TWI555826B - Polymerizable liquid crystal composition and alignment film - Google Patents

Description

Polymeric liquid crystal composition and alignment film

The present invention relates to a polymerizable liquid crystal composition, a polymer obtained by using the same, and an alignment film. In particular, a display device or a material having optical characteristics such as a recording material, and a polymerizable liquid crystal composition suitable for use in an optical compensation film such as a polarizing plate for a liquid crystal display or a phase difference plate, and the like are used. A polymer, and a mixed alignment film obtained using the same.

In order to improve the display quality of the liquid crystal display device or to reduce the weight of the liquid crystal display device, it is required to improve the molecular alignment structure in which the molecular alignment structure of the optical compensation film such as a polarizing plate or a retardation film is controlled. In response to this demand, a film utilizing optical anisotropy which is possessed by a polymerizable liquid crystal compound has been developed.

The polymerizable liquid crystal compound used herein generally has a polymerizable group and a liquid crystal compound (having a structure portion having a spacer portion and a liquid crystal portion), and a propylene group is widely used as the polymerizable group.

The polymerizable liquid crystal compound is generally formed into a polymer (thin film) by a method of polymerizing radiation such as ultraviolet rays.

For example, a method in which a specific polymerizable liquid crystal compound having a propenyl group is supported between a support, and the compound is maintained in a liquid crystal state, and radiation is irradiated to obtain a polymer (Patent Document 1) is known, or a propylene group is known. a mixture of two polymeric liquid crystal compounds or a mixture of the palms in the mixture A method of adding a photopolymerization initiator to a composition of a liquid crystal and irradiating ultraviolet rays to obtain a polymer (Patent Document 2).

The polymer (film) obtained by the above-described methods can be used not only in a display device such as a display or a television, but also in a high-temperature environment such as an automobile, as a polarizing plate or a film for a phase difference plate. Display device. Therefore, maintaining transparency in a high-temperature environment is extremely important as a material for a display device.

However, when the glass transition temperature (hereinafter referred to as Tg) of the film obtained from the polymerizable liquid crystal compound is below the temperature of the use environment, particularly in a high-temperature environment, the microscopic sway of the molecules may occur, resulting in disorder of alignment. The problem of significantly decreasing optical anisotropy.

In addition, in the field of displays, in recent years, it has been actively reviewed to make these materials simple as a process for using In Cell retardation films. The materials used in the In Cell technology require higher thermal stability and chemical resistance.

In addition, it has been reported that various alignment films such as horizontal, vertical, and mixed alignment can be obtained, and various types of alignment films having various average tilt angles can be obtained (Patent Document 3).

Here, not only a specific compound is added in a small amount in the liquid crystal composition, but also an alignment pattern (for example, a horizontal type or a mixed type) of the obtained film can be simply controlled, and it can be widely applied to the field of liquid crystal displays.

Further, when a horizontal or hybrid alignment film can be easily produced by using a material to change the process, it is expected to be widely used in the field of liquid crystal displays.

It is described in Patent Document 4 that polymerization having a propylene group can be used. A polyfunctional polymerizable compound (0 to 20%) having no liquid crystallinity is added to the liquid crystal composition of the liquid crystal compound. However, the addition of the polyfunctional polymerizable compound is to improve the heat resistance of the film, and there is no description about the effect of controlling the alignment pattern.

Further, it has been reported that the tilt angle can be controlled by combining a polymerizable liquid crystal compound for a vertical and horizontal alignment film. Among them, although it is reported that the inclination angle of the O-plate film can be controlled, data other than the inclination angle (Δnd, haze value) is not reported (Patent Document 3).

[Practical Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 62-70407

[Patent Document 2] Japanese Patent Laid-Open No. Hei 9-208957

[Patent Document 3] International Publication No. 2008/052376

[Patent Document 4] International Publication No. 98/04651

The present invention has been made in view of the circumstances to provide a polymer which has excellent optical anisotropy and which can stably maintain a retardation value and transparency even at a high temperature, and which is excellent in chemical resistance and heat resistance, and is easy to provide. The polymerizable liquid crystal composition of the alignment type is controlled, and a polymer obtained by using the product and a mixed alignment film obtained by using the above are used.

In order to solve the above problems, the present inventors have further studied the results of the review and found that the level is aligned by containing a polymerizable liquid crystal compound. A small amount of a polyvalent acrylate compound is added to the polymer liquid crystal composition for a film, and the alignment type can be easily controlled. Further, a stable polymerizable liquid crystal composition can be obtained, and a polymer or film obtained from the polymerizable liquid crystal composition can have excellent optical anisotropy and heat resistance, and a mixed alignment film can be obtained. this invention.

