TWI521048B - A polymerizable liquid crystal compound, a polymerizable liquid crystal composition, and a alignment film - Google Patents

Description

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

The present invention relates to a polymerizable liquid crystal compound having a polymerizable property and a liquid crystal property, a composition containing the same, and a polymer and an alignment film obtained by using the same, and can be suitably used, for example, for having a display device or a recording material. A material of an optical property, in particular, a polymerizable liquid crystal compound of an optical compensation film such as a polarizing plate or a phase difference plate for a liquid crystal display, a composition containing the same, and a polymer and an alignment film obtained by using the same.

In the optical compensation film such as a polarizing plate or a phase difference plate, the demand for a polymer film for controlling the internal molecular alignment structure is increasing as the display quality of the liquid crystal display device is improved or reduced. In order to meet this requirement, a film utilizing optical anisotropy of a polymerizable liquid crystal compound has been developed.

The polymerizable liquid crystal compound used herein generally has a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (having a structure portion of a spacer portion and a mesogen portion), and an acrylic group can be widely used as the polymerizable group.

Such a polymerizable liquid crystal compound is generally formed by a method of polymerizing radiation such as ultraviolet rays to form a polymer (film).

For example, a method in which a polymerizable liquid crystal compound having a specific acryl group is supported between a support, and the compound is held in a liquid crystal state while irradiating radiation to obtain a polymer is known (see Patent Document 1) or A mixture of two types of polymerizable liquid crystal compounds having an acrylic group, or a mixture of a photopolymerization initiator added to a composition of a palm liquid crystal, and a polymer obtained by irradiating ultraviolet rays to obtain a polymer (see Patent Document 2) .

The polymer (film) obtained by the above-mentioned methods is used for a polarizing plate or a film for a phase difference plate, and the display device such as a monitor or a television is mounted on a high-temperature environment such as a car. The display device used. Therefore, in a high temperature environment, it is very important to maintain transparency as a material for a display device.

However, when the film obtained from the polymerizable liquid crystal compound has a glass transition temperature (hereinafter referred to as Tg) which is equal to or lower than the temperature of the use environment, particularly in a high-temperature environment, molecular microscopic oscillation occurs, so that the alignment is disordered, and sometimes the optical The anisotropy is significantly reduced.

Further, in the field of displays, research on the simplification of the process of using such materials as In Cell retardation films has been actively conducted in recent years. Materials that can be used with this In Cell technology further require high thermal stability and chemical resistance.

In addition, various alignment films such as horizontal, vertical, and mixed alignment can be obtained depending on the alignment mode of the polymerizable liquid crystal compound, and a mixed alignment film which exhibits various average tilt angles has also been reported (see Patent Document 3). Among them, the additive of the liquid crystal composition can be widely used in the field of liquid crystal displays by controlling the average tilt angle of the obtained film with a low addition amount.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-62-70407

[Patent Document 2] Japanese Patent Publication No. 9-208957

[Patent Document 3] International Publication No. 08/052376

The present invention has been made in view of such a problem, and an object thereof is to provide an optical anisotropy excellent in stability and a stable retardation value and transparency even at a high temperature, and further excellent in chemical resistance and heat resistance. The polymerizable liquid crystal compound, the polymerizable liquid crystal composition containing the polymerizable liquid crystal composition, and the polymer and alignment film obtained from the polymerizable liquid crystal composition can be controlled at a low level.

The inventors of the present invention have found that a specific polymerizable liquid crystal compound having an α-methylene-γ-butyrolactone moiety has liquid crystallinity and is excellent in polymerizability in order to solve the above problems. The low addition amount controls the average angle of the mixed alignment film, and at the same time, obtains a stable liquid crystal composition, and the polymer or film obtained from the liquid crystal composition has excellent heat resistance in optical anisotropy and transparency, and finally The present invention has been completed.

That is, the present invention is

A polymerizable liquid crystal compound characterized by the following formula [1], (wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, G is a -C(=O)O- or -OC(=O)- group, and n is an integer from 4 to 10).

A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to item 1.

3. The polymerizable liquid crystal composition according to the second aspect, which further comprises a liquid crystalline compound having one or more polymerizable groups in one molecule.

4. The polymerizable liquid crystal composition according to the third aspect, wherein the liquid crystal compound is a compound having one or more polymerizable groups represented by the following formula [2] or [3] in one molecule; (In the formula, the dotted line indicates the bonding hand).

5. The polymerizable liquid crystal composition according to Item 3 or 4, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formula [4] or [5]; (wherein X represents a fluorine atom, a cyano group or a carbon number 4 to 8 one-valent hydrocarbon group, and f1 and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9, M ¹ and M ² And M ³ independently represent a group represented by the following formula [2] or [3]; (In the formula, the dotted line indicates the bonding hand).

A polymer obtained by the polymerizable liquid crystal composition according to any one of items 2 to 5.

A film obtained by the polymerizable liquid crystal composition according to any one of items 2 to 5.

An alignment film obtained by the polymerizable liquid crystal composition according to any one of items 2 to 5.

An optical member comprising the polymer of item 6 or the alignment film of item 8.

A compound characterized by the following formula [6]; (wherein Y represents -OH or -COOH, and k represents an integer of 4 to 10).

The polymerizable liquid crystal compound of the present invention and the composition containing the same have not only excellent optical anisotropy, but also a polymer which is stable in a high temperature environment and has a stable transparency.

Further, the polymerizable liquid crystal compound of the present invention has an advantage that the tilt of the optical anisotropy containing the composition can be controlled with a small addition amount.

Therefore, the polymer obtained from the composition containing the polymerizable liquid crystal compound can be suitably used as an optical anisotropic film such as a polarizing plate or a retardation film.

[Formation for implementing the invention]

The terms used in this specification are as follows.

The term "polymerizable liquid crystal compound" means a compound having a polymerizable site such as an acrylic group or an α-methylene lactone ring and a liquid crystal structure in the molecule and exhibiting a liquid crystal phase. The term "liquid crystal structure" means a structure which can be used for a liquid crystal molecule and has a spacer portion and a crystal former portion. The "liquid crystal composition" means a composition having characteristics exhibiting a liquid crystal phase. "Liquidity Means to present a liquid crystal phase.

Hereinafter, the present invention will be described in more detail.

[Polymerized liquid crystal compound]

The polymerizable liquid crystal compound of the present invention is characterized by the following formula [1], (wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, G is a -C(=O)O- or -OC(=O)- group, and n is an integer from 4 to 10).

The compound represented by the formula [1] is a compound having a lactone ring and a liquid crystal structure, and has a polymerizable liquid crystal compound having an α-methylene-γ-butyrolactone moiety.

Among the α-alkylidene-γ-butyrolactone having a polymerizable group, the α-alkylene-γ-butyrolactone is less affected by steric hindrance, and exhibits excellent effects of high polymerizability. . Further, the polymer obtained by using this compound is effective because it imparts high Tg or heat resistance.

In the formula [1], the repeating portion of the methylene group is referred to as a portion called a spacer portion. Here, n represents the number of repetitions of methylene groups, and is an integer of 4 to 10, But it should be an integer from 4 to 6.

R in the formula [1] represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

Here, the halogen atom may, for example, be fluorine, chlorine, bromine or iodine atoms, but in the present invention, it is preferably a fluorine atom.

The alkyl group may be any of a straight chain, a branch, and a ring, and the carbon number thereof is not particularly limited. However, in the present invention, it is preferably a linear alkyl group having 1 to 10 carbon atoms.

Specific examples of the above alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, t-butyl, t-butyl, cyclobutyl, and Pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like.

The alkyl group constituting the alkoxy group may be any of a straight chain, a branch, and a ring, and the carbon number thereof is not particularly limited. However, in the present invention, the carbon number is preferably 1 to 10 in a straight chain. Alkyl alkoxy group.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. N-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy and the like.

