WO2010044384A1 - Polymerizable liquid crystal compound, polymerizable liquid crystal composition and oriented film - Google Patents

Abstract

Polymerizable liquid crystal compounds represented by formula (i) and polymerizable liquid crystal compositions that contain the polymerizable compounds can provide optically anisotropic films that have excellent optical anisotropy, that stably maintain retardation values and transparency even at high temperatures, and that additionally have excellent retardation value frequency dispersion characteristics. (In the formula, n represents an integer of 3-10, and m an integer of 4-8.)

Description

Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and alignment film

The present invention relates to a polymerizable liquid crystal compound having polymerizability and liquid crystallinity, a composition containing the same, and a polymer obtained by using these, for example, a material having optical characteristics such as a display device and a recording material, In particular, the present invention relates to a polymerizable liquid crystal compound, a composition containing the polymerizable liquid crystal compound, and a polymer obtained by using these, which can be suitably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays.

Due to demands for improving the display quality and weight reduction of liquid crystal display devices, there is an increasing demand for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, development of a film utilizing the optical anisotropy of the polymerizable liquid crystal compound has been made.
The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (structure part having a spacer part and a mesogen part), and an acrylic group is widely used as the polymerizable group. ing.

Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.
For example, a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and a polymer is obtained by irradiating radiation while maintaining the compound in a liquid crystal state (see Patent Document 1), or an acrylic group is used. A method is known in which a photopolymerization initiator is added to a mixture of two kinds of polymerizable liquid crystal compounds, or a composition in which chiral liquid crystals are mixed with this mixture, and a polymer is obtained by irradiation with ultraviolet rays (Patent Document 2). reference).

The polymer (film) obtained by each of the above methods is not only a display device such as a monitor or a television but also a display device used in a high-temperature environment such as an automobile as a polarizing plate or a retardation film. Mounted on. For this reason, maintaining transparency in a high temperature environment is very important as a display device material.
In the field of displays, in recent years, studies on process simplification using these materials as In Cell retardation films have been actively promoted. The material used for this In Cell technology is required to have higher thermal stability and chemical resistance.
Furthermore, when compared with an optically anisotropic film obtained from another process (for example, stretching of a polyvinyl alcohol film), a film obtained from a polymerizable liquid crystal compound has a high wavelength dependency of optical anisotropy. There is.

JP-A-62-70407 JP-A-9-208957

The present invention has been made in view of such circumstances, and has excellent optical anisotropy, the retardation value and transparency are kept stable even at high temperatures, and the retardation value has excellent wavelength dispersion characteristics. Another object of the present invention is to provide a polymerizable liquid crystal compound capable of providing an optically anisotropic film, a polymerizable liquid crystal composition containing the same, and a polymer thereof.

As a result of intensive investigations to solve the above problems, the present inventor has found that a predetermined polymerizable liquid crystal compound having an α-methylene-γ-butyrolactone moiety has liquid crystallinity and itself is excellent in polymerizability. In addition, the present invention provides a stable liquid crystal composition, and that the polymer and film obtained from the liquid crystal composition have excellent heat resistance in optical anisotropy, transparency, and wavelength dispersion, and completed.

That is, the present invention
1. A polymerizable liquid crystal compound represented by the following formula [i]:

(In the formula, n represents an integer of 3 to 10, and m represents an integer of 4 to 8.)
2. A liquid crystal composition containing 1 polymerizable liquid crystal compound,
3. Furthermore, two liquid crystal compositions containing a liquid crystal compound having one polymerizable group in one molecule,
4). 3. The liquid crystal composition according to 3, wherein the liquid crystal compound is a compound having one polymerizable group represented by the following formula [ii] or formula [iii] in one molecule;

5). 3 or 4 liquid crystal compositions, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formula [vi]:

(In the formula, X is a fluorine atom, a cyano group, or a monovalent hydrocarbon group having 4 to 8 carbon atoms, f is an integer of 2 to 9, and M is represented by the following formula [ii] or [iii]: Group.)

6). A polymer obtained from the liquid crystal composition of any one of 2 to 5,
7). A film obtained from the liquid crystal composition of any one of 2 to 5,
8). An alignment film obtained from the liquid crystal composition of any one of 2 to 5,
9. An optical member comprising 6 polymers or 8 oriented films is provided.

The polymerizable liquid crystal compound of the present invention and the composition containing the same exhibit not only a chemical resistance with high optical anisotropy, and a polymer having stable anisotropy and transparency under a high temperature environment, It shows wavelength dependency with low optical anisotropy.
Therefore, a polymer obtained from the composition containing the polymerizable liquid crystal compound can be used as an optically anisotropic film such as a polarizing plate or a retardation plate, and is particularly suitable for use in a high temperature environment.

Terms used in this specification are as follows.
“Polymerizable liquid crystal compound” means a compound having a polymerizable portion such as an acrylic group or an α-methylene lactone ring and a liquid crystal structure portion in a molecule and exhibiting a liquid crystal phase. The “liquid crystal structure” means a structure having a spacer portion and a mesogen portion, which is generally used for representing liquid crystal molecules. “Liquid crystal composition” means a composition having a characteristic of exhibiting a liquid crystal phase. "Liquid crystallinity" means exhibiting a liquid crystal phase.

Hereinafter, the present invention will be described in more detail.
[Polymerizable liquid crystal compound]
The polymerizable liquid crystal compound according to the present invention is represented by the following formula [i].

(In the formula, n represents an integer of 3 to 10, and m represents an integer of 4 to 8.)

The compound represented by the formula [i] is a polymerizable liquid crystal compound having a lactone ring and a liquid crystal structure site and having an α-methylene-γ-butyrolactone site.
α-Methylene-γ-butyrolactone is less affected by steric hindrance than α-alkylidene-γ-butyrolactone having a polymerizable group, and can exhibit a very excellent effect of having high polymerizability. And it is effective in order to provide high Tg and heat resistance to the polymer obtained using this compound.

In formula [i], the repeating part of the methylene group is a part called a spacer part. Here, n represents the number of repeating methylene groups and is an integer of 3 to 10, preferably an integer of 4 to 9, and more preferably an integer of 4 to 6.
On the other hand, m represents the number of repeating methylene groups and is an integer of 4 to 8, preferably an integer of 4 to 6.
The polymerizable liquid crystal compound represented by the above formula [i] exhibits a liquid crystal phase such as a smectic phase or a nematic phase. This characteristic is useful in the field of application using optical anisotropy such as a polarizing plate and a retardation plate.
Examples of the polymerizable liquid crystal compound include the following compounds (1) to (30), but are not limited thereto.