In other words, the invention is related

1. A polymerizable liquid crystal composition comprising (A) at least one selected from the group consisting of polymerizable liquid crystal compounds represented by the following formula [1], and (B) selected from the group consisting of the polymerization represented by the following formula [2] At least one of the liquid crystal compounds, and (C) is selected from the group consisting of at least one selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or at least one selected from the group consisting of At least one of a polyol having three or more oxygen atoms and 50 or less polyacrylate compounds obtained by using acrylic acid or a derivative thereof, [wherein R ¹ , R ³ and R ⁴ are each independently an organic group represented by the following formula [3] or [4], (wherein X is a hydrogen atom or a methyl group; a dotted line is a bonding bond)

R ² represents a hydrogen atom, a halogen atom, a cyano group or a methoxy group; n1, n2 and n3 each independently represent an integer of 2 to 10; q represents 0 or 1; and when p is q, it is 1, q is 1 is 0 or 1; r is 1 or 2; s is 1 when r is 1, and 0 when r is 2.

The polymerizable liquid crystal composition according to the item 2.1, wherein the polybasic acrylate compound (C) is represented by the following formula [5] or [6]. (wherein R ⁵ represents a methyl group or an organic group represented by the following formula [7] or [8], N4~n10 are each an integer of 0~10; n11 is an integer of 4~10; the dotted line is a key bond).

3. The polymerizable liquid crystal composition according to 1 or 2, wherein the polymerizable liquid crystal compound (B) is represented by the following formula [9]. (wherein n2, n3, r and s are the same as described above).

4. A polymer obtained from the polymerizable liquid crystal composition according to any one of 1 to 3.

A film obtained from the polymerizable liquid crystal composition according to any one of 1 to 3.

A mixed alignment film obtained from the polymerizable liquid crystal composition according to any one of 1 to 3.

7. An optical member comprising an alignment film of 6.

The polymerizable liquid crystal composition of the present invention not only has excellent optical anisotropy, but also provides a polymer which is stable to anisotropy and transparency even in a high-temperature environment. Further, the polymerizable liquid crystal composition of the present invention has an advantage of being able to easily control the alignment type (horizontal, mixed type) of the film thus obtained by containing a small amount of the polyvalent acrylate compound (C).

Further, the polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film which is a polarizing plate or a phase difference plate.

[In order to implement the invention]

The terms used in this specification are as follows.

[Polymerizable liquid crystal compound] A compound having a polymerizable portion such as an acryl group or an α-methylene-γ-butyrolactone ring in a molecule and a liquid crystal structure portion, and exhibiting a liquid crystal phase. In general, the term "liquid crystal structure" means a structure having a spacer portion and a mesogen portion used when liquid crystal molecules are used. The "liquid crystal composition" means a composition having characteristics exhibiting a liquid crystal phase. "Liquid crystallinity" means a liquid crystal phase.

The polymerizable liquid crystal compounds (A) and (B) used in the present invention have a liquid crystal structure site and have either or both of an acryl group and an α-methylene-γ-butyrolactone ring structure.

Α-methylene-γ-butyrolactone exhibits little influence on steric hindrance even in α-alkyl-γ-butyrolactone having a polymerizable group, and has high aggregation. Extremely excellent results. Therefore, it is extremely effective in imparting high Tg or heat resistance to the polymer obtained by using the compound.

[Polymerizable liquid crystal compound (A)]

The polymerizable liquid crystal compound (A) used in the present invention is represented by the following formula [1].

In the formula [1], R ¹ is an organic group represented by the following formula [3] or [4].

(wherein X represents a hydrogen atom or a methyl group. The dotted line is a bonding bond.)

In the formula [1], R ² represents a hydrogen atom, a halogen atom, a cyano group or a methoxy group. The above halogen atom is particularly preferably a fluorine atom. R ^{2 is} preferably a hydrogen atom, a methoxy group or a cyano group, and more preferably a hydrogen atom or a cyano group.

The repeating part of the methylene group is called the part of the spacer. The n1 system represents a repeating number of methylene groups, each of which is an independent integer of 2 to 10, and preferably an integer of 3 to 6.

q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1.

The polymerizable liquid crystal compound (A) is a liquid crystal phase which represents a dish phase or a nematic phase. This characteristic is useful in the field of use of optical anisotropy such as a polarizing plate or a phase difference plate.

Specific examples of the polymerizable liquid crystal compound (A) include, for example, the compounds represented by the following formulas (1) to (25), but are not limited thereto. Further, in the formula, Me represents a methyl group.

[Polymerizable liquid crystal compound (B)]

The polymerizable liquid crystal compound (B) used in the present invention is represented by the following formula [2].

In the formula [2], R ³ and R ⁴ are synonymous with the above R ¹ and may be the same or different from each other. N2 and n3 represent the number of repetitions of methylene groups, each independently being an integer of 2 to 10, preferably an integer of 3 to 6. r is 1 or 2. s is 1 when r is 1, and 0 when r is 2.

In the formula [2], at least one of R ³ and R ⁴ is preferably an organic group represented by the formula [3]. The polymerizable liquid crystal compound (B) is more preferably those represented by the following formula [9].

(where n2, n3, r, and s are the same as above)

Specific examples of the polymerizable liquid crystal compound (B) are compounds represented by the following formulas (26) to (116), but are not limited thereto.