The alkyl group constituting the alkoxycarbonyl group may be any of a straight chain, a branch, and a ring, and the carbon number thereof is not particularly limited, but in the present invention, it is preferably a linear carbon number 1~ Alkyloxycarbonyl group of 10 alkyl.

Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, and a n-butoxycarbonyl group. Isobutoxycarbonyl, second butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-decyloxycarbonyl, positive Alkoxycarbonyl and the like.

At least one of the hydrogen atoms of the alkyl group, the alkoxy group and the alkoxycarbonyl group may be further substituted with another substituent such as a halogen atom.

Among the above R-based substituents, a hydrogen atom, a halogen atom and an alkoxycarbonyl group are particularly preferable, and a hydrogen atom, a fluorine atom or an alkoxycarbonyl group having a linear alkyl group having 1 to 5 carbon atoms is more preferable.

The polymerizable liquid crystal compound represented by the above formula [1] represents a liquid crystal phase of a so-called smectic phase or a nematic phase. This characteristic can be used in the field of application using optical anisotropy such as a polarizing plate or a phase difference plate.

Specific examples of the polymerizable liquid crystal compound include compounds represented by the following formulas (1) to (35), and the like, and are not limited thereto.

[Synthesis of Polymeric Liquid Crystal Compound]

The polymerizable liquid crystal compound of the present invention can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited.

A compound having an α-methylene-γ-butyrolactone structure can be synthesized by a method such as that proposed by Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990)). This method is a method of reacting 2-(bromomethyl)propenoic acid with aldehyde and a ketone using SnCl ₂ as shown by the following synthesis mechanism (A1).

Further, 2-(bromomethyl)acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, D. J. O'Donnell and K. D. Berlin, Organic Synthesis, Vol. 61, 56-59 (1983)).

(wherein R' represents a monovalent organic group, and Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm & Hass Co., Ltd. Et represents an ethyl group)

Further, in the reaction using 2-(bromomethyl)acrylic acid of SnCl _{2 ,} the aldehyde or ketone is substituted by the reaction with the corresponding acetal or ketal, and the α-methylene-γ-butyrolactone structure can also be obtained. .

The acetal or ketal may, for example, have a dimethyl acetal or a diethyl acetal. a compound such as 1,3-dioxyl or 1,3-dioxolane. The synthesis method and protecting group in the case of showing an acetal or a ketal in the following synthesis mechanism (A2).

(wherein R' represents the same meaning as described above. The broken line indicates the bonding hand).

The intermediate compound for synthesizing the compound represented by the formula [1] can be synthesized by the following synthesis mechanism (B) or (C) using the above-described synthesis mechanism (A1) or (A2).

(wherein, n represents the same meaning as above. Me means methyl. PCC means pyridinium chlorochromate)

(wherein n represents the same meaning as described above).

Next, as shown in the following synthesis means (D) or (E), the intermediate is reacted with a phenol-based compound to be esterified, whereby a polymerizable liquid crystal compound represented by the formula [1] can be obtained.

(wherein n, X ¹ to X ⁴ and R are the same meanings as described above. DCC means dicyclohexylcarbonyldiimide, and DMAP means N,N-dimethyl-4-aminopyridine)

(wherein, n, X ¹ to X ⁴ and R represent the same meaning as described above).

[Polymerized liquid crystal composition]

The polymerizable liquid crystal composition of the present invention may be one containing at least one polymerizable liquid crystal compound represented by the above formula [1], but the polymerizable liquid crystal composition of the present invention is a mixed formula [1]. The polymerizable liquid crystal compound and the compound having a liquid crystal structure (hereinafter referred to as a specific compound) can provide a mixed alignment film. Therefore, it is preferable to contain at least one polymerizable liquid crystal compound represented by the formula [1] and the above specific compound. By.

Further, the specific compounds to be mixed may be used singly or in combination of plural kinds.

In this case, the specific compound may have a polymerizable group such as an acrylic group or a lactone ring, or may not. The specific compound having a polymerizable group may be monofunctional or polyfunctional.

The specific compound is a compound which does not have a polymerizable group, and exhibits a liquid crystal property, a compound having a polymerizable group and a liquid crystal property, and a compound other than the polymerizable liquid crystal compound of the present invention.

The polymerizable group which the above specific compound has is, for example, a group represented by the following formula [2] or [3].

(where the dotted line indicates the keying hand)

The specific compound having the above polymerizable group is preferably a group represented by the following formula [4] or [5].

(wherein M ¹ , M ² and M ³ are each independently a group represented by the following formula [2] or [3]. X represents a hydrogen atom, a cyano group or a carbon number 4 to 8 one-valent hydrocarbon group, f1 And f2 independently represent integers from 2 to 9, and g is an integer from 2 to 9)

The blending ratio of the above-mentioned specific compound is not particularly limited, but is 200 to 1900 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound of the formula [1], preferably based on the polymerizable liquid crystal compound 100 of the formula [1]. The mass parts are 400 to 900 parts by mass.

Specific examples of the specific compound described above include, for example, the compounds represented by the formulas (36) to (126) described below, or the nematic according to the handbook of International Publication No. 06/115033 and International Publication No. 06/115112. The liquid crystal, the ferroelectric liquid crystal, and a commercially available liquid crystal composition are not limited thereto.

In the polymerizable liquid crystal compound of the present invention, the polymerization reactivity is improved. For the purpose, a photopolymerization initiator, a thermal polymerization initiator, a photosensitizer, or the like may be added.

Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, acetophenones such as diethoxyacetamethylene, and benzoyl benzyl ketal. Ketal ketones and the like. The photopolymerization initiator may be used singly or in combination of plural kinds.

The amount of the photopolymerization initiator added is 100 masses based on the total amount of the polymerizable liquid crystal compound represented by the formula [1] and the specific compound exhibiting liquid crystallinity (hereinafter, referred to as a total of the liquid crystal compound) The amount is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass.

The above thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile or the like. The thermal polymerization initiator may be used alone or in combination of a plurality of them, and the amount thereof is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass, per 100 parts by mass of the total liquid crystal compound.

The photosensitizing agent may, for example, be a quinone-based photosensitizer such as hydrazine. The light sensitizer may be used alone or in combination of a plurality of them, and the amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the total liquid crystal compound.

Further, the photopolymerization initiator may be used in combination with at least one of a thermal polymerization initiator and a photosensitizer.

In the polymerizable liquid crystal composition of the present invention, a stabilizer may be added for the purpose of improving the preservation stability.

Examples of the stabilizer include hydroquinone monoalkyl ethers such as hydroquinone and hydroquinone monomethyl ether, and 4-tert-butylcatechol. The stabilizer may be used singly or in combination of plural kinds, and the amount added is based on the total liquid crystal compound. 100 parts by mass of the substance is preferably 0.1 part by mass or less.

In the polymerizable liquid crystal composition of the present invention, for the purpose of improving the adhesion to the substrate, an adhesion promoter may be added.

The adhesion promoter may, for example, be a chlorodecane such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane or chloromethyldimethylchlorosilane; trimethylmethoxy Alkynes such as decane, dimethyldiethoxydecane, methyldimethoxydecane, dimethylvinylethoxysilane, diphenyldimethoxydecane, phenyltriethoxydecane Nitroxide; hexamethyldiazepine, N,N'-bis(trimethyldecyloxy)urea, dimethyltrimethyldecyloxyamine, trimethyldecyloxyimidazole, etc. Alkanes; vinyl trichlorodecane, γ-chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-epoxy a decane such as propoxypropyltrimethoxydecane or γ-(N-hexahydropyridyl)propyltrimethoxydecane; benzotriazole, benzimidazole, anthracene, imidazole, 2-hydrogenthio a heterocyclic compound such as benzimidazole, 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, ureazazole, thiouracil, hydrothioimidazole, thiopyrimidine; 1,1- Dimethylurea, 1,3-dimethyl Etc. The urea compound; urea sulfur compounds.