[Synthesis of polymerizable liquid crystal compound]
The polymerizable liquid crystal compound of the present invention can be synthesized by combining techniques in organic synthetic chemistry, and the synthesis method is not particularly limited.
The compound having an α-methylene-γ-butyrolactone structure is represented by, for example, Taraga et al. (P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990)) represented by the following synthesis scheme (A1). ) Can be synthesized using the method proposed by). This method is a method of reacting 2- (bromomethyl) acrylic acid with aldehyde or ketone using SnCl ₂ .
Incidentally, 2- (bromomethyl) propenoic acid can be obtained by a method proposed by K. Ramarajan et al (K. Ramarajan, K. Kamalingam, DJO'Donnell). and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983)).

(In the formula, R ′ represents a monovalent organic group, and Amberlyst 15 is a registered trademark of Rohm and Haas.)

In addition, in the reaction of 2- (bromomethyl) propenoic acid using SnCl ₂ , α-methylene-γ-butyrolactone is obtained by reaction with the corresponding acetal or ketal instead of aldehyde or ketone. A structure can also be obtained.
Examples of the acetal or ketal include a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group, and a 1,3-dioxolane group. The synthesis method and protecting group are shown in the following scheme (A2).

The compound (intermediate) represented by the formula [2] can be synthesized by the method of the following synthesis scheme (B) applying the method of the synthesis scheme (A1).

(In the formula, n represents the same meaning as described above. Me represents a methyl group. The same shall apply hereinafter.)

A compound represented by the formula [i] is obtained by reacting a compound represented by the above formula [2] with a phenolic compound for esterification. Details of these reactions are shown in the following synthesis scheme (C).

(In the formula, n and m have the same meaning as described above.)

The phenolic compound can be obtained, for example, by a method proposed by Hikmet et al. (RAMHikmet et al) represented by the following synthesis scheme (D) (RAMHikmet, J.Lub, and AJWTol) , Macromolecules, vol.28, 3313-3327 (1995)).

(In the formula, m represents the same meaning as described above.)

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition according to the present invention contains at least one polymerizable liquid crystal compound represented by the above formula [i]. When two or more kinds of polymerizable liquid crystal compounds represented by the formula [i] contained in the polymerizable liquid crystal composition are used, the polymerizable liquid crystal compounds may be appropriately selected and mixed, and the combination thereof is arbitrary.
The polymerizable liquid crystal composition of the present invention exhibits the effect of suppressing the wavelength dispersibility of the optically anisotropic film by including the compound of the above formula [i].

In the polymerizable liquid crystal composition of the present invention, a compound having a liquid crystal structure site (hereinafter referred to as a specific compound) can be mixed with the polymerizable liquid crystal compound of the above formula [i]. The specific compound to mix can also be used in combination of multiple types.
In this case, the specific compound may be either a compound exhibiting liquid crystallinity or a compound not exhibiting liquid crystallinity, and may or may not have a polymerizable group such as an acryl group or a lactone ring. Also good. The specific compound having a polymerizable group may be monofunctional or polyfunctional.
Examples of such a specific compound include a compound having no polymerizable group and exhibiting liquid crystallinity, a compound having no polymerizable group and not exhibiting liquid crystallinity, a compound having a polymerizable group and liquid crystallinity. These are compounds other than the polymerizable liquid crystal compound of the present invention, and compounds having a polymerizable group and not exhibiting liquid crystallinity.

When the specific compound has a polymerizable group, the polymerizable group is not particularly limited, but is preferably a group represented by the following formula [ii] or [iii], and particularly represented by the formula [ii]. More preferred are the groups

Preferably, it is a specific compound having liquid crystallinity, more preferably a specific compound having a polymerizable group and liquid crystallinity, for example, a liquid crystal compound having a polymerizable group represented by the following formula [vi] Is preferred. This compound is easily compatible with the compound of the formula [i] described above.

(Wherein X represents a fluorine atom, a cyano group, or a monovalent hydrocarbon group having 4 to 8 carbon atoms, f represents an integer of 2 to 9, and M represents the above formula [ii] or [iii]. A group of formula [ii].)

The compounding ratio of the specific compound is not particularly limited, but when the specific compound to be mixed exhibits liquid crystallinity, 900 to 5 parts by mass is preferable with respect to 100 parts by mass of the polymerizable liquid crystal compound of the formula [i]. More preferably, it is 200 to 15 parts by mass.
On the other hand, when the specific compound to mix does not show liquid crystallinity, 20 mass parts or less are preferable with respect to 100 mass parts of polymerizable liquid crystal compounds of Formula [i], More preferably, it is 5 mass parts or less.

Specific examples of the specific compound described above include compounds represented by the following formulas (31) to (129) described in WO06 / 115033 pamphlet and WO06 / 115112 pamphlet, and nematics: A liquid crystal, a ferroelectric liquid crystal, a commercially available liquid crystal composition, etc. can be mentioned, However, It is not limited to these.

In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator or a photosensitizer can be added for the purpose of improving the polymerization reactivity.
Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, benzophenones such as benzophenone, acetophenones such as diethoxyacetophenone, and benzyl ketals such as benzyldimethyl ketal. Such a photoinitiator can also be used in combination of multiple types.
The addition amount of the photopolymerization initiator is the total amount of the polymerizable liquid crystal compound represented by the formula [i], or the polymerizable liquid crystal compound represented by the formula [i], a polymerizable group, and a liquid crystal Is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass based on 100 parts by mass of the total amount with the specific compound exhibiting the property (hereinafter collectively referred to as the total polymerizable liquid crystal compound). Part by mass.

Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile. The thermal polymerization initiator may be used in combination of two or more kinds, and the addition amount thereof is preferably 5 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the total polymerizable liquid crystalline compound represented by the formula [i] 0.5 to 2.0 parts by mass.
Examples of the photosensitizer include anthracene photosensitizers such as anthracene. Multiple photosensitizers can be used in combination, and the amount added is preferably 5 parts by mass or less with respect to 100 parts by mass of the total polymerizable liquid crystalline compound.
The above photopolymerization initiator can be used in combination with at least one of a thermal polymerization initiator and a photosensitizer.