[Multivalent acrylate compound (C)]

The polyvalent acrylate compound (C) used in the present invention is condensed by having at least one structure selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or at least one selected from the group consisting of The structure is a polyvalent acrylate compound obtained by a polyvalent alcohol having an oxygen atom of 3 or more and 50 or less, and acrylic acid or a derivative thereof.

Specifically, for example, it is represented by the following formula [5] or [6].

(wherein R ⁵ is a methyl group or an organic group represented by the following formula [7] or [8].

The n4~n10 series are each an integer of 0~10. N11 is an integer from 4 to 10. The dotted line is the bond key. )

Specific examples of the polyvalent acrylate compound (C) are, for example, compounds represented by the following formulas (117) to (127), but are not limited thereto.

As the polyvalent acrylate compound (C), a commercially available product such as KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., PET30, ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., ADPH, or the like can be used.

[Polymerized liquid crystal composition]

The polymerizable liquid crystal composition of the present invention contains at least one polymerizable liquid crystal compound (A), at least one polymerizable liquid crystal compound (B), and at least one polyvalent acrylate compound (C). Further, the polyvalent acrylate compound (C) is preferably a compound represented by the above formula [5] or [6].

The content of the polymerizable liquid crystal compound (A) is from 100 to 1,900 parts by mass, preferably from 400 to 900 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound (B). The content of the polyvalent acrylate compound (C) is 0.5 to 100 parts by mass based on the total mass of the polymerizable liquid crystal compounds (A) and (B) (the combination of the two is referred to as a total of the liquid crystal compound). 5 mass points are better, preferably 1 to 3 mass points.

In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator, and a photosensitizer may be added for the purpose of improving the polymerization reactivity.

The photopolymerization initiator is, for example, a benzoin ether such as benzoin methyl ether, an acetophenone such as diethoxyacetophenone, or a benzyl ketal such as benzyldimethylketal. The photopolymerization initiator may be used singly or in combination of two or more. The amount of the photopolymerization initiator to be added 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 of the liquid crystal compound.

The photopolymerization initiator is, for example, 2,2'-azobisisobutyronitrile or the like. The thermal polymerization initiator may be used singly or in combination of plural kinds. The amount of addition 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 of the liquid crystal compound.

A photosensitizer such as a ruthenium-based photo sensitizer. The photosensitizer may be used alone or in combination of plural kinds. The amount of addition is preferably 5 parts by mass or less based on 100 parts by mass of the total of the liquid crystal compound.

Further, the photopolymerization initiator described above may be used in combination of 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 storage stability. The stabilizer is, for example, hydroquinone monoalkyl ether such as hydroquinone or hydroquinone monomethyl ether, or 4-t-butylcatechol. The stabilizer can be used alone or in combination of plural kinds. The amount of addition is preferably 0.1 parts by mass or less based on 100 parts by mass of the total of the liquid crystal compound.

Further, in the polymerizable liquid crystal composition of the present invention, in order to improve the adhesion to the substrate, an adhesion promoter may be added. a adhesion promoter such as trimethylchloromethane, dimethylvinylchlorodecane, methyldiphenylchlorodecane, chloromethyldimethylchlorodecane, vinyltrichloromethane or the like; chlorodecane; Oxy decane, dimethyl diethoxy decane, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, diphenyl dimethoxy decane, phenyl triethoxy decane, γ- Chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropoxypropyltrimethoxydecane, γ-glycine methoxypropyltrimethoxydecane, γ- Alkoxydecanes such as (N-piperidinyl)propyltrimethoxydecane; hexamethyldioxane, N,N'-double Amidoxime such as (trimethylmethylalkyl) urea, dimethyltrimethylformamidine, N-trimethylformamimidazole, benzotriazole, benzimidazole, carbazole, imidazole, a heterocyclic compound such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptooxazole, ureazazole, thiouracil, mercapthylimid, pyridylpyrimidine, etc.; 1,1-dimethylurea, 1, a urea compound such as 3-dimethylurea; a sulfur urea compound or the like.

The adhesion promoter may be used alone or in combination of plural kinds. The amount of addition is preferably 1 part by mass or less based on 100 parts by mass of the total liquid crystal compound.

Further, in the polymerizable liquid crystal composition of the present invention, an organic solvent may be added for the purpose of adjusting the viscosity and the like. At this time, the state containing an organic solvent may not exhibit liquid crystallinity.

An organic solvent such as an ether such as tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene or xylene; or a polar solvent such as N,N-dimethylformamide or N-methyl-2-pyrrolidone; Esters of ethyl acetate, butyl acetate, ethyl lactate, etc.; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, 2-methoxy Alkoxylates such as ethyl propyl propionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene Ethylene glycol monoalkyl ethers such as alcohol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. Ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether acetate, card Ethylene glycol monoalkyl ether esters such as alcohol alcohol acetate and ethyl cellosolve acetate; ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, etc. are preferable in terms of the safety of the earth environment and the working environment.