The adhesion promoter may be used alone or in combination of a plurality of them, and the amount thereof is preferably 1 part by mass or less based on 100 parts by mass of the total liquid crystal compound.

Further, the polymerizable liquid crystal composition of the present invention may be added with an organic solvent for the purpose of adjusting the viscosity and the like. At this time, liquid crystallinity may not be exhibited in the 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; and N,N-dimethylformamide and N-methyl-2-pyrrolidone. Polar solvent; esters of ethyl acetate, butyl acetate, ethyl lactate, etc.; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, 2 - alkoxy esters such as ethyl methoxypropionate, ethyl 3-ethoxypropionate or ethyl 2-ethoxypropionate; ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc. Glycol dialkyl ether; diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; diethylene glycol monomethyl ether, diethyl Diethylene glycol monoalkyl ethers such as diol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, carbitol acetate, ethyl solution Glycol monoalkyl ether esters such as cellulose acetate Cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, etc. ketones. These organic solvents may be used alone or in combination of two or more types.

Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate are preferable from the viewpoint of safety in the global environment and the working environment.

Further, the amount of the organic solvent used is preferably from about 60 to 95% by mass in the polymerizable liquid crystal compound.

Further, in the polymerizable liquid crystal compound of the present invention, a surfactant may be added for the purpose of improving the affinity with the substrate. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant and a polyfluorene-based interface. The active agent, the nonionic surfactant, and the like are preferably a fluorine-based surfactant having a high affinity improving effect on the substrate.

Specific examples of the fluorine-based surfactant include, for example, (hereinafter, trade name), EFTOP EF 301, EF 303, EF 352 (manufactured by Tochem Products), Megfac F171, F173, R-30 (DIC). System, Fluorad FC 430, FC 431 (Sumitomo 3M (share) system), Asahiguard AG 710, Surflon S-382, SC101, SC102, SC 103, SC 104, SC 105, SC 106 (Asahi Glass Co., Ltd.) However, it is not limited to this. In addition, the surfactant may be used alone or in combination of a plurality of them, and the amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the total liquid crystal compound.

A suitable example of the polymerizable liquid crystal composition of the present invention is, for example, 100 parts by mass of the polymerizable liquid crystal compound represented by the formula [1], 400-900 parts by mass of the specific compound exhibiting liquid crystallinity, and the mass of the photoinitiator 5 The liquid crystal composition or the like composed of the following is not limited thereto.

The polymerizable liquid crystal composition described above can be suitably used as a composition or a coating liquid for forming an alignment film.

The preparation method of the polymerizable liquid crystal composition of the present invention is not particularly limited, and the components constituting the polymerizable liquid crystal composition may be mixed at once or sequentially. The order of addition of each component in the case of sequential mixing is arbitrary.

Further, when a plurality of compounds are used for one component, the mixture in which the mixture is mixed may be mixed with other components in advance, or may be separately mixed with other components.

When the polymerizable liquid crystal composition of the present invention is used to produce an optical isomer, The initiation of thermal polymerization which is not intended in the photopolymerization of the liquid crystal state is avoided, and the uniform alignment state of the molecules is easily fixed, and it is preferable to exhibit a mutually variable liquid crystal phase at room temperature (20 to 40 ° C or lower). Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferable to use a liquid crystal phase which is mutually denatured at room temperature when the solvent is removed.

[Polymer and film]

The polymerizable liquid crystal composition of the present invention described above can be subjected to light irradiation or heat treatment to obtain a polymer.

In addition, a state in which the polymerizable liquid crystal composition is held between the two substrates, or a state in which the polymerizable liquid crystal composition is applied to the substrate by spin coating or casting, or the like, is subjected to light irradiation treatment to obtain a film.

At this time, a plastic sheet or a film such as glass, quartz, a color filter, or triacetyl cellulose (TAC) can be used for the substrate. Further, in one of the two substrates, a glass, a plastic sheet, a plastic film or stainless steel in which a functional film such as ITO is formed, or a metal plated with chromium or aluminum may be used. Body or drum.

In order to enhance the blending orientation of the obtained film, it is preferable to carry out an alignment treatment which can obtain a tilt. The method of the alignment treatment is to apply an alignment material containing a polyimide precursor, a polyimide, a polyvinyl cinnamate, or the like, rubbing or irradiating a polarized ultraviolet ray obliquely to form a cerium oxide. A known method such as a method of depositing a vapor deposited film or a method of forming an LB film is appropriately selected and used, but it is preferable to use an available oblique alignment method in any of them.

A method of holding a polymerizable liquid crystal composition between two substrates by using a spacer or the like to form a cell in which a space is formed between two substrates, by a capillary image method, or by a void of a reduced-pressure unit cell or the like. In the method, after the polymerizable liquid crystal composition is injected into the unit cell, the light is irradiated and polymerized.

Moreover, a more simple method is a method in which a polymerizable liquid crystal composition is placed on a substrate provided with a spacer or the like, and the other substrate is stacked thereon to form a unit cell, and the light is irradiated and polymerized. In this case, the polymerizable liquid crystal composition may be fluidized, or may be placed on a substrate and then fluidized by heating or the like. However, it is necessary to flow the polymerizable liquid crystal composition before overlapping the other substrate. Chemical.

Further, since the method of holding the polymerizable liquid crystal composition between the two substrates is to obtain the mixed alignment, it is necessary to perform the processing of the single-piece substrate without the alignment treatment or the vertical alignment.

The method of applying the polymerizable liquid crystal composition may be a step of applying a polymerizable liquid crystal composition, and a step of heating with a hot plate or the like as needed in the middle of the step of polymerizing by light or heat. In this step, in particular, when a polymerizable liquid crystal composition (coating liquid) containing an organic solvent is used, a means for removing an organic solvent from the composition is effective.

In the method of any of the above, the polymerizable liquid crystal composition is polymerized in a state of exhibiting a liquid crystal phase, and a film having an optical anisotropy of alignment can be obtained.

In order to obtain a polymer having a plurality of regions in different orientations in each adjacent region, a method of performing multi-regionization in the step of polymerization or a method of multi-regionizing the substrate may be used.

The method of performing multi-regionization by a polymerization method is a liquid crystalline liquid crystal composition in which a liquid crystal state is exposed, and ultraviolet rays are exposed through a mask to form a polymerized region, and the remaining regions are, for example, polymerized in an isotropic liquid state. The method.

Further, a method of multi-regionizing the substrate is, for example, a method of rubbing the alignment material formed on the substrate via a mask, or a method of irradiating ultraviolet rays through a mask.

By this method, it is possible to obtain a multi-regional substrate in which the rubbed region and the region irradiated with ultraviolet rays are subjected to the alignment treatment and the other untreated portions. The polymerizable liquid crystal composition formed on the substrate which is multi-regionized is affected by the alignment layer and is multi-regionized.

Further, 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 can be obtained, and the film can be suitably used for a polarizing plate or a phase difference plate. Moreover, since this film is excellent in transparency at a high temperature, it can be suitably used for an electronic device used in a high-temperature environment such as a vehicle display device.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the examples described below. Moreover, the measurement method and measurement conditions of each physical property in the Example are as follows.

[1] NMR

The compound was dissolved in chloroform (CDCl ₃ ) or dimethyl hydrazine (DMSO-d6), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Diol Co., Ltd.).

[2] Observation of liquid crystal phase

In the identification of the liquid crystal phase, the sample was heated on a heating stage (MATS-2002S, manufactured by Tokai Sea), and observed using a polarizing microscope (manufactured by Nikon Co., Ltd.). The phase transition temperature was measured by a Bruker AXS (share) differential scanning calorimeter (DSC 3100 SR, hereinafter referred to as DSC) at a scan rate of 10 ° C/min.