A stabilizer may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving its storage stability.
Examples of the stabilizer include hydroquinone monoalkyl ethers such as hydroquinone and hydroquinone monomethyl ether, and 4-t-butylcatechol. A stabilizer can also be used in combination of several types, and the addition amount is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the total polymerizable liquid crystalline compound.

In addition, an adhesion promoter may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the adhesion to the substrate.
Adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltri Alkoxysilanes such as ethoxysilane; silazanes such as hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-amino Propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Silanes such as (N-piperidinyl) propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, And heterocyclic compounds such as mercaptopyrimidine; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds.
The adhesion promoter can be used in combination of plural kinds, and the addition amount is preferably 1 part by mass or less with respect to 100 parts by mass of the total polymerizable liquid crystalline compound.

Furthermore, an organic solvent can be added to the polymerizable liquid crystal composition of the present invention for the purpose of adjusting the viscosity. In this case, liquid crystal properties may not be exhibited in a state containing an organic solvent.
Examples of the organic solvent include ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as butyl acetate and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxypropionic acid Alkoxy esters such as ethyl; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Diglycol dialkyl ethers such as ethyl ether and dipropylene glycol dimethyl ether; glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; diethylene glycol monomethyl ether and diethylene glycol mono Diglycol monoalkyl ethers such as ethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether; Glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; cyclohexanone, methyl ethyl ketone Emissions, methyl isobutyl ketone, and the like ketones such as 2-heptanone. These organic solvents can be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate are preferable from the viewpoint of safety to the global environment and work environment.
The amount of the organic solvent used is preferably about 60 to 95% by mass in the polymerizable liquid crystal composition.

In addition, a surfactant may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the affinity with the substrate. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like, and are not particularly limited, but a fluorine-based surfactant having a high effect of improving affinity with a substrate is preferable.
Specific examples of fluorosurfactants (hereinafter referred to as trade names), EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by DIC Corporation) , FLORARD FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc. Is not to be done. In addition, surfactant can also be used in combination of multiple types.

Preferred examples of the polymerizable liquid crystal composition of the present invention include 100 parts by mass of the polymerizable liquid crystal compound represented by the formula [i], 20 parts by mass or less of a specific compound that does not exhibit liquid crystallinity, and 5 parts by mass of a photopolymerization initiator. A liquid crystal composition comprising: 100 parts by mass of a polymerizable liquid crystal compound represented by formula [i]; 200 to 15 parts by mass of a specific compound exhibiting liquid crystallinity; and 5 parts by mass or less of a photopolymerization initiator. Is mentioned.
The polymerizable liquid crystal composition described above can be suitably used as a composition for forming an orientation film or a coating solution.

The preparation method of the polymerizable liquid crystal composition of the present invention is not particularly limited, and each component constituting the polymerizable liquid crystal composition may be mixed at one time or sequentially. The order of adding the components in the sequential mixing is arbitrary.
In addition, when using several types of compounds for one component, the mixture which mixed them previously and another component may be mixed, and you may mix with another component separately, respectively.
The polymerizable liquid crystal composition of the present invention avoids unintentional induction of thermal polymerization in photopolymerization in a liquid crystal state and facilitates fixing of a uniform alignment state of molecules when producing an optical anisotropic body. It is preferable that a stable liquid crystal phase is exhibited at room temperature (20 to 40 ° C., hereinafter the same). When the polymerizable liquid crystal composition contains an organic solvent, it is preferable that a stable liquid crystal phase is exhibited at room temperature when the solvent is removed.

[Polymer and film]
A polymer can be obtained by subjecting the polymerizable liquid crystal composition of the present invention described above to light irradiation or heat treatment.
In addition, the film can be obtained by light irradiation treatment in a state where the polymerizable liquid crystal composition is sandwiched between two substrates, or in a state where the polymerizable liquid crystal composition is applied to the substrate by spin coating or casting method. can get.
At this time, a plastic film or sheet such as glass, quartz, a color filter, or triacetyl cellulose (TAC) can be used for the substrate. Of the two substrates, one of the substrates is a belt or drum on which a functional thin film such as ITO is formed, a plastic sheet, a plastic film, and stainless steel, or a metal such as chromium or aluminum. Can also be used.

The substrate to be used is preferably subjected to an orientation treatment for the purpose of improving the orientation of the obtained film. As a method of alignment treatment, a method of applying an alignment material containing a polyimide precursor, polyimide, polyvinyl cinnamate, etc., and irradiating with rubbing or polarized ultraviolet rays, a method of forming a silicon dioxide oblique deposition film Any known method such as a method for forming a Langmuir film can be selected as appropriate.

In the method of sandwiching the polymerizable liquid crystal composition between two substrates, a cell in which a gap is formed between the two substrates by using a spacer or the like is produced, and a method using a capillary phenomenon, a pressure reduction of the gap in the cell, or the like. After injecting the polymerizable liquid crystal composition into the cell by the method, the light is irradiated to polymerize it.
As a simpler method, a polymerizable liquid crystal composition is placed on a substrate provided with a spacer and the like, and a cell is produced by stacking the other substrate on the substrate, and light is irradiated to polymerize the cell. There is also a method.
At that time, the polymerizable liquid crystal composition may be fluidized, or may be fluidized by heating after being placed on the substrate. It is necessary to fluidize the liquid crystal composition.

In the method of applying the polymerizable liquid crystal composition, a step of heating with a hot plate or the like may be added as needed during the step of applying the polymerizable liquid crystal composition and the step of polymerizing with light or heat. This step is particularly effective as a means for removing the organic solvent from the composition when a polymerizable liquid crystal composition (coating liquid) containing the organic solvent is used.
In any of the above methods, an oriented film having optical anisotropy can be obtained by polymerization in a state where the polymerizable liquid crystal composition exhibits a liquid crystal phase.