These organic solvents may be used alone or in combination of plural kinds. The amount of the organic solvent to be used is preferably from about 60 to 95% by mass in the polymerizable liquid crystal composition.

Further, in the polymerizable liquid crystal composition 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, a polyfluorene-based surfactant, and a nonionic surfactant. However, a fluorine-based surfactant having a high effect of improving affinity with a substrate is preferred. .

Specific examples of the fluorine-based surfactant are, for example, the following (trade name), EFTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F173, R-30 (DIC (shareholding)), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), ASAHI GUARD AG710, SAFLONS-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc., are not limited by these. Further, the surfactant may be used singly or in combination of plural kinds.

A suitable example of the polymerizable liquid crystal composition of the present invention is a polyvalent acrylate compound (400 parts by mass to 900 parts by mass) based on 100 parts by mass of the polymerizable liquid crystal compound (A) with respect to the polymerizable liquid crystal compound (B). C) in terms of 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) The amount of the photoinitiator to be formed in an amount of 5 parts by mass or less based on 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) is not limited thereto.

The method for preparing 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 may be sequentially mixed. When sequentially mixed, the order of addition of each component may be arbitrary.

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

The polymerizable liquid crystal composition of the present invention is used at the time of photopolymerization in the case of photopolymerization in a liquid crystal state, in order to avoid inducing undesired thermal polymerization and to easily fix a uniform alignment state of molecules. Preferably, the liquid crystal phase exhibiting an enantiomer at 20 to 40 ° C, the same below. Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferred to exhibit an enantiomeric liquid crystal phase at room temperature when the solvent is removed.

The polymerizable liquid crystal composition of the present invention can be suitably used as a composition for forming an alignment film or a coating liquid.

[Polymer and film]

The polymerizable liquid crystal composition of the present invention described above is obtained by light irradiation or heat treatment to obtain a polymer. Further, a polymerizable liquid crystal composition is applied onto a substrate by spin coating or casting, and a film is obtained by light irradiation treatment.

At this time, the substrate can use glass, quartz, color filter, triethylene fluorene fiber Plastic sheets or films such as TAC.

When the substrate to be used is used for the purpose of improving the mixed alignment of the obtained film, it is preferred to carry out the alignment treatment so as to obtain an inclination angle. For the method of the alignment treatment, a method of applying an alignment material containing a polyimide precursor, a polyimide, a polyvinyl cinnamate, or the like, and performing an alignment treatment by rubbing or obliquely irradiating a polarized ultraviolet ray may be appropriately selected. A method of forming a smectite vapor-deposited film of cerium oxide, a method of forming a Langeir film, and the like are preferably used. In order to produce a mixed alignment film, an alignment method using a tilt angle is preferable.

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

In any of the above methods, by performing polymerization in a state in which the polymerizable liquid crystal composition exhibits a liquid crystal phase, a film having an aligned optical anisotropy can be obtained.

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, a phase difference plate or the like. Further, since the film is excellent in transparency at a high temperature, it can be suitably used in an electronic device used in a high-temperature environment such as an automobile display device.

[Examples]

In the following, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the examples. Further, the measurement methods and measurement conditions of the respective physical properties of the examples are as follows.

[1] NMR

The compound was dissolved in hydrogen halide (CDCl ₃ ) or deuterated dimethyl hydrazine (DMSO-d6), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Geeol Corporation).

[2] Observation of liquid crystal phase

The liquid crystal phase was fixed, and the sample was heated on a high temperature stage (MATS-2002S, manufactured by Tokai), and observed using a polarizing microscope (Ricon). The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) manufactured by Bruker AXS Co., Ltd. at a scanning 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 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

The average tilt angle was measured using AxoScan ^TM Mueller Matrix Polarimeter (AXOMETRIX Corporation).

[Synthesis Example 1] Synthesis of Polymerizable Liquid Crystal Compound (A1) [1] Synthesis of intermediate compound (I1)

To a 500 mL eggplant type flask equipped with a cooling tube, 9.8 g (50.0 mmol) of 4-cyano-4'-hydroxybiphenyl, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, and 13.8 g of potassium carbonate were added ( 100 mmol) and acetone 15 mL were formed to form a mixture, and the mixture was stirred at 64 ° C for 48 hours to carry out a reaction. After completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow-yellow solid. Then, the solid and 140 mL of water were mixed, and 100 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. The organic layer was separated and dried over anhydrous magnesium sulfate, and after filtration, the solvent was evaporated under reduced pressure to give a yellow solid. This solid was purified by recrystallization using a mixed solvent of hexane / ethyl acetate = 2 / 1 (v / v) to obtain 8.7 g of a white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was the intermediate compound (I1) (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 (A1)