[3] Depreciation

The enthalpy of the film was measured using a Spectral Haze Meter (TC-1800H) manufactured by Tokyo Electric Co., Ltd.

[4] film retardation value

The retardation value at a wavelength of 590 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).

[5] Average tilt angle of the film

And a measurement wavelength of 590nm using the average inclination angle AxoScan ^TM Mueller Matrix Polarimeter (AXOMETRIX Corporation).

[Synthesis Example 1] Synthesis of Polymerizable Liquid Crystal Compound (E1)

[1] Synthesis of intermediate compound (A1)

In a 500 ml eggplant flask with a cooling tube, 9.8 g (50.0 mmol) of 4-cyano-4'-hydroxybiphenyl group, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, and 13.8 g of potassium carbonate (100 mmol) were added. And 150 ml of acetone was formed to form a mixture, and the mixture was stirred while stirring at 64 ° C for 48 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow solid. Thereafter, the solid and 140 ml of water were mixed, and then 100 ml of diethyl ether was added thereto for extraction. The extraction system was carried out 3 times. The organic layer was separated and dried over anhydrous magnesium sulfate. After filtered, the solvent was evaporated under reduced pressure to give a yellow solid. This solid was purified by recrystallization using a mixed solution of hexane / ethyl acetate = 2 / 1 (v / v) to give 8.7 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid was the 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) )

[2] Synthesis of polymerizable liquid crystal compound (E1)

12.0 g of the obtained intermediate compound (A1) and 7.7 ml of triethylamine and a small amount of BHT (2,6-di-t-butyl-p-cresol) were dissolved in tetrahydrofuran (THF) 40 ml at room temperature. The mixture was stirred under a water bath, and a solution of 4.6 ml of acrylonitrile chloride dissolved in 40 ml of THF was added dropwise over 15 minutes. After the dropwise addition, the mixture was stirred for 30 minutes, and the water bath was removed to return to room temperature while stirring was continued overnight to filter the precipitated triethylamine hydrochloride. From the obtained filtrate, about 3/4 of THF was distilled off, and 50 ml of dichloromethane was added, and the organic layer was washed successively with 50 ml of a saturated aqueous sodium hydrogencarbonate solution, 50 ml of 0.5 mol/liter hydrochloric acid, and 50 ml of a saturated brine, and dried over magnesium sulfate. Thereafter, the solvent was distilled off to obtain a product. After recrystallization from ethanol, 6.0 g of a polymerizable liquid crystal 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)

[1] Synthesis of intermediate compound (A2)

To a 100 ml eggplant flask with a cooling tube, 5.0 g (25.6 mmol) of 4-cyano-4'-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, and 7.0 g of potassium carbonate (50 mmol) were added. And 50 ml of acetone was formed to form a mixture, and the mixture was stirred while stirring at 64 ° C for 24 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow solid. Thereafter, 70 ml of this solid and water were mixed, and 50 ml of diethyl ether was further added thereto for extraction. The extraction system was carried out 3 times.

The organic layer to be separated was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was dissolved in 3 ml of ethyl acetate and analyzed by chromatography on a column of cerium oxide gel column (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) =1/1 (v/v)) refined. The solvent was distilled off from the obtained solution to obtain 6.9 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid was the 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)

[2] Synthesis of intermediate compound (B2)

Then, 2.2 g of PCC (10.0 mmol) and 30.0 ml of CH ₂ Cl ₂ were added to a 200 ml three-necked flask, and the mixture was stirred and mixed, and 2.95 g (10.0 mmol) of the intermediate compound (A2) obtained above was added dropwise. The solution was dissolved in 50.0 ml of CH ₂ Cl _{2 and} further stirred at 40 ° C for 0.5 hour. Then, the solution of the oily substance adhered to the wall of the flask was removed, and 90 ml of diethyl ether was added thereto, followed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid.

The solid was dissolved in 3 ml of ethyl acetate and analyzed by a color column of cerium oxide gel column (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) =1/1 (v/v)) refined. The solvent was distilled off from the obtained solution to obtain 2.8 g of a colorless solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid was the 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)

[3] Synthesis of polymerizable liquid crystal compound (E2)

Finally, 3.0 g (10.0 mmol) of the intermediate compound (B2) obtained above, 2-(bromomethyl) was added to a 50 ml eggplant type flask equipped with a cooling tube. 1. 1.65 g (10.0 mmol) of acrylic acid, 15 1.6 g of Amberlyst (registered trademark), 16.0 ml of THF, 1.9 g (10.0 mmol) of tin (II) chloride, and 4.0 ml of pure water to form a mixture, and stirred at 70 ° C. Reaction on an hourly basis. After the completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 30 ml of pure water, and then 50 ml of diethyl ether was added thereto for extraction. The extraction system was carried out 3 times.

Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give a yellow solid. The solid was dissolved in 2 ml of ethyl acetate and analyzed by chromatography on a column of cerium oxide gel column (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) =2/1 (v/v)) refined. The solvent was distilled off from the obtained solution to obtain 1.5 g of a white solid. The NMR measurement results of this solid are shown below. From the result, the polymerizable liquid crystal compound (E2) for the purpose of the white solid was confirmed (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 phase of the polymerizable liquid crystal compound (E2), it was in an isotropic liquid state at 84 ° C, and was transferred to the liquid crystal phase (nematic phase) at 61 ° C when the temperature was lowered.

[Synthesis Example 3] Synthesis of polymerizable liquid crystal compound (E3)

[1] Synthesis of intermediate compound (A3)

In a 200 ml eggplant flask with a cooling 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 70 ml of acetone were added. The mixture was formed and reacted while stirring at 64 ° C for 24 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated to vacuo to give a yellow solid. The solid was analyzed by a color column of a ceria gel column (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 1/1 (v/) v)) Refined. The solvent was distilled off from the obtained solution to obtain 11.3 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid was the intermediate compound (A3) (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 intermediate compound (B3)

Then, 2.2 g (10.0 mmol) of PCC and 15.0 ml of CH ₂ Cl _{2 were} placed in a three-necked flask equipped with a cooling tube, and the mixture was stirred and mixed, and 2.5 g (10.0 mmol) of the intermediate compound (A3) obtained above was added dropwise thereto. A solution of 15.0 ml of CH ₂ Cl ₂ was dissolved and further stirred at room temperature for 6 hours. Then, the solution of the oily substance adhered to the wall of the flask was removed, and 90 ml of diethyl ether was added thereto, followed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid.

The solid was analyzed by a color column of cerium oxide gel column (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 2/1 (v/v) ))refined. The solvent was distilled off from the obtained solution to obtain 1.3 g of a colorless solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid was the intermediate compound (B3) (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 intermediate compound (C3)

Then, 1.25 g (5.0 mmol) of the intermediate compound (B3) obtained above, 0.83 g (5.0 mmol) of 2-(bromomethyl)acrylic acid, and Amberlyst (registered trademark) were added to a 50 ml eggplant type flask. 15 0.8 g, THF 8.0 ml, tin chloride (II) 0.95 g (5.0 mmol), and pure water 2.0 ml were formed to form a mixture, and the mixture was stirred at 70 ° C for 5 hours while reacting. After the completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 40 ml of pure water, and then 50 ml of diethyl ether was added thereto for extraction. The extraction system was carried out 3 times.

Anhydrous magnesium sulfate was added to the organic layer after the extraction, and dried. The solvent was evaporated from vacuo. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid was the intermediate compound (C3) (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 intermediate compound (D3)

In a 100 ml eggplant type flask equipped with a cooling tube, 35 ml of ethanol, 1.5 g (4.7 mmol) of the intermediate compound (C3) obtained above, and 5 ml of a 10% by mass aqueous sodium hydroxide solution were added to form a mixture, and the mixture was stirred at 85 ° C. Reaction on an hourly basis. After the completion of the reaction, 300 ml of water and a reaction liquid were added to a 500 ml beaker, and the mixture was stirred at room temperature for 30 minutes, and then 5 ml of a 10% by mass aqueous HCl solution was added dropwise thereto, followed by filtration to obtain a white solid (1.3 g).