In order to obtain a polymer in a multi-domain state having different orientations for adjacent domains, a method of multi-domaining in a polymerization process or a method of multi-domaining a substrate orientation treatment is used.
The method of forming a multi-domain by a polymerization method is a method in which a polymerizable liquid crystal composition in a liquid crystal state is exposed to ultraviolet rays through a mask to form a polymerized domain, and the remaining domains are polymerized in an isotropic liquid state. Etc.
In addition, examples of the method of making the alignment treatment of the substrate multi-domain include a method of rubbing the alignment material formed on the substrate through a mask and a method of irradiating ultraviolet rays through the mask.
By these methods, it is possible to obtain a multi-domained substrate in which the rubbed domain and the domain irradiated with ultraviolet rays are subjected to orientation treatment, and the others are untreated portions. The polymerizable liquid crystal composition formed on the multi-domained substrate is multi-domained under the influence of the alignment material layer.
In addition to the above alignment treatment method, a method using an electric field or a magnetic field may be used.

By using the polymerizable liquid crystal composition of the present invention, a film having optical anisotropy with low wavelength dependency is obtained, and this film can be suitably used for a polarizing plate, a phase difference plate and the like. Moreover, since this film has good transparency at high temperatures, it can be suitably used for electronic devices used in high-temperature environments such as in-vehicle display devices.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the measurement method and measurement conditions of each physical property in the examples are as follows.
[1] NMR
The compound was dissolved in deuterated chloroform (CDCl ₃ ) or deuterated dimethyl sulfoxide (DMSO-d6), and ¹ H-NMR at 300 MHz was measured using a nuclear magnetic resonance apparatus (manufactured by Diol).
[2] Observation of liquid crystal phase The liquid crystal phase was identified by heating the sample on a hot stage (MATS-2002S, manufactured by Tokai Hit) and observing it using a polarizing microscope (manufactured by Nikon). The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) (hereinafter referred to as DSC) manufactured by Mac Science Co., under a scan rate of 10 ° C./min.
[3] Haze value The haze value of the film was measured using a Spectral Haze Meter (TC-1800H) manufactured by Tokyo Denshoku.
[4] Retardation A retardation value at a wavelength of 590 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).

[1] Polymerizable liquid crystal compound [Synthesis Example 1] Synthesis of polymerizable liquid crystal compound (E1)

In a 500 ml eggplant flask equipped with a condenser tube, 9.8 g (50.0 mmol) of 4-cyano-4′-hydroxybiphenol, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, 13.8 g (100 mmol) of potassium carbonate , And 150 ml of acetone were added to form a mixture, which was reacted at 64 ° C. with stirring for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid was mixed with 140 ml of water, and 100 ml of diethyl ether was added thereto for extraction. Extraction was performed three times. The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was purified by recrystallization using a mixed solvent of hexane / ethyl acetate = 2/1 to obtain 8.7 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (A1) (yield 70%).
¹ H-NMR (CDCl ₃ ) δ: 2.09 (m, 2H), 3.90 (t, 2H), 4.20 (t, 2H), 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H ).

12.0 g of the intermediate compound (A1) obtained above was dissolved in 40 ml of THF together with 7.7 ml of triethylamine and a small amount of butylhydroxytoluene (hereinafter referred to as BHT), stirred at room temperature, cooled to 40 ml of THF under cooling with a water bath. A solution in which 4.6 ml of acryloyl chloride was dissolved was added dropwise over 15 minutes. After dropping, the mixture was stirred for 30 minutes, and the water bath was removed, and stirring was continued overnight while returning to room temperature, and the precipitated triethylamine hydrochloride was filtered. About 3/4 of THF was distilled off from the obtained filtrate, 50 ml of methylene chloride was added, and the organic layer was washed successively with 50 ml of saturated aqueous sodium hydrogen carbonate solution, 50 ml of 0.5N HCl, and 50 ml of saturated brine, After drying with magnesium sulfate, the solvent was distilled off to obtain the product. After recrystallization from ethanol, 6.0 g of compound (E1) was obtained.
¹ H-NMR (CDCl ₃ ) δ: 2.20 (m, 2H), 4.10 (t, 2H), 4.40 (t, 2H), 5.81 (d, 1H), 6.15 (m, 1H), 6.41 (d, 1H ), 6.99 (d, 2H), 7.55 (d, 2H), 7.66 (m, 4H).

[Synthesis Example 2] Synthesis of polymerizable liquid crystal compound (E2)

In a 100 ml eggplant flask equipped with a condenser tube, 5.0 g (25.6 mmol) of 4-cyano-4′-hydroxybiphenol, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, 7.0 g (50 mmol) of potassium carbonate And acetone (50 ml) were added to form a mixture, which was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 70 ml of water were mixed and extracted by adding 50 ml of diethyl ether. Extraction was performed three times.
The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 3 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the resulting solution to obtain 6.9 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (A2) (yield 91%).
¹ H-NMR (DMSO-d6) δ: 1.26 (m, 6H), 1.69 (m, 2H), 3.37 (t, 2H), 4.03 (t, 2H), 7.06 (d, 2H), 7.69 (d, 2H), 7.85 (m, 4H).

Next, 2.2 g (10.0 mmol) of pyridinium chlorochromate (hereinafter referred to as PCC) and 30.0 ml of CH ₂ Cl ₂ were added to a 200 ml three-necked flask equipped with a cooling tube, and the mixture was stirred and mixed. A solution of 2.95 g (10.0 mmol) of the obtained intermediate compound (A2) in CH ₂ Cl ₂ (50.0 ml) was added dropwise, and the mixture was further stirred at 40 ° C. for 0.5 hour. Thereafter, 90 ml of diethyl ether was added to the solution excluding the oily substance adhering to the flask wall and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was dissolved in 3 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the obtained solution was distilled off to obtain 2.8 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (B2) (yield 93%).
¹ H-NMR (CDCl ₃ ) δ: 1.84 (m, 6H), 2.50 (m, 2H), 4.02 (m, 2H), 6.99 (d, 2H), 7.53 (d, 2H), 7.91 (m, 4H ), 9.80 (s, 1H).