12.0 g of the intermediate compound (I1) obtained above, and 7.7 mL of triethylamine and a small amount of 2,6-di-t-butyl-p-cresol (BHT) were simultaneously dissolved in 40 mL of tetrahydrofuran (THF). The mixture was stirred at room temperature, cooled by a water bath, and a solution of 4.6 mL of a chlorinated propenyl group dissolved in 40 mL of THF was added dropwise thereto over 15 minutes. After the completion of the dropwise addition, stirring was carried out for 30 minutes, and the water bath was removed, and the mixture was returned to room temperature, and stirred overnight, and the precipitated triethylamine hydrochloride was filtered. Distilled about 3/4 of THF from the obtained liquid, and added 50 mL of dichloromethane, and the organic layer was washed with 50 mL of a saturated aqueous sodium hydrogencarbonate solution, 50 mL of 0.5 mol/L hydrochloric acid, and 50 mL of saturated brine, and sulfuric acid was used. After the magnesium is dried, the solvent is distilled off to obtain a product. After recrystallization by ethanol, 6.0 g of a polymerizable liquid crystal compound (A1) 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 (A2) [1] Synthesis of intermediate compound (I2)

To a 100 mL eggplant type flask equipped 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 were added ( 50 mmol) and acetone 50 mL were combined to form a mixture, and the mixture was stirred at 64 ° C for 24 hours to carry out a reaction. After completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow-yellow solid. Then, 70 mL of the solid and water were mixed, and 50 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. The organic layer was separated and dried over anhydrous magnesium sulfate, and 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 a ceria gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/acetic acid) Ethyl ester = 1/1 (v/v) was purified, and the solvent was evaporated to give 6.9 g of a white solid. The NMR measurement results of the solid were as follows. From the results, it was confirmed that the white solid was in the middle. Compound (I2) (yield 91%).

¹ H-NMR (DMSO-d ₆ ) 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 (F2)

Then, 2.2 g (10.0 mmol) of chlorochromate pyridinium salt (PCC) and 30.0 mL of dichloromethane were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was added dropwise to 50.0 mL of dichloromethane while stirring and mixing. A solution of 2.95 g (10.0 mmol) of the intermediate compound (I2) obtained above was dissolved, and the mixture was stirred at 40 ° C for 0.5 hour. Then, 90 mL of diethyl ether was added to the solution of the oily substance adhering to the wall of the flask, and the mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a dark green solid. The solid was dissolved in 3 mL of ethyl acetate, and analyzed by ruthenium dioxide gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/ethyl acetate) The solvent was distilled off from the obtained solution to obtain 2.8 g of a colorless solid. The NMR measurement results of the solid were as follows. From the results, it was confirmed that the colorless solid was an intermediate compound. (F2) (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 (A2)

Finally, 2.9 g (10.0 mmol) of the intermediate compound (F2) obtained above, 1.65 g (10.0 mmol) of 2-(brominated methyl)acrylic acid, and Amberlyst (registered trademark) were added to a 50 mL eggplant type flask equipped with a cooling tube. 15 (Rome & Haas brand name) 1.6 g, THF 16.0 mL, tin (II) chloride 1.9 g (10.0 mmol), and pure water 4.0 mL were formed to form a mixture, and the mixture was stirred at 70 ° C for 7 hours to carry out a reaction. 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. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the extracted organic layer to dryness, and the solvent was filtered off from the filtrate under reduced pressure to give a yellow solid. The solid was dissolved in 2 mL of ethyl acetate and analyzed by a ceria gel column chromatography (column: cerium oxide gel 60, 0.063-0.200 mm, manufactured by Merck, eluate: hexane/acetic acid) Ethyl acetate = 2/1 (v/v) was purified, and the solvent was distilled off from the obtained solution to obtain 1.5 g of a white solid. The NMR measurement results of the solid were as follows. From this result, the white solid was confirmed. Polymerizable liquid crystal compound (A2) (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 crystallinity of the polymerizable liquid crystal compound (A2), an isotropic liquid state was formed at 84 ° C, and when the temperature was lowered, the phase was transferred to a liquid crystal phase (nematic phase) at 61 ° C.

[Synthesis Example 3] Synthesis of Polymerizable Liquid Crystal Compound (B1) [1] Synthesis of intermediate compound (I3)

To a 200 mL eggplant type flask equipped 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 was formed to form a mixture, which was stirred at 64 ° C (heated reflux) for 24 hours and reacted. After completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated to vacuo. The solid was subjected to ceria gel column chromatography (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 away from the obtained solution to obtain 11.3 g of a white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was the objective intermediate compound (I3) (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 (F3)

Then, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane were placed in a 100 mL three-necked flask equipped with a cooling tube, and the intermediate compound obtained above was dissolved in 15.0 mL of dichloromethane while stirring and mixing. (I3) A solution of 2.5 g (10.0 mmol) was stirred at room temperature for 6 hours. Then, 90 mL of diethyl ether was added to the solution which removed the oil which adhered to the wall of the flask, and after filtration under reduced pressure, the solvent was distilled off under reduced pressure to obtain a dark green moist solid. The solid was analyzed by cerium oxide gel 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 off from the obtained solution to obtain 1.3 g of a colorless solid. The NMR measurement results of the solid were as follows. From the results, it was confirmed that the colorless solid was the intermediate compound (F3) (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 (G3)