Then, in a 50 ml eggplant type flask with a cooling tube, the obtained one is added. 1.1 g of a white solid, Amberlyst (registered trademark) 15 1.0 g, and 20.0 ml of THF were mixed to form a mixture, and the mixture was stirred while stirring at 70 ° C for 5 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow solid. This yellow solid was purified by recrystallization (hexane/ethyl acetate = 1/1 (v/v)) to afford 0.9 g of white solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was the intermediate compound (D3) (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 Compound (P3)

19.2 g (138.0 mmol) of 3-bromo-1-propanol and 18.9 ml of triethylamine were dissolved in 100 ml of THF together with a small amount of BHT, stirred at room temperature, and cooled in a water bath, and dissolved in THF for 15 minutes. 50 ml of propylene sulfonium chloride (12.2 ml (150 mmol)) was stirred for 30 minutes, and the water bath was removed and returned to room temperature while stirring was continued overnight. The precipitated TEA hydrochloride was filtered, and THF was distilled off from the filtrate, and 100 ml of diethyl ether was added thereto, and the organic layer was washed successively with 80 ml of a saturated aqueous sodium hydrogencarbonate solution, 0.5 mol/liter of hydrochloric acid, and saturated brine. After drying over magnesium sulfate, the solvent is distilled off to obtain a compound (P3) 18.2g. The results of the measurement of the solid by NMR are shown below.

¹ H-NMR (CDCl ₃ ) δ: 2.20 (m, 2H), 3.45 (t, 2H), 4.33 (t, 2H), 5.84 (d, 1H), 6.13 (m, 1H), 6.44 (d, 1H) )

[6] Synthesis of intermediate compound (G3)

In a 500 ml eggplant type flask equipped with a cooling tube, 17.6 g (94.3 mmol) of biphenol, 18.2 g (94.3 mmol) of the compound (P3), 24.0 g (190 mmol) of potassium carbonate, and 250 ml of acetone were added to form a mixture, and the mixture was stirred at a temperature of 54 ° C. 20 hours at the same time and react. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated to vacuo to give a yellow solid. This solid was purified by column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 2/1 (v/v)). The solvent was distilled away from the solution obtained here to obtain 6.1 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this white solid was the intermediate compound (G3) (yield 22%).

¹ H-NMR (CDCl ₃ ) δ: 2.21 (m, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 4.99 (s, 1H), 5.87 (d, 1H), 6.15 (m, 1H) ), 6.40 (d, 1H), 6.87 (d, 2H), 6.99 (d, 2H), 7.46 (m, 4H)

[7] Synthesis of intermediate compound (E3)

6.1 g (20.0 mmol) of the intermediate compound (D3) obtained above, 6.0 g (20.0 mmol) of the intermediate compound (G3), 0.08 g of DMAP and a small amount of BHT were stirred at room temperature, and suspended in dichloromethane. In 10 ml, 4.7 g (23.0 mmol) of DCC dissolved in 20 ml of dichloromethane was added and stirred overnight, and the precipitated DCC urea was filtered, and the filtrate was sequentially added with 0.5 ml/liter of hydrochloric acid and saturated hydrogen carbonate in 60 ml each. The sodium aqueous solution and the saturated aqueous sodium chloride solution were washed twice, and dried over magnesium sulfate, and the solvent was evaporated, and then recrystallized from ethanol to obtain 8.8 g (yield: 75%) of the polymerizable liquid crystal compound (E3).

¹ H-NMR (CDCl ₃ ) δ: 1.53 (m, 6H), 1.81 (m, 2H), 2.20 (m, 2H), 2.60 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H) ), 4.12 (t, 2H), 4.40 (t, 2H), 4.54 (m, 1H), 5.63 (d, 1H), 5.85 (d, 1H), 6.10 (m, 1H), 6.24 (d, 1H) , 6.42 (d, 1H), 6.97 (d, 2H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (E3), the phase transition was carried out at 109 ° C to form a smectic X phase at a temperature rise, and the phase was transferred to a nematic phase at 144 ° C, and became an isotropic liquid at 168 ° C. status.

[Example 1] Synthesis of Compound (Z1)

[1] Synthesis of intermediate compound (P1)

To a 200 ml eggplant flask with a cooling tube, 4-(4-hydroxyphenyl) Benzoic Acid Ethyl Ester was added to 12.1 g (50.0 mmol), 11-bromo-1- 12.5 g (50.0 mmol) of decyl alcohol, 13.8 g (100 mmol) of potassium carbonate, and 100 ml of acetone were mixed to form a mixture, and the mixture was stirred at 64 ° C for 24 hours while allowing to react. After the completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain 20.3 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this white solid was the intermediate compound (P1) (yield 98%).

¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 19H), 1.81 (m, 2H), 3.67 (m, 2H), 4.02 (m, 2H), 4.42 (t, 2H), 6.97 (d) , 2H), 7.57 (d, 2H), 7.62 (d, 2H), 8.09 (d, 2H)

[2] Synthesis of intermediate compound (Q1)

Then, 11 g of PCC (51 mmol) and 100 ml of CH ₂ Cl _{2 were} placed in a 500 ml three-necked flask, and the mixture was stirred and mixed, and 20 g (49 mmol) of the obtained intermediate compound (P1) was dissolved in CH _{2 .} A solution of Cl ₂ 100 ml was further stirred at room temperature for 5 hours. Then, the solution of the oily substance adhered to the wall of the flask was removed, and 100 ml of diethyl ether was added thereto, followed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid.

This solid was purified by a cyanite gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: ethyl acetate). The solvent was distilled off from the obtained solution to obtain 12.4 g of a colorless solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this colorless solid was the intermediate compound (Q1) (yield 62%).

¹ H-NMR (CDCl ₃ ) δ: 1.20-1.65 (m, 19H), 1.81 (m, 2H), 2.41 (t, 2H), 4.11 (t, 2H), 4.42 (m, 2H), 6.99 (d) , 2H), 7.57 (d, 2H), 7.63 (d, 2H), 8.01 (d, 2H), 9.77 (s, 1H)

[3] Synthesis of intermediate compound (R1)

Then, 12.4 g (30 mmol) of the intermediate compound (Q1) obtained above, 5.4 g (33 mmol) of 2-(bromomethyl)acrylic acid, 75 ml of THF, and tin chloride (II) were added to a 200 ml eggplant type flask. 6.3 g (33 mmol) and 24 ml of a 10% by mass aqueous HCl solution were formed to form a mixture, which was stirred while stirring at 70 ° C for 24 hours. After the completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain 15 g of a white solid. The results of the measurement of the solid by NMR are shown below. From the result, the white intermediate was identified as the intermediate compound (R1).

¹ H-NMR (CDCl ₃ ) δ: 1.30 (m, 12H), 1.41 (t, 3H), 1.47 (m, 12H), 1.58 (m, 2H), 1.81 (m, 2H), 2.54 (m, 1H) ), 3.06 (m, 1H), 4.13 (m, 2H), 4.48 (m, 2H), 4.55 (m, 1H), 5.66 (s, 1H), 6.23 (s, 1H), 7.00 (d, 2H) , 7.55 (d, 2H), 7.66 (d, 2H), 8.11 (d, 2H)

[4] Synthesis of Compound (Z1)

In a 500 ml eggplant type flask equipped with a cooling tube, 200 ml of ethanol, 15 g of the intermediate compound (R1) obtained above, and 80 ml of a 10% by mass aqueous sodium hydroxide solution were added to form a mixture, and the mixture was stirred while stirring at 85 ° C for 5 hours. After the completion of the reaction, 500 ml of water and a reaction liquid were poured into a 1000 ml beaker, and the mixture was stirred at room temperature for 30 minutes, and then 50 ml of a 10% by mass aqueous HCl solution was added dropwise thereto, followed by filtration to obtain a white solid.