Finally, in a 50 ml eggplant flask equipped with a cooling tube, 3.0 g (10.0 mmol) of the intermediate compound (B2) obtained above, 1.65 g (10.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 1.6 g, tetrahydrofuran (THF) 16.0 ml, tin (II) chloride 1.9 g (10.0 mmol), and pure water 4.0 ml were added to form a mixture. The reaction was stirred for 7 hours at ° C. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 30 ml of pure water, and 50 ml of diethyl ether was added thereto for extraction. Extraction was performed three times.
The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a yellow solid. This solid was dissolved in 2 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent of the obtained solution was distilled off to obtain 1.5 g of a white solid. As a result of measuring this solid by NMR, it was confirmed that this white solid was the target polymerizable liquid crystal compound (E2) (yield 41%).
¹ H-NMR (CDCl ₃ ) δ: 1.57 (m, 6H), 1.85 (m, 2H), 2.60 (m, 1H), 3.05 (m, 1H), 4.01 (t, 2H), 4.54 (m, 1H ), 5.63 (m, 1H), 6.23 (m, 1H), 7.00 (d, 2H), 7.52 (d, 2H), 7.68 (m, 4H).
Further, as a result of observing the liquid crystal properties of this polymerizable liquid crystal compound (E2), it became an isotropic liquid state at 84 ° C., and phase transitioned to a liquid crystal phase (nematic phase) at 61 ° C. when the temperature was lowered.

[Example 1] Synthesis of polymerizable liquid crystal compound (Z1) (1) Synthesis of compound (P1)

In a 200 ml eggplant flask with a condenser tube, 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and acetone 70 ml was added to form a mixture, and the mixture was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the resulting solution to obtain 11.3 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P1) (yield 90%).
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d , 2H).

(2) Synthesis of compound (Q1)

Next, in a 100 ml three-necked flask with a condenser tube, PCG 2.2 g (10.0 mmol) and CH ₂ Cl ₂ 15.0 ml were added and stirred and mixed, 2.5 g of the intermediate compound (P1) obtained above. A solution prepared by dissolving (10.0 mmol) in CH ₂ Cl ₂ (15.0 ml) was added dropwise, and the mixture was further stirred at room temperature for 6 hours. Thereafter, 90 ml of diethyl ether was added to the solution excluding the oily substance adhering to the wall of the flask and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (Q1) (yield 50%).
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d , 2H), 9.78 (s, 1H).

(3) Synthesis of compound (R1)

Next, 1.25 g (5.0 mmol) of the intermediate compound (Q1) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 0.8 g, THF 8.0 ml, tin (II) chloride 0.95 g (5.0 mmol) and pure water 2.0 ml were added to form a mixture, and the mixture was kept at 70 ° C. for 5 hours. Stir to react. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 40 ml of pure water, and extracted with 50 ml of diethyl ether. Extraction was performed three times.
To the organic layer after extraction, anhydrous magnesium sulfate was added and dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.5 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (R1) (yield 94%).
¹ H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H).

(4) Synthesis of compound (S1)

To a 100 ml eggplant flask equipped with a condenser tube, 35 ml of ethanol, 1.5 g (4.7 mmol) of the compound (R1) obtained above, and 5 ml of 10% aqueous sodium hydroxide solution were added to form a mixture, and the mixture was stirred at 85 ° C. for 3 hours. It was made to react. After completion of the reaction, 300 ml of water and the reaction solution were added to a 500 ml beaker and stirred for 30 minutes at room temperature. Then, 5 ml of 10% HCl aqueous solution was added dropwise, followed by filtration to obtain 1.3 g of a white solid.
Next, 1.1 g of the obtained white solid, Amberlyst (registered trademark) 15 (trade name of Rohm End Haas Co., Ltd.) 1.0 g, and 20.0 ml of tetrahydrofuran were added to a 50 ml eggplant flask equipped with a cooling tube to obtain a mixture. The reaction was stirred at 5 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off from the solution after the reaction solution was filtered under reduced pressure to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1) to obtain 0.9 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a compound (S1) (yield 71%).
¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H).

(5) Synthesis of polymerizable liquid crystal compound (Z1)

Compound (S1) 6.1 g (20.0 mmol), 6- (4-hydroxyphenoxy) hexyl acrylate 5.3 g (20.0 mmol), N, N-dimethyl-4-aminopyridine (hereinafter referred to as DMAP) 0. 1 g and a small amount of BHT were suspended in 100 ml of methylene chloride under stirring at room temperature, and a solution in which 5.1 g (25.0 mmol) of dicyclohexylcarbodiimide (hereinafter referred to as DCC) was dissolved was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 100 ml of 0.5N HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated brine successively, dried over magnesium sulfate, and then the solvent under reduced pressure. Was distilled off to obtain a yellow solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the solution obtained here was distilled off to obtain 4.3 g of the target polymerizable liquid crystal compound (Z1) (yield 39%).
¹ H-NMR (CDCl ₃ ) δ: 1.53 (m, 10H), 1.72 (m, 2H), 1.79 (m, 4H), 2.58 (m, 1H), 3.07 (m, 1H), 3.96 (t, 2H ), 4.05 (t, 2H), 4.18 (t, 2H), 4.54 (m, 1H), 5.64 (d, 1H), 5.81 (d, 1H), 6.14 (m, 1H), 6.24 (d, 1H) , 6.40 (d, 1H), 6.97 (m, 4H), 7.09 (d, 2H), 8.14 (d, 2H).
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z1), an isotropic liquid state was obtained at 59 ° C. when the temperature was increased. Further, the phase transitioned to the smectic X phase at 55 ° C. when the temperature was lowered.

[Example 2] Synthesis of polymerizable liquid crystal compound (Z2) (1) Synthesis of compound (P2)

In a 200 ml eggplant flask with a condenser tube, methyl 4-hydroxybenzoate 5.5 g (36.0 mmol), 5-bromo-1-pentanol 6.0 g (36.0 mmol), potassium carbonate 9.0 g (72 mmol), and Acetonitrile (80 ml) was added to form a mixture, which was reacted at 80 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the solution obtained here to obtain 1.8 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P2) (yield 21%).
¹ H-NMR (CDCl ₃ ) δ: 1.5-1.7 (m, 4H), 2.85 (m, 2H), 3.67 (t, 2H), 3.88 (s, 3H), 4.02 (t, 2H), 6.90 (d , 2H), 7.99 (d, 2H).