Next, 1.25 g (5.0 mmol) of the intermediate compound (F3) obtained above, 0.83 g (5.0 mmol) of 2-(brominated methyl)acrylic acid, and Amberlyst (registered trademark) were placed in a 50 mL eggplant type flask equipped with a cooling tube. 15 (Rome & Haas brand name) 0.8 g, THF 8.0 mL, tin (II) chloride 0.95 g (5.0 mmol), and pure water 2.0 mL, and a mixture was formed, and the mixture was stirred at 70 ° C for 5 hours to carry out a reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 40 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off from the filtrate under reduced pressure to obtain 1.5 g of a colorless solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the colorless solid was the intermediate compound (G3) (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 (H3)

In a 100 mL eggplant type flask equipped with a cooling tube, 35 mL of ethanol, 1.5 g (4.7 mmol) of the obtained intermediate compound (G3), 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. The reaction was carried out in an hour. After 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 1.3 g of a white solid. Then, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 (trade name of Rome & Haas Co., Ltd.), and 20.0 mL of THF were added to a 50 mL eggplant type flask equipped with a cooling tube to form a mixture, which was stirred at 70 ° C. The reaction was carried out for 5 hours. After completion of the reaction, the solvent was filtered off from the reaction mixture under reduced pressure to give a yellow solid. The yellow solid was purified by recrystallization (hexane/ethyl acetate = 1/1 (v/v)) to yield a white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was the objective compound (H3) (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 (TEA) and a small amount of BHT were simultaneously dissolved in 100 mL of THF, stirred at room temperature, and cooled by a water bath. A solution of 12.2 mL (150 mmol) of chlorinated propenylhydrazine was dissolved in 50 mL of THF over 15 minutes. After the completion of the dropwise addition, stirring was carried out for 30 minutes, and the water bath was removed, and the mixture was returned to room temperature and stirred overnight, and the precipitated TEA hydrochloride was filtered. The 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/L hydrochloric acid, and brine, dried over magnesium sulfate, and then evaporated. Solvent, the compound (P3) was obtained in an amount of 18.2 g. The solid was measured by NMR as 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 (J3)

In a 500 mL eggplant type flask equipped with a cooling tube, 14.6 g (94.3 mmol) of 4-hydroxy-4'-bisphenol, 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. The mixture was formed and stirred at a temperature of 54 ° C for 20 hours and the reaction was carried out. After completion of the reaction, the reaction solution was filtered under reduced pressure and the solvent was evaporated to vacuo to yield a yellow wet 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). The solvent was distilled off from the solution obtained here to give 6.1 g of white solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the white solid was an intermediate compound (J3) (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 polymerizable liquid crystal compound (B1)

6.1 g (20.0 mmol) of the intermediate compound (H3) obtained above, intermediate compound (J3) 6.0 g (20.0 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.08g and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) were suspended in 10 mL of dichloromethane at room temperature with stirring, and 20 mL of dichloromethane was dissolved therein. Dichlorocyclohexylcarboxydiimide (DCC) 4.7 g (23.0 mmol), after stirring overnight, the separated DCC urea was filtered, and the filtrate was sequentially placed with 60 mL of 0.5 mol/L hydrochloric acid and saturated hydrogen carbonate. After the sodium aqueous solution and the saturated aqueous sodium chloride solution were washed twice, and dried over magnesium sulfate, the solvent was distilled off, and recrystallization was carried out by ethanol to obtain 8.8 g (yield: 75%) of the polymerizable liquid crystal compound (B1). The solid was measured by NMR as shown below.

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, 4H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)

Further, as a result of observing the liquid crystallinity of the polymerizable liquid crystal compound (B1), the phase was transferred to a discotic X phase at a temperature of 109 ° C at a temperature rise, and the phase was transferred to a nematic phase at 144 ° C, and formed at 168 ° C. Square liquid state.

[Examples, Comparative Examples] Polymeric 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 used in Examples 1 to 8 are shown in Table 1, and the compositions of the compositions used in Comparative Examples 1 to 5 are shown in Table 2.

Further, the following compounds (C1), (C2), (C3), (C5), and (E1) are products of Shin-Nakamura Chemical Industry Co., Ltd., and the compound (C4) is a Japanese chemical (share). The product (E2) is a product of Tokyo Chemical Industry Co., Ltd. Compound (E3) is known.

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

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 9 mg of the polyvalent acrylate compound (C1), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

The polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by a spin coater (1,000 rpm, 20 seconds), and calcined on a hot plate at 100 ° C for 60 seconds. Allow to cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with a liquid crystal alignment film used here is attached to the ITO surface of the ITO-attached glass substrate by spin The transfer coater was coated with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries Co., Ltd.), and fired at 230 ° C to form a film having a thickness of 100 nm, and then subjected to a rubbing treatment.