Then, the resulting white solid, 200 ml of THF, and 10% by mass aqueous HCl solution were added to a cooling tube 50 ml eggplant flask to form a mixture, which was stirred at 70 ° C for 5 hours to react. After the completion of the reaction, 500 ml of water and the reaction liquid were placed in a 1000 ml beaker, and filtered to obtain 12 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, the compound (Z1) for the purpose of this white solid was confirmed. (Yield 89%, yield from Q1).

¹ H-NMR (DMSO-d6) δ: 1.32 (m, 14H), 1.57 (m, 2H), 1.71 (m, 2H), 2.54 (m, 1H), 3.09 (m, 1H), 4.01 (m, 2H), 4.55 (m, 1H), 5.69 (s, 1H), 6.02 (s, 1H), 7.05 (d, 2H), 7.67 (d, 2H), 7.73 (d, 2H), 7.97 (d, 2H) ), 12.89(s, broad, 1H)

[Example 2] Synthesis of Compound (Z2)

[1] Synthesis of intermediate compound (P2)

To a 500 ml eggplant flask with a cooling tube, 15.0 g (72 mmol) of ethyl 4-(4-hydroxyphenyl)benzoate and 17.4 g (50.0 mmol) of 4-bromobutyl-1,3-dioxolane were added. A mixture of 19.3 g (140 mmol) of potassium carbonate and 200 ml of acetone was formed, and the mixture was stirred at 64 ° C for 48 hours while allowing to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain 26.1 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this white solid was the intermediate compound (P2) (yield 98%).

¹ H-NMR (CDCl ₃ ) δ: 1.41 (t, 3H), 1.55-2.00 (m, 6H), 3.86 (m, 2H), 3.99 (m, 4H), 4.39 (m, 2H), 4.89 (m) , 1H), 6.97 (d, 2H), 7.61 (m, 4H), 8.07 (d, 2H)

[2] Synthesis of intermediate compound (R2)

Then, 18.5 g (50 mmol) of the intermediate compound (P2) obtained above, 9.1 g (55 mmol) of 2-(bromomethyl)acrylic acid, 114 ml of THF, and tin chloride were added to a 300 ml eggplant type flask equipped with a cooling tube. II) 10.4 g (55 mmol) and 36 ml of a 10 mass% HCl aqueous solution were formed to form a mixture, and the mixture was stirred at 70 ° C for 20 hours to carry out a reaction. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain 18.7 g of a white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this colorless solid was the intermediate compound (R2) (yield 95%).

¹ H-NMR (CDCl ₃ ) δ: 1.42 (t, 3H), 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.03 (t, 2H), 4.42 (m) , 2H), 4.58 (m, 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.99 (d, 2H), 7.63 (m, 4H), 8.12 (d, 2H)

[3] Synthesis of intermediate compound (Z2)

To a 500 ml eggplant type flask equipped with a cooling tube, 200 ml of ethanol, 18.7 g (47 mmol) of the intermediate compound (R2) obtained above, and 50 ml of a 10% by mass aqueous sodium hydroxide solution were added to form a mixture, which was stirred at 85 ° C for 5 hours. Respond at one side. After the reaction is finished, 600 ml of water and the reaction solution It was placed in a 1000 ml beaker, stirred at room temperature for 30 minutes, and filtered to give a white solid.

Then, a mixture of the obtained white solid, 200 ml of THF, and 50 ml of a 10% by mass aqueous HCl solution was added to a cooling tube 50 ml eggplant type flask to form a mixture, which was stirred at 70 ° C for 5 hours to carry out a reaction. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain 15.9 g of a white solid. The results of the measurement of the solid by NMR are shown below. From the result, the target compound (Z2) (yield: 92%) of this white solid was confirmed.

¹ H-NMR (DMSO-d6) δ: 1.50 (m, 2H), 1.75 (m, 4H), 2.58 (m, 1H), 3.12 (m, 1H), 4.04 (m, 2H), 4.59 (m, 1H), 5.72 (s, 1H), 6.03 (s, 1H), 7.04 (d, 2H), 7.76 (m, 4H), 7.97 (d, 2H), 12.91 (s, broad, 1H)

[Example 3] Synthesis of polymerizable liquid crystal compound (Z3)

1.0 g (2.7 mmol) of the compound (Z2) obtained in Example 2, 0.3 g (3.1 mmol) of phenol, 0.010 g of DMAP and a small amount of BHT were stirred at room temperature, suspended in 20 ml of dichloromethane, and then added. The solution was dissolved in 5 ml of dichloromethane (0.7 g (3.5 mmol)) and stirred overnight. filter The DCC urea was separated, and the filtrate was washed twice with 0.5 ml/L hydrochloric acid 50 ml, saturated sodium bicarbonate 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and the solvent was evaporated. The crystal was purified to obtain 0.4 g (yield 36%) of the objective polymerizable liquid crystal compound (Z3).

¹ H-NMR (CDCl ₃ ) δ: 1.6~1.9 (m, 6H), 2.63 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H), 4.57 (m, 1H), 5.64 (d) , 1H), 6.24 (d, 1H), 6.99 (d, 2H), 7.24 (d, 3H), 7.45 (m, 2H), 7.59 (m, 2H), 7.71 (m, 2H), 8.25 (d, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z3), the phase was transferred to a smectic phase at 101 ° C at the time of temperature rise, and the phase was transferred to a nematic phase at 114 ° C, and thermally polymerized at 122 ° C.

[Example 4] Synthesis of polymerizable liquid crystal compound (Z4)

2.0 g (5.5 mmol) of the compound (Z2) obtained in Example 2, and a compound (Q4) (methyl 4-hydroxybenzoate, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.9 g (6.0 mmol), DMAP 0.005 g, and a small amount of BHT in After stirring at room temperature, it was suspended in 25 ml of dichloromethane, and a solution of DCC 1.4 g (7.0 mmol) dissolved in 5 ml of dichloromethane was added and stirred overnight. The DCC urea precipitated was filtered, and the filtrate was washed twice with 0.5 ml/L hydrochloric acid 50 ml, saturated sodium bicarbonate aqueous solution 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and the solvent was evaporated. The crystal was recrystallized and purified to obtain 2.1 g (yield: 76%) of the desired polymerizable liquid crystal compound (Z4).

¹ H-NMR (CDCl ₃ ) δ: 1.60~1.95 (m, 6H), 2.61 (m, 1H), 3.07 (m, 1H), 3.98 (s, 3H), 4.01 (t, 2H), 4.54 (m) , 1H), 5.64 (d, 1H), 6.25 (d, 1H), 6.99 (d, 2H), 7.26 (d, 2H), 7.62 (m, 2H), 7.71 (m, 2H), 8.15 (d, 2H), 8.24 (d, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z4), the phase was transferred to a smectic phase at 105 ° C at a temperature rise, and the mixture was thermally polymerized at 130 ° C.

[Example 5] Synthesis of polymerizable liquid crystal compound (Z5)

3.0 g (6.7 mmol) of the compound (Z1) obtained in Example 1, and a compound (Q5) (2,3-difluorophenol, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.9 g (6.7 mmol), DMAP 0.05 g and a small amount of BHT were stirred at room temperature, suspended in 30 ml of dichloromethane, and then a solution of DCC 1.9 g (9.0 mmol) dissolved in 10 ml of dichloromethane was added and stirred. night. The DCC urea precipitated was filtered, and the filtrate was washed twice with 0.5 ml/L hydrochloric acid 50 ml, saturated sodium bicarbonate aqueous solution 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and the solvent was evaporated. The crystal was recrystallized to obtain 2.9 g (yield: 77%) of the desired polymerizable liquid crystal compound (Z5).