(2) Synthesis of compound (Q2)

Next, 1.7 g (7.6 mmol) of PCC and 15.0 ml of CH ₂ Cl ₂ were added to a 100 ml three-necked flask equipped with a condenser tube, and 1.8 g of the intermediate compound (P2) obtained above was stirred and mixed. A solution prepared by dissolving (7.6 mmol) in CH ₂ Cl ₂ (15.0 ml) was added dropwise, and the mixture was further stirred at room temperature for 6 hours. Thereafter, 90 ml of diethyl ether was added to the solution excluding the oily substance adhering to the wall of the flask and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the solution obtained here was distilled off to obtain 1.2 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was intermediate compound (Q2) (yield 67%).
¹ H-NMR (CDCl ₃ ) δ: 1.85 (m, 4H), 2.54 (t, 2H), 3.88 (s, 3H), 4.01 (t, 2H), 6.91 (d, 2H), 7.99 (d, 2H ), 9.80 (s, 1H).

(3) Synthesis of compound (R2)

Next, in a 50 ml eggplant flask equipped with a cooling tube, 1.20 g (5.0 mmol) of the intermediate compound (Q2) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 0.8 g, THF 8.0 ml, tin (II) chloride 0.95 g (5.0 mmol) and pure water 2.0 ml were added to form a mixture, and the mixture was kept at 70 ° C. for 5 hours. Stir to react. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 40 ml of pure water, and extracted with 50 ml of diethyl ether. Extraction was performed three times.
The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.3 g of a colorless solid. As a result of measuring this solid by NMR, it was confirmed that this solid was the compound (R2) (yield 85%).
¹ H-NMR (CDCl ₃ ) δ: 1.5-1.9 (m, 6H), 2.63 (m, 1H), 3.06 (m, 1H), 3.88 (s, 3H), 4.03 (t, 2H), 4.54 (m , 1H), 5.63 (s, 1H), 6.23 (s, 1H), 6.90 (d, 2H), 7.99 (d, 2H).

(4) Synthesis of compound (S2)

To a 100 ml eggplant flask with a condenser tube, 35 ml of ethanol, 1.3 g (4.3 mmol) of the compound (R2) obtained above, and 5 ml of 10% aqueous sodium hydroxide solution were added to form a mixture and stirred at 85 ° C. for 3 hours. While reacting. After completion of the reaction, 300 ml of water and the reaction solution were added to a 500 ml beaker and stirred for 30 minutes at room temperature. After 5 ml of 10% HCl aqueous solution was added dropwise and filtered, 1.0 g of a white solid was obtained.
Next, 1.0 g of the obtained white solid, Amberlyst (registered trademark) 15 (trade name of Rohm End Haas Co., Ltd.), and 20.0 ml of tetrahydrofuran are added to a 50 ml eggplant flask with a cooling tube to obtain a mixture. The reaction was stirred at 70 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off from the solution after the reaction solution was filtered under reduced pressure to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / tetrahydrofuran, 2/1) to obtain 0.9 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a compound (S2) (yield 72%).
¹ H-NMR (DMSO-d6) δ: 1.4-1.8 (m, 6H), 2.60 (m, 1H), 3.10 (m, 1H), 4.06 (m, 2H), 4.58 (m, 1H), 5.71 ( s, 1H), 6.03 (s, 1H), 7.00 (d, 2H), 7.88 (d, 2H).

(5) Synthesis of polymerizable liquid crystal compound (Z2)

0.5 g (1.7 mmol) of the compound (S2) obtained above, 0.5 g (1.7 mmol) of 6- (4-hydroxyphenoxy) hexyl acrylate, 0.01 g of DMAP, and a small amount of BHT were stirred at room temperature. The solution was suspended in 15 ml of methylene chloride, and a solution in which 0.4 g (1.9 mmol) of DCC was dissolved was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 30 ml of 0.5N HCl, 30 ml of saturated aqueous sodium hydrogen carbonate solution and 60 ml of saturated brine successively, dried over magnesium sulfate, and then the solvent under reduced pressure. Was distilled off to obtain a yellow solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the solution obtained here was distilled off to obtain 0.3 g of the target polymerizable liquid crystal compound (Z2) (yield 30%).
¹ H-NMR (CDCl ₃ ) δ: 1.53 (m, 8H), 1.70 (m, 2H), 1.81 (m, 4H), 2.58 (m, 1H), 3.08 (m, 1H), 3.93 (t, 2H ), 4.05 (t, 2H), 4.18 (t, 2H), 4.56 (m, 1H), 5.64 (d, 1H), 5.81 (d, 1H), 6.14 (m, 1H), 6.24 (d, 1H) , 6.40 (d, 1H), 6.95 (m, 4H), 7.09 (d, 2H), 8.14 (d, 2H).
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z2), the liquid crystal phase became an isotropic liquid state at 56 ° C. when the temperature was increased. In addition, the phase transitioned to the smectic X phase at 26 ° C. when the temperature was lowered.

[Example 3] Synthesis of polymerizable compound (Z3) (1) Synthesis of compound (P3)

In a 200 ml eggplant flask equipped with a condenser tube, 16.0 g (105.0 mmol) of methyl 4-hydroxybenzoate, 25.0 g (105.0 mmol) of 10-bromo-1-decanol, 29.0 g (210.0 mmol) of potassium carbonate, And 200 ml of acetonitrile was added to make a mixture, which was reacted at 80 ° C. with stirring for 48 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the solution obtained here to obtain 21.4 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P3) (yield 66%).
¹ H-NMR (CDCl ₃ ) δ: 1.2-1.6 (m, 14H), 1.8 (m, 2H), 3.63 (t, 2H), 3.88 (s, 3H), 4.02 (t, 2H), 6.90 (d , 2H), 7.99 (d, 2H).

(2) Synthesis of compound (Q3)

Next, 21.4 g of the intermediate compound (P3) obtained above in a state in which 15.0 g (69.5 mmol) of PCC and 100.0 ml of CH ₂ Cl ₂ were put in a 500 ml three-necked flask equipped with a condenser and stirred and mixed. A solution prepared by dissolving (69.5 mmol) in CH ₂ Cl ₂ (100.0 ml) was added dropwise, and the mixture was further stirred at room temperature for 6 hours. Thereafter, 200 ml of diethyl ether was added to the solution excluding the oily substance adhering to the wall of the flask and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent of the solution obtained here was distilled off to obtain 16.2 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (Q3) (yield 76%).
¹ H-NMR (CDCl ₃ ) δ: 1.26 (m, 10H), 1.62 (m, 2H), 1.79 (m, 2H), 2.42 (m, 2H), 3.88 (s, 3H), 4.00 (t, 2H ), 6.91 (d, 2H), 7.99 (d, 2H), 9.76 (s, 1H).