Next, the coating film formed on the substrate with the liquid crystal alignment film was irradiated with a methane lamp under a nitrogen atmosphere at a light intensity of 2,000 mJ/cm ² to polymerize the polymerizable liquid crystal composition.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 117 nm and the haze value was 1.44.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 109 nm and the haze value was 1.30.

[Example 2] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the polyvalent acrylate compound (C2), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator. 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). Blocking The value was 121 nm and the haze value was 0.66.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 109 nm and the haze value was 0.38.

[Example 3] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the polyvalent acrylate compound (C3), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 115 nm and the haze value was 0.08.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 98 nm and the haze value was 0.07.

[Example 4] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 9 mg of the polyvalent acrylate compound (C4), and a photopolymerization initiator manufactured by Ciba Geigy Co., Ltd. 4 mg of Irgacure 369 (trade name) and 0.6 mg of R30 (manufactured by DIC Co., Ltd.) of a surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 101 nm and the haze value was 0.05.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 92 nm and the haze value was 0.07.

[Example 5] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the polyvalent acrylate compound (C4), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). Blocking The value was 96 nm and the haze value was 1.15.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 95 nm and the haze value was 2.18.

[Example 6] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 3 mg of the polyvalent acrylate compound (C5), and Irgacure 369 (produced by Ciba Geigy Co., Ltd.) as a photopolymerization initiator 4 mg of the product and 0.6 mg of R30 (manufactured by DIC) of the surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 106 nm and the haze value was 0.03.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 99 nm and the haze value was 0.08.

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

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 15 mg of the compound (E1), and a photopolymerization initiator, Irgacure, Ciba Geigy Co., Ltd. 4 mg of 369 (trade name) and 0.6 mg of R30 (manufactured by DIC) of a surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.7 μm, and it was confirmed by a polarizing microscope that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 296 nm and the haze value was 0.08.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 201 nm and the haze value was 0.08.

[Comparative Example 2] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of a polymerizable liquid crystal compound (A1), 90 mg of a polymerizable liquid crystal compound (A2), 60 mg of a polymerizable liquid crystal compound (B1), 30 mg of a compound (E2), and a photopolymerization initiator, Irgacure 369 (trade name), manufactured by Ciba Geigy Co., Ltd., 4 mg And 0.6 mg of R30 (manufactured by DIC) of the surfactant was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.9 μm, and it was confirmed by a polarizing microscope that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 261 nm and the haze value was 0.08.

After the film was heated on a hot plate at 200 ° C for 30 minutes, the retardation value was At 144 nm, the haze value was 0.08.

[Comparative Example 3] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of a polymerizable liquid crystal compound (A1), 90 mg of a polymerizable liquid crystal compound (A2), 60 mg of a polymerizable liquid crystal compound (B1), 30 mg of a compound (E3), and a photopolymerization initiator, Irgacure 369 (trade name), manufactured by Ciba Geigy Co., Ltd., 4 mg And 0.6 mg of R30 (manufactured by DIC) of the surfactant was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.9 μm, and it was confirmed by a polarizing microscope that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 328 nm and the haze value was 0.16.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 265 nm and the haze value was 0.16.

[Comparative Example 4] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 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 prepare a polymerizable liquid crystal composition.

The same procedure as in Example 1 was carried out except that the polymerizable liquid crystal composition was used. As a film. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 289 nm and the haze value was 0.16.

After the film was heated on a hot plate at 200 ° C for 30 minutes, the retardation value was 209 nm and the haze value was 0.16.

[Comparative Example 5] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 150 mg of the polymerizable liquid crystal compound (A2), 9 mg of the polyvalent acrylate compound (C4), and 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., Ltd. as a photopolymerization initiator, and a surfactant 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.

A film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was used. Further, the polymerizable composition on the substrate after the pre-baking is in a liquid crystal state.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface (inclination angle < 10°). The retardation value was 258 nm and the haze value was 1.49.

After heating the film on a hot plate at 200 ° C for 30 minutes, the retardation value was 18 nm and the haze value was 0.24.

The results of the above Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 3 below. Moreover, the thermal stability (%) of the Δnd value in Table 3 is relative to the firing. The ratio of the Δnd value after firing is the Δnd value.

Further, the retardation values of the films prepared in the above Examples 1 to 6 at a wavelength of 590 nm are as shown in Fig. 1, and the films prepared in the above Comparative Examples 1 to 5 have a retardation angle at a wavelength of 590 nm. The correlation is shown in Figure 2.

Next, the embodiment will be described with respect to controlling the alignment pattern (horizontal or hybrid type) by the alignment film forming step.