¹ H-NMR (CDCl ₃ ) δ: 1.25~1.95 (m, 18H), 2.55 (m, 1H), 3.08 (m, 1H), 4.04 (t, 2H), 4.54 (m, 1H), 5.62 (d) , 1H), 6.23 (d, 1H), 6.99 (d, 2H), 7.13 (m, 3H), 7.62 (m, 2H), 7.72 (m, 2H), 8.23 (d, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z5), the phase was transferred to a layer A phase at 91 ° C at the time of temperature rise, and it became an isotropic liquid state at 106 °C.

[Example 6] Synthesis of polymerizable liquid crystal compound (Z6)

[1] Synthesis of intermediate compound (Q6)

To a 100 ml eggplant type flask equipped with a cooling tube, a compound (P6) (2-fluoro-4-hydroxybenzoic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount of 5.0 g ( 32 mmol), n-butanol 50 ml (55 mmol), and 2 ml of sulfuric acid to form a mixture, and the mixture was stirred at 105 ° C for 2 hours to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water and mixed, and then 100 ml of diethyl ether was added thereto for extraction. Anhydrous magnesium sulfate was added to the organic layer after extraction and dried, and the solvent was evaporated from vacuo. The results of the measurement of the solid by NMR are shown below. From the results, it was confirmed that this solid was the intermediate compound (Q6) (yield: 97%).

¹ H-NMR (CDCl ₃ ) δ: 0.98 (t, 3H), 1.47 (m, 2H), 1.74 (m, 2H), 4.32 (m, 2H), 6.27 (s, 1H), 6.47 (m, 2H) ), 7.88 (m, 1H)

[2] Synthesis of polymerizable liquid crystal compound (Z6)

2.3 g (5.0 mmol) of the compound (Z1) obtained in Example 1, 1.1 g (5.0 mmol) of the intermediate compound (Q6) obtained above, 0.040 g of DMAP and a small amount of BHT were stirred at room temperature, and suspended. After turbid in 20 ml of dichloromethane, a solution of DCC 1.4 g (7.0 mmol) dissolved in 5 ml of dichloromethane was added and stirred overnight. Filter out the precipitated DCC urea, The filtrate was washed twice with 50 ml of 0.5 mol/liter hydrochloric acid, 50 ml of a saturated aqueous sodium hydrogencarbonate solution and 50 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. The solvent was evaporated, and then recrystallized from ethanol to give the objective. The polymerizable liquid crystal compound (Z6) was 2.5 g (yield 76%).

¹ H-NMR (CDCl ₃ ) δ: 1.15 (t, 3H), 1.25 to 1.90 (m, 22H), 2.56 (m, 1H), 3.10 (m, 1H), 4.05 (t, 2H), 4.37 (t) , 2H), 4.56 (m, 1H), 5.63 (d, 1H), 6.24 (d, 1H), 7.02 (d, 2H), 7.14 (m, 2H), 7.60 (d, 2H), 7.72 (d, 2H), 8.05 (m, 1H), 8.23 (d, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z6), the phase was transferred to a layer A phase at 58 ° C at a temperature rise, and the mixture was thermally polymerized at 127 °C.

[Example 7] Synthesis of polymerizable liquid crystal compound (Z7)

2.5 g (7.4 mmol) of the compound (Z2) obtained in Example 2, 0.84 g (7.5 mmol) of 4-fluorophenol, 0.1 g of DMAP and a small amount of BHT were stirred at room temperature, and suspended in 30 ml of dichloromethane. Then, add a solution of DCC 2.1g (10.0mmol) dissolved in 10ml of dichloromethane and stir it. night. The DCC urea precipitated was filtered, and the filtrate was washed twice with 0.5 ml/L hydrochloric acid 50 ml, saturated sodium bicarbonate aqueous solution 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and the solvent was evaporated. The crystal was recrystallized and purified to obtain 1.4 g (yield: 41%) of the desired polymerizable liquid crystal compound (Z7).

¹ H-NMR (CDCl ₃ ) δ: 1.67 (m, 2H), 1.80 (m, 2H), 1.90 (m, 2H), 2.64 (m, 1H), 3.10 (m, 1H), 4.04 (m, 2H) ), 4.57 (m, 1H), 5.65 (m, 1H), 6.25 (m, 1H), 6.99 (d, 2H), 7.10 (m, 2H), 7.20 (m, 2H), 7.61 (d, 2H) , 7.71 (d, 4H), 8.24 (d, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z7), the phase was transferred to a smectic phase at 79 ° C at a temperature rise, and the phase was transferred to a nematic phase at 120 ° C to carry out thermal polymerization at 129 ° C.

[Example 8] Synthesis of Compound (Z8)

[1] Synthesis of intermediate compound (P8)

In a 500 ml eggplant type flask equipped with a cooling tube, 18.6 g (100 mmol) of biphenol, 10.0 g (48 mmol) of 4-bromobutyl-1,3-dioxolane, 13.8 g (100 mmol) of potassium carbonate, and 200 ml of acetone were added. Forming a mixture The mixture was stirred at 64 ° C for 24 hours while allowing to react. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain a white solid. This solid was mixed with 150 ml of methanol, and the solvent was evaporated to give a white solid. Next, this solid was mixed with 70 ml of chloroform, and after filtration, the solvent was evaporated to give 7.2 g of white solid. The results of the measurement of the solid by NMR are shown below. From this result, it was confirmed that this white solid was the intermediate compound (P8) (yield 48%).

¹ H-NMR (CDCl ₃ ) δ: 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H) ), 6.87 (m, 4H), 7.42 (m, 4H)

[2] Synthesis of compound (Z8)

Then, 7.2 g (23 mmol) of the intermediate compound (P8) obtained above, 4.1 g (25 mmol) of 2-(bromomethyl)acrylic acid, 60 ml of THF, and tin chloride (II) were added to a 300 ml eggplant type flask equipped with a cooling tube. 4.7 g (25 mmol) and 19 ml of a 10% by mass aqueous HCl solution were added to form a mixture, and the mixture was stirred while stirring at 70 ° C for 5 hours. After the completion of the reaction, the reaction solution was poured into 200 ml of pure water to obtain 6.1 g of a white solid.

The results of the measurement of the solid by NMR are shown below. From this result The compound (Z8) for the purpose of this white solid was confirmed (yield: 78%).

¹ H-NMR (CDCl ₃ ) δ: 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.02 (t, 2H), 4.60 (m, 1H), 4. , 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.94 (d, 2H), 7.44 (m, 4H)

[Example 9] Synthesis of polymerizable liquid crystal compound (Z9)

0.9 g (2.5 mmol) of the compound (Z8) obtained in Example 8, 0.4 g (2.5 mmol) of 4-fluorobenzoic acid, 0.03 g of DMAP and a small amount of BHT were stirred at room temperature, and suspended in dichloromethane (15 ml). Further, a solution of 0.7 g (3.5 mmol) of DCC dissolved in 5 ml of dichloromethane was added and stirred overnight. The DCC urea precipitated was filtered, and the filtrate was washed twice with 0.5 ml/L hydrochloric acid 50 ml, saturated sodium bicarbonate aqueous solution 50 ml, and saturated brine 50 ml, dried over magnesium sulfate, and the solvent was evaporated. The crystal was recrystallized and purified to obtain 0.9 g (yield: 82%) of the desired polymerizable liquid crystal compound (Z9). The results of the measurement of the solid by NMR are shown below. From this result, the polymerizable liquid crystal compound (Z9) was confirmed.