(3) Synthesis of compound (R3)

Next, in a 300 ml eggplant flask equipped with a cooling tube, 16.2 g (53.0 mmol) of the intermediate compound (Q3) obtained above, 8.8 g (53.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 7.4 g, THF 85.0 ml, tin (II) chloride 10.1 g (53.0 mmol), and pure water 20.0 ml were added to form a mixture, and the mixture was kept at 70 ° C. for 20 hours. Stir to react. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 100 ml of pure water, and extracted with 100 ml of diethyl ether. Extraction was performed three times.
To the organic layer after extraction, anhydrous magnesium sulfate was added and dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 16.4 g of a colorless solid. As a result of measuring this solid by NMR, it was confirmed that this colorless solid was the compound (R3) (yield 83%).
¹ H-NMR (CDCl ₃ ) δ: 1.28 (m, 12H), 1.60 (m, 2H), 1.72 (m, 2H), 2.51 (m, 1H), 3.06 (m, 1H), 3.85 (s, 3H ), 4.04 (t, 2H), 4.54 (m, 1H), 5.69 (s, 1H), 6.02 (s, 1H), 7.01 (d, 2H), 7.88 (d, 2H).

(4) Synthesis of compound (S3)

To a 500 ml eggplant flask equipped with a condenser tube, 100 ml of ethanol, 16.4 g (43.8 mmol) of compound (R3) and 60 ml of 10% aqueous sodium hydroxide solution were added to form a mixture and reacted at 85 ° C. with stirring for 5 hours. After completion of the reaction, 1000 ml of water and the reaction solution were added to a 2000 ml beaker and stirred at room temperature for 30 minutes, and then 60 ml of 10% HCl aqueous solution was added dropwise and filtered to obtain 14.6 g of a white solid.
Next, 14.6 g of the obtained white solid, Amberlyst (registered trademark) 15 (trade name of Rohm End Haas Co.), and 100 ml of tetrahydrofuran are added to a 300 ml eggplant flask equipped with a cooling tube to obtain a mixture, and the mixture is prepared at 70 ° C. The reaction was stirred for 5 hours. After completion of the reaction, the solvent was distilled off from the solution after the reaction solution was filtered under reduced pressure to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / tetrahydrofuran, 2/1) to obtain 11.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (S3) (yield 73%).
¹ H-NMR (DMSO-d6) δ: 1.32 (m, 12H), 1.60 (m, 2H), 1.80 (m, 2H), 2.59 (m, 1H), 3.02 (m, 1H), 4.00 (t, 2H), 4.50 (m, 1H), 5.61 (s, 1H), 6.02 (s, 1H), 6.90 (d, 2H), 7.98 (d, 2H).

(5) Synthesis of polymerizable compound (Z3)

Compound (S3) 2.0 g (5.6 mmol), 6- (4-hydroxyphenoxy) hexyl acrylate 1.5 g (5.6 mmol), DMAP 0.03 g, and a small amount of BHT were stirred at room temperature with 20 ml of methylene chloride. A solution in which 1.3 g (6.2 mmol) of DCC was dissolved was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 0.5 N HCl (50 ml), saturated aqueous sodium hydrogen carbonate solution (50 ml) and saturated brine (100 ml), dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Was distilled off to obtain a yellow solid. This solid was purified by recrystallization using ethanol to obtain 1.3 g of a white solid (yield 38%). The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (Z3).
¹ H-NMR (CDCl ₃ ) δ: 1.33 (m, 10H), 1.50 (m, 8H), 1.72 (m, 2H), 1.80 (m, 4H), 2.58 (m, 1H), 3.07 (m, 1H ), 3.96 (t, 2H), 4.05 (t, 2H), 4.14 (t, 2H), 4.55 (m, 1H), 5.63 (d, 1H), 5.82 (d, 1H), 6.14 (m, 1H) , 6.24 (d, 1H), 6.40 (d, 1H), 6.97 (m, 4H), 7.09 (d, 2H), 8.12 (d, 2H).
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z3), it became an isotropic liquid state at 68 ° C. when the temperature was increased. Further, the phase transitioned to the smectic X phase at 53 ° C. when the temperature was lowered.

[2] Polymerizable liquid crystal composition and polymer (film) thereof
The compounds used in the following examples and comparative examples are as follows. The compositions of Examples 4 to 12 and Comparative Example 1 are shown in Table 1 (unit: mg).

[Example 4] Polymerizable liquid crystal composition and polymer (film) thereof
2. 70.0 mg of a polymerizable liquid crystal compound (E1), 65.0 mg of a polymerizable liquid crystal compound (E2), 15.0 mg of a polymerizable liquid crystal compound (Z1), Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
This polymerizable liquid crystal composition was applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1000 rpm, 20 seconds), pre-baked on a 100 ° C. hot plate for 60 seconds, and then allowed to cool to room temperature. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The substrate with a liquid crystal alignment film used here was coated with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) on the ITO surface of a glass substrate with ITO by spin coating, and baked at 230 ° C. to have a thickness of 100 nm. After the thin film is formed, a rubbing treatment is performed.

Next, the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having an intensity of 2000 mJ / cm ² in air using a metal halide lamp to polymerize the polymerizable liquid crystal composition.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 191 nm and haze value was 0.05. Further, Δn (400 nm) / Δn (550 nm) was 1.253.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 148 nm and the haze value was 0.00. Δn (400 nm) / Δn (550 nm) was 1.227.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 128 nm and the haze value was 0.03. Δn (400 nm) / Δn (550 nm) was 1.233.

[Example 5] Polymerizable liquid crystal composition and polymer (film) thereof
2. Polymerizable liquid crystal compound (E1) 45.0 mg, Polymerizable liquid crystal compound (E2) 75.0 mg, Polymerizable liquid crystal compound (Z1) 30.0 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.4 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 194 nm and haze value was 0.02. Further, Δn (400 nm) / Δn (550 nm) was 1.256.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 149 nm and the haze value was 0.03. Δn (400 nm) / Δn (550 nm) was 1.233.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 127 nm and the haze value was 0.05. Δn (400 nm) / Δn (550 nm) was 1.232.