[Example 7] Polymerizable liquid crystal composition and polymer (film) thereof

150 mg of the polymerizable liquid crystal compound (A1), 90 mg of the polymerizable liquid crystal compound (A2), 60 mg of the polymerizable liquid crystal compound (B1), 4.5 mg of the polyvalent acrylate compound (C4), and Irgacure 369 manufactured by Ciba Geigy Co., Ltd. as a photopolymerization initiator. (trade name) 4 mg and R30 (manufactured by DIC Co., Ltd.) of 0.6 mg of a surfactant were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

The polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by a spin coater (1,000 rpm, 20 seconds), and calcined on a hot plate at 100 ° C for 60 seconds. Allow to cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with a liquid crystal alignment film used here is coated on a ITO surface of a glass substrate with ITO, and a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries Co., Ltd.) is coated by a spin coater at 130 After firing at a temperature of ° C to form a film having a thickness of 200 nm, a polarized UV light of 500 mJ/cm ^{2 was} irradiated from an oblique angle (40°).

Next, the coating film formed on the substrate with the liquid crystal alignment film was irradiated with a methane lamp under a nitrogen atmosphere at a light intensity of 2,000 mJ/cm ² to polymerize the polymerizable liquid crystal composition.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was mixed and aligned on the substrate surface (average inclination angle: 40°). The retardation value was 143 nm and the haze value was 0.13.

[Example 8] Polymerizable liquid crystal composition and polymer (film) thereof

The polymerizable liquid crystal composition obtained in Example 7 was coated on a liquid crystal alignment film surface of a substrate with a liquid crystal alignment film by a spin coater (1,000 rpm, 20 seconds), and calcined on a hot plate at 100 ° C. After 60 seconds, let cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with a liquid crystal alignment film used here is coated on a ITO surface of a glass substrate with ITO, and a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries Co., Ltd.) is coated by a spin coater at 130 After firing at a temperature of ° C to form a film having a thickness of 200 nm, a polarized UV light of 1000 mJ/cm ² was irradiated from directly above.

Next, the coating film formed on the substrate with the liquid crystal alignment film was irradiated with a methane lamp under a nitrogen atmosphere at a light intensity of 2,000 mJ/cm ² to polymerize the polymerizable liquid crystal composition.

The film thickness of the obtained film was 1.8 μm, and when observed by a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. The retardation value was 306 nm and the haze value was 0.13.

The angle dependence of the retardation values of the films prepared in the above Examples 7 and 8 at a wavelength of 590 nm is shown in Fig. 3.

[Industry use value]

The polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film which is a polarizing plate or a phase difference plate.

[Fig. 1] is a graph showing the angular dependence of the retardation values of the films obtained in Examples 1 to 6 at a wavelength of 590 nm.

[Fig. 2] is a graph showing the angular correlation of the retardation values of the films obtained in Comparative Examples 1 to 5 at a wavelength of 590 nm.

[Fig. 3] is a graph showing the angular dependence of the retardation values of the films obtained in Examples 7 to 8 at a wavelength of 590 nm.

Claims (8)

A polymerizable liquid crystal composition comprising (A) at least one selected from the group consisting of polymerizable liquid crystal compounds represented by the following formula [1], and (B) selected from the group consisting of polymerizable liquid crystals represented by the following formula [2] At least one of the compounds, and (C) is at least one selected from the group consisting of a polyvalent acrylate compound having at least one selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure. a structure obtained by condensing at least one selected from the group consisting of a polyol, an acrylic acid or a derivative thereof, having a structure in which at least one of these is condensed, and having three or more oxygen atoms in total [wherein R ¹ , R ³ and R ⁴ are each independently an organic group represented by the following formula [3] or [4], (wherein X represents a hydrogen atom or a methyl group; the broken line represents a bond; R ² represents a hydrogen atom, a halogen atom, a cyano group or a methoxy group; and n1, n2 and n3 each independently represent 2 to 10; An integer; q is 0 or 1; p is 1 when q is 0, 0 or 1 when q is 1, r is 1 or 2; s is 1 when r is 1, when r is 2 o'clock is 0]. The polymerizable liquid crystal composition according to claim 1, wherein the polybasic acrylate compound (C) is represented by the following formula [5] or [6]. (wherein R ⁵ represents a methyl group or an organic group represented by the following formula [7] or [8], N4~n10 are each independently an integer from 0 to 10; n11 is an integer from 4 to 10; the dotted line indicates a bonding key). The polymerizable liquid crystal composition according to claim 1 or 2, wherein the polymerizable liquid crystal compound (B) is represented by the following formula [9]. (wherein n2, n3, r and s are the same as described above). The polymerizable liquid crystal composition of the first aspect of the invention, wherein the content of the polymerizable liquid crystal compound (A) is from 100 to 1,900 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound (B), and the polyvalent acrylate The content of the compound (C) is 0.5 to 5 parts by mass based on 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B). a polymer characterized by the first to fourth aspects of the patent application The polymerizable liquid crystal composition of any one of the items. A film obtained by the polymerizable liquid crystal composition according to any one of claims 1 to 4 of the patent application. A hybrid alignment film obtained by the polymerizable liquid crystal composition according to any one of claims 1 to 4. An optical member characterized by comprising an alignment film according to item 7 of the patent application.