¹ H-NMR (CDCl ₃ ) δ: 1.59 (m, 2H), 1.70 (m, 2H), 1.86 (m, 2H), 2.59 (m, 1H), 3.08 (m, 1H), 4.00 (m, 2H) ), 4.57 (m, 1H), 5.64 (m, 1H), 6.25 (m, 1H), 6.96 (d, 2H), 7.20 (m, 4H), 7.50 (m, 2H), 7.60 (d, 2H) , 8.20 (m, 2H)

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z9), the phase was transferred to a smectic phase at 99 ° C at a temperature rise, and the phase was transferred to a nematic phase at 112 ° C to carry out thermal polymerization at 123 ° C.

[Examples 10 to 15, Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) thereof

The compounds used in the following examples and comparative examples are as follows. Further, the compositions of the compositions prepared in Examples 10 to 15 and Comparative Example 1 are shown in Table 1 (unit: mg).

[Example 10] Polymerizable liquid crystal composition and polymer (film) thereof

120 mg of the polymerizable liquid crystal compound (E1), 90 mg of the polymerizable liquid crystal compound (E2), 60 mg of the polymerizable liquid crystal compound (E3), 30 mg of the polymerizable liquid crystal compound (Z3), and Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (photopolymerization initiator) Product name: 4 mg of R30 (manufactured by DIC Co., Ltd.) of 4 mg and a surfactant was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

This polymerizable liquid crystal composition was applied onto a liquid crystal alignment film attached to a liquid crystal alignment film substrate by spin coating (1000 rpm, 20 seconds), prebaked on a hot plate at 100 ° C for 60 seconds, and then allowed to cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. Liquid crystal alignment film substrate system used herein A liquid crystal alignment agent (SE-1410, manufactured by Nissan Chemical Industries Co., Ltd.) was applied onto the ITO surface of the ITO glass substrate by spin coating, and the film was fired at 230 ° C to form a film having a thickness of 100 nm, and then subjected to a rubbing treatment.

Then, the coating film formed on the liquid crystal alignment film substrate was irradiated with a strong light of 2000 mJ/cm ² using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition.

The film thickness of the obtained film was 1.9 μm, and after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay value was 302 nm and the 霾 value was 0.32.

After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 238 nm, and the enthalpy value was 0.17. Further, the film was heated at 160 ° C for 30 minutes. After heating on a hot plate at 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation value was 213 nm, and the enthalpy value was 0.08.

[Example 11] Polymerizable liquid crystal composition and polymer (film) thereof

A polymerizable liquid crystal composition was obtained in the same manner as in Example 10 except that the polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z4).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. Further, the composition on the substrate after prebaking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the retardation value was 29 nm and the enthalpy value was 0.24.

After the film was heated on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 30 nm, and the enthalpy value was 0.24. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation value was 33 nm, and the enthalpy value was 0.16.

[Example 12] Polymerizable liquid crystal composition and polymer (film) thereof

90 mg of the polymerizable liquid crystal compound (E1), 90 mg of the polymerizable liquid crystal compound (E2), 60 mg of the polymerizable liquid crystal compound (E3), 60 mg of the polymerizable liquid crystal compound (Z4), and Irgacure 369 manufactured by Ciba Geigy Co., Ltd. Product name: 4 mg of R30 (manufactured by DIC Co., Ltd.) of 4 mg and a surfactant was dissolved in 0.7 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 10. Further, the composition on the substrate after prebaking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay value is 1 nm and the 霾 value is 0.00.

After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 1 nm, and the enthalpy value was 0.09. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate of 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation value was 1 nm, and the enthalpy value was 0.01.

[Example 13] Polymerizable liquid crystal composition and polymer (film) thereof

Polymerization was obtained in the same manner as in Example 12 except that the polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z5). Liquid crystal composition.

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. Further, the composition on the substrate after prebaking is in a liquid crystal state.

The film thickness of the obtained film was 1.9 μm, and after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the retardation value was 2 nm, and the 霾 value was 0.21.

After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 2 nm, and the enthalpy value was 0.14. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation value was 2 nm, and the enthalpy value was 0.08.

[Example 14] Polymerizable liquid crystal composition and polymer (film) thereof

A polymerizable liquid crystal composition was obtained in the same manner as in Example 10 except that the polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z7).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. Further, the composition on the substrate after prebaking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay value was 305 nm and the 霾 value was 0.29.

After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 260 nm, and the enthalpy value was 0.24. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation value was 232 nm, and the enthalpy value was 0.16.

[Example 15] Polymerizable liquid crystal composition and polymer (film) thereof

A polymerizable liquid crystal composition was obtained in the same manner as in Example 12 except that the polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z7).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. Further, the composition on the substrate after prebaking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and after observing it with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. Then, the delay value was 86 nm and the 霾 value was 0.09.

After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 86 nm, and the enthalpy value was 0.08. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 200 ° C for 1 hour, the film thickness was 1.6 μm, the retardation value was 85 nm, and the enthalpy value was 0.08.

[Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) thereof

120 mg of the polymerizable liquid crystal compound (E1), 120 mg of the polymerizable liquid crystal compound (E2), 60 mg of the polymerizable liquid crystal compound (E3), and 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., Ltd., and a surfactant of a photopolymerization initiator. 0.6 mg of R30 (manufactured by DIC Co., Ltd.) was dissolved in 0.7 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 10. Further, the composition on the substrate after prebaking is in a liquid crystal state.

The obtained film was 1.9 μm thick and was observed by a polarizing microscope. Thereafter, it was confirmed that the film was horizontally aligned to the substrate surface. Then, the delay value is 299 nm and the 霾 value is 0.09.

After heating the film on a hot plate at 160 ° C for 30 minutes, the film thickness was 1.7 μm, the retardation value was 234 nm, and the enthalpy value was 0.08. Further, after heating the film heated at 160 ° C for 30 minutes on a hot plate at 200 ° C for 1 hour, the film thickness was 1.7 μm, the retardation value was 205 nm, and the enthalpy value was 0.08.

The above-described Examples 10 to 15 and Comparative Example 1 are summarized in Table 2.

Further, the retardation angle dependence of the wavelength of 590 nm of the films produced in the above Examples 10 to 15 and Comparative Example 1 is shown in Fig. 1.

Further, the results of measuring the average tilt angles of the wavelengths of 590 nm of the films produced in the above Examples 10 to 15 and Comparative Example 1 are also shown in Table 2.

As shown in Table 2, it can be seen that the films produced in Examples 10 to 15 are guaranteed. The value of the enthalpy after baking is very low (i.e., high thermal stability), and the addition of the polymerizable liquid crystal compound of the present invention can control the average angle.

Fig. 1 is a graph showing the dependence of the retardation angle on the wavelength of 590 nm of each of the films obtained in Examples 10 to 15 and Comparative Example 1.

Claims (10)

A polymerizable liquid crystal compound characterized by the following formula [1], (wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, G is a -C(=O)O- or -OC(=O)- group, and n is an integer from 4 to 10). A polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the first aspect of the patent application. The polymerizable liquid crystal composition according to the second aspect of the invention, which further comprises a liquid crystalline compound having one or more polymerizable groups in one molecule. The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystal compound is a compound having one or more polymerizable groups represented by the following formula [2] or [3] in one molecule; (In the formula, the dotted line indicates the bonding hand). The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formula [4] or [5]; (wherein X represents a fluorine atom, a cyano group or a carbon number 4 to 8 one-valent hydrocarbon group, and f1 and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9, M ¹ and M ² And M ³ independently represent a group represented by the following formula [2] or [3]; (In the formula, the dotted line indicates the bonding hand). A polymer obtained by the polymerizable liquid crystal composition according to any one of claims 2 to 5. A film obtained by the polymerizable liquid crystal composition according to any one of claims 2 to 5. An alignment film which is according to items 2 to 5 of the patent application scope Any of the polymerizable liquid crystal compositions obtained. An optical member comprising a polymer as claimed in claim 6 or an alignment film according to item 8 of the patent application. a compound characterized by the following formula [6]; (wherein Y represents -OH or -COOH, and k represents an integer of 4 to 10).