerizable liquid crystal compositions K and K1 The above compound (2Bb-3), the above compound (2Bb-5), the above compound (2Cc-CN) and the above compound (2Da-3-CN) were mixed with 24: Polymerization liquid crystal composition K was prepared by mixing at 22:30:24 (molar ratio). Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition K to obtain a polymerizable liquid crystal composition K1.

[Example 30]
Coating was performed on a glass substrate in the same manner as in Example 19 except that the polymerizable liquid crystal composition A1 was changed to the polymerizable liquid crystal composition K1 obtained in Example 29. Although the film thickness was about 1 μm, when observed with a polarizing microscope, domains were generated and a uniform alignment state was not obtained. After the application, irradiation with ultraviolet rays was carried out in the same manner as in Example 19. As a result, the polymerizable liquid crystal composition K1 was cured to obtain a polymer, but scattering was intense and a transparent optical element could not be obtained.

[Example 31] Preparation of polymerizable liquid crystal compositions L and L1 The above compound (2Eb-3), the above compound (2Eb-5) and the following compound (2Ga-6-Me) were mixed in 27.5: 27.5: 45 ( The polymerizable liquid crystal composition L was prepared by mixing at a molar ratio. Next, 2% by mass of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition L to obtain a polymerizable liquid crystal composition L1.

[Example 32]
Coating was performed on a glass substrate in the same manner as in Example 19 except that the polymerizable liquid crystal composition A1 was changed to the polymerizable liquid crystal composition L1 obtained in Example 31. Although the film thickness was about 1 μm, when observed with a polarizing microscope, domains were generated and a uniform alignment state was not obtained. After the application, ultraviolet irradiation was performed in the same manner as in Example 19. As a result, the polymerizable liquid crystal composition L1 was cured to obtain a polymer, but scattering was intense and a transparent optical element could not be obtained.

The polymerizable liquid crystal composition prepared by using the unsaturated fatty acid ester of the present invention is suitable for application over a wide area because the film thickness unevenness and the alignment disorder are simultaneously suppressed, and crystals are difficult to precipitate even when left at room temperature. Therefore, the production of the polymer film is facilitated. In addition, an optically anisotropic material excellent in transparency and heat resistance is manufactured, and can be effectively used as a material such as a phase plate for modulating polarization.

The specification, claims, and abstract of Japanese Patent Application No. 2006-232120 filed on August 29, 2006 and Japanese Patent Application No. 2006-346617 filed on December 22, 2006 are as follows. The entire contents are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims (9)

Unsaturated fatty acid ester represented by the following formula (1).
CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -OE ^1- (E ² ) _k- (E ³ ) _h -E ⁴ -R ² (1)
However, the symbol in Formula (1) is as follows.
R ^F : a polyfluoroalkylene group having 2 to 12 carbon atoms or a group represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ — (x is an integer of 1 to 6).
R ¹ : a hydrogen atom or a methyl group.
R ² : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group.
E ^{1 is a} 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.
E ² , E ³ , E ⁴ : each independently a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and a hydrogen atom bonded to a carbon atom in the group is a fluorine atom or a chlorine atom Alternatively, it may be substituted with a methyl group.
m: An integer of 1 to 3.
n: An integer of 1 to 3.
k: 0 or 1.
h: 0 or 1. A polymerizable liquid crystal composition comprising an unsaturated fatty acid ester represented by the following formula (1) and a polymerizable liquid crystal compound not corresponding to the following formula (1).
CH ₂ = CR ¹ -COO- (CH ₂ ) _m -R ^F- (CH ₂ ) _n -OE ^1- (E ² ) _k- (E ³ ) _h -E ⁴ -R ² (1)
However, the symbol in Formula (1) is as follows.
R ^F : a polyfluoroalkylene group having 2 to 12 carbon atoms or a group represented by —CF ₂ — (OCF ₂ CF ₂ ) _x —OCF ₂ — (x is an integer of 1 to 6).
R ¹ : a hydrogen atom or a methyl group.
R ² : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group.
E ^{1 is a} 1,4-phenylene group, and a hydrogen atom bonded to a carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.
E ² , E ³ , E ⁴ : each independently a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and a hydrogen atom bonded to a carbon atom in the group is a fluorine atom or a chlorine atom Alternatively, it may be substituted with a methyl group.
m: An integer of 1 to 3.
n: An integer of 1 to 3.
k: 0 or 1.
h: 0 or 1.   The polymerizable liquid crystal composition according to claim 2, wherein the unsaturated fatty acid ester represented by the formula (1) is a polymerizable liquid crystal compound having liquid crystallinity. The polymerizable liquid crystal composition according to claim 2 or 3, wherein at least a part of the polymerizable liquid crystal compound not corresponding to the formula (1) is a compound represented by the following formula (2).
CH ₂ = CR ³ -COO- (CH ₂ ) _t- (O) _p -E ⁵ -wE ^6- (E ⁷ ) _q- (E ⁸ ) _s -R ⁴ (2)
However, the symbol in Formula (2) is as follows.
R ³ : a hydrogen atom or a methyl group.
R ⁴ : an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a cyano group.
E ⁵ , E ⁶ , E ⁷ , E ⁸ : each independently a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and a hydrogen atom bonded to a carbon atom in the group is a fluorine atom , May be substituted with a chlorine atom or a methyl group.
w: -OCO- or a single bond.
t: An integer from 0 to 8.
p: 0 when t is 0, 1 when t is 1-8.
q: 0 or 1.
s: 0 when q is 0, 0 or 1 when q is 1.   The total amount of the unsaturated fatty acid ester represented by the formula (1) and the polymerizable liquid crystal compound not corresponding to the formula (1) is 70% by mass or more based on the polymerizable liquid crystal composition. The polymerizable liquid crystal composition according to any one of the above.   The amount of the unsaturated fatty acid ester represented by the formula (1) is 5 to 5 with respect to the total amount of the unsaturated fatty acid ester represented by the formula (1) and the polymerizable liquid crystal compound not corresponding to the formula (1). The polymerizable liquid crystal composition according to any one of claims 2 to 5, which is 50 mol%.   An optically anisotropic material obtained by polymerizing the polymerizable liquid crystal composition according to claim 2 in a state where the polymerizable liquid crystal compound in the composition exhibits a liquid crystal phase and is aligned.   A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 2 to 6 in a state where the polymerizable liquid crystal compound in the composition exhibits a liquid crystal phase and is aligned, and the polymer. An optical element having a support to support.   The optical element according to claim 8, which is used as a phase plate.