[Example 6] Polymerizable liquid crystal composition and polymer (film) thereof
2. 55.0 mg of a polymerizable liquid crystal compound (E1), 50.0 mg of a polymerizable liquid crystal compound (E2), 45.0 mg of a polymerizable liquid crystal compound (Z1), Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 169 nm and haze value was 0.00. Δn (400 nm) / Δn (550 nm) was 1.228.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 138 nm and the haze value was 0.00. Δn (400 nm) / Δn (550 nm) was 1.227.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 117 nm and the haze value was 0.03. Δn (400 nm) / Δn (550 nm) was 1.222.

[Example 7] Polymerizable liquid crystal composition and polymer (film) thereof
2. Polymerizable liquid crystal compound (E1) 40.0 mg, polymerizable liquid crystal compound (E2) 50.0 mg, polymerizable liquid crystal compound (Z1) 60.0 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 135 nm and haze value was 0.00. Δn (400 nm) / Δn (550 nm) was 1.228.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 122 nm and the haze value was 0.03. Further, Δn (400 nm) / Δn (550 nm) was 1.209.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 97 nm and the haze value was 0.05. Δn (400 nm) / Δn (550 nm) was 1.222.

[Example 8] Polymerizable liquid crystal composition and polymer (film) thereof
2. 15.0 mg of a polymerizable liquid crystal compound (E1), 35.0 mg of a polymerizable liquid crystal compound (E2), 90.0 mg of a polymerizable liquid crystal compound (Z1), Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 119 nm and haze value was 0.05. Further, Δn (400 nm) / Δn (550 nm) was 1.207.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 111 nm and the haze value was 0.05. Further, Δn (400 nm) / Δn (550 nm) was 1.179.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 95 nm and the haze value was 0.07. Further, Δn (400 nm) / Δn (550 nm) was 1.184.

[Example 9] Polymerizable liquid crystal composition and polymer (film) thereof
2. 15.0 mg of a polymerizable liquid crystal compound (E1), 15.0 mg of a polymerizable liquid crystal compound (E2), 120.0 mg of a polymerizable liquid crystal compound (Z1), Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 103 nm and haze value was 0.03. Further, Δn (400 nm) / Δn (550 nm) was 1.156.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 96 nm and the haze value was 0.01. Further, Δn (400 nm) / Δn (550 nm) was 1.169.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 83 nm and the haze value was 0.11. Δn (400 nm) / Δn (550 nm) was 1.174.

[Example 10] Polymerizable liquid crystal composition and polymer (film) thereof
2. Polymerizable liquid crystal compound (E1) 7.5 mg, polymerizable liquid crystal compound (E2) 15.0 mg, polymerizable liquid crystal compound (Z1) 127.5 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 116 nm and haze value was 0.05. Further, Δn (400 nm) / Δn (550 nm) was 1.156.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 107 nm and the haze value was 0.07. Further, Δn (400 nm) / Δn (550 nm) was 1.167.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 93 nm and the haze value was 0.03. Δn (400 nm) / Δn (550 nm) was 1.173.

[Example 11] Polymerizable liquid crystal composition and polymer (film) thereof
2. 60.0 mg of a polymerizable liquid crystal compound (E1), 60.0 mg of a polymerizable liquid crystal compound (E2), 30.0 mg of a polymerizable liquid crystal compound (Z2), Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 149 nm and haze value was 0.07. In addition, Δn (400 nm) / Δn (550 nm) was 1.237.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 120 nm and the haze value was 0.07. Δn (400 nm) / Δn (550 nm) was 1.227.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 101 nm and the haze value was 0.04. Further, Δn (400 nm) / Δn (550 nm) was 1.201.

[Example 12] Polymerizable liquid crystal composition and polymer (film) thereof
2. 55.0 mg of a polymerizable liquid crystal compound (E1), 50.0 mg of a polymerizable liquid crystal compound (E2), 45.0 mg of a polymerizable liquid crystal compound (Z3), Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator. 0 mg and 0.3 mg of surfactant R-30 (DIC Corporation) were dissolved in 0.35 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.3 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 173 nm and haze value was 0.00. Further, Δn (400 nm) / Δn (550 nm) was 1.209.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 146 nm and the haze value was 0.05. Δn (400 nm) / Δn (550 nm) was 1.222.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 112 nm and the haze value was 0.03. Δn (400 nm) / Δn (550 nm) was 1.228.

[Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (E1) 400 mg, Polymerizable liquid crystal compound (E2) 350 mg, Ciba Geigy Irgacure 369 (trade name) 15.0 mg as a photopolymerization initiator, and surfactant R-30 (DIC Corporation) ) 0.8 mg was dissolved in 1.75 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 4. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.5 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 240 and the haze value was 0.07. Δn (400 nm) / Δn (550 nm) was 1.266.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 2.9 nm and the haze value was 0.45.
Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the retardation value was 0 nm and the haze value was 0.09.

The summary of Examples 4 to 12 and Comparative Example 1 is shown in Table 2.

Claims (9)

1. A polymerizable liquid crystal compound represented by the following formula [i].
   

   

   (In the formula, n represents an integer of 3 to 10, and m represents an integer of 4 to 8.)
2. A liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1.
3. The liquid crystal composition according to claim 2, further comprising a liquid crystalline compound having one polymerizable group in one molecule.
4. The liquid crystal composition according to claim 3, wherein the liquid crystal compound is a compound having one polymerizable group represented by the following formula [ii] or [iii] in one molecule.
   

   
5. The liquid crystal composition according to claim 3 or 4, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formula [vi].
   

   

   (In the formula, X is a fluorine atom, a cyano group, or a monovalent hydrocarbon group having 4 to 8 carbon atoms, f is an integer of 2 to 9, and M is represented by the following formula [ii] or [iii]: Group.)
   

   
6. A polymer obtained from the liquid crystal composition according to any one of claims 2 to 5.
7. A film obtained from the liquid crystal composition according to any one of claims 2 to 5.
8. An alignment film obtained from the liquid crystal composition according to any one of claims 2 to 5.
9. An optical member comprising the polymer according to claim 6 or the oriented film according to claim 8.