KR20180109968A - Liquid crystal composition and single-layer coated horizontally oriented film - Google Patents

Abstract

(A) a polymer containing a repeating unit represented by the following formula [1a], [1b] and [1c], (B) a polymer containing a repeating unit represented by the following formula [7a], [7b] , And (C) an organic solvent.

Description

Liquid crystal composition and single-layer coated horizontally oriented film

The present invention relates to a liquid crystal composition and a single layer-applied horizontally oriented film. And more particularly to a liquid crystal composition having optical characteristics suitable for use in display devices and recording materials and particularly suitable for producing an optical compensation film such as a polarizing plate and a retarder for a liquid crystal display and a single layer coating type horizontal And an orientation film.

There has been an increasing demand for a polymer film whose inner molecular alignment structure is controlled as an optical compensation film such as a polarizing plate or a retardation plate due to demands for improvement in display quality and light weight of a liquid crystal display device. In order to meet this demand, development of a film using optical anisotropy of a polymerizable liquid crystal compound has been made. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (a structural portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group.

Such a polymerizable liquid crystal compound is generally a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays. For example, there is a method (Patent Document 1) in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and irradiated with radiation while maintaining the compound in a liquid crystal state (Patent Document 1) A method of adding a photopolymerization initiator to a composition of a liquid crystal compound or a mixture of the mixture with a chiral liquid crystal and irradiating ultraviolet rays to obtain a polymer (Patent Document 2) is known.

(Patent Documents 3 and 4) using a polymerizable liquid crystal compound or polymer that does not require a liquid crystal alignment film, or an orientation film (Patent Documents 5 and 6) using a polymer containing a photo-crosslinking site Oriented films have been reported.

The present inventors have reported a material for enabling the production of a single layer coated horizontally oriented film having a high refractive index anisotropy (? N) by a simple process (Patent Document 7). However, a film having a higher refractive index anisotropy (? N) is required.

Japanese Patent Laid-Open No. 62-70407 Japanese Patent Application Laid-Open No. 9-208957 European Patent Application Publication No. 1090325 International Publication No. 2008/031243 Japanese Patent Application Laid-Open No. 2008-164925 Japanese Patent Application Laid-Open No. 11-189665 International Publication No. 2013/133078

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a liquid crystal composition capable of producing a single layer coating type horizontally oriented film having a higher refractive index anisotropy (? N) and a single layer coating type horizontally oriented film obtained from the liquid crystal composition .

As a result of intensive investigations to solve the above problems, the present inventors have found that a polymer having a? -Butyrolactone skeleton in its main chain and having a cinnamate ester structure on a side chain extending from the? -Position of a lactone ring, And that a film obtained from a composition containing an organic solvent can be subjected to low-temperature treatment, whereby a horizontally oriented film having a higher refractive index anisotropy (? N) is obtained, thereby completing the present invention.

That is, the present invention provides the following liquid crystal composition and a single layer-applied horizontally oriented film.

1. A polymer comprising (A) a repeating unit represented by the following formula [1a], [1b] and [1c]

(B) a compound which does not exhibit liquid crystallinity, represented by the following formula [7a], [7b] or [7c]

(C) an organic solvent

≪ / RTI >

[Wherein X and Y are each independently a group represented by the following formula [2] or [3]

(Wherein R < ¹ > is a hydrogen atom or a methyl group, and the broken line is a bonding hand).

M ¹ is a group represented by the following formula [4], M ² is a group represented by the following formula [5] or [6]

(Wherein, s1, s2, s3, s4, s5 and s6 is 1 or 2, each independently, and G ¹ and G ² represents a single bond, -COO- or -OCO-, each independently, R ² and R ³ A halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and the broken line indicates a bonded bond.

A is a linear or branched alkyl group having 2 to 15 carbon atoms,

m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0? p? 0.5 and m + n + p?

q and r each independently represent an integer of 2 to 9.]

(Wherein, R ⁵ and R ⁶ are each independently selected from _{-OH, -OCH 3, -C (=} O) OH, -C (= O) OCH 3, -C (= O) OCH 2 CH 3 or -OC (= O) is CH _3, R ⁷ and R ⁸ are each independently a hydrogen _{atom, -OH, -OCH 3, -C (} = O) OH, -C (= O) OCH 3, -C (= O) OCH ₂ CH ₃ or -OC (═O) CH ₃ , G ³ is a single bond, -C (═O) -O- or -OC (═O) -, G ⁴ is a single bond, -CH═CH - or -CH ₂ CH ₂ -.

2. Horizontally oriented film of single layer coated type prepared by using liquid crystal composition.

3. An optical member comprising a single-layer coating type horizontally oriented film.

A process for producing a single-layer coating type horizontally oriented film, comprising the step of applying the liquid crystal composition of 4.1 to a substrate, the step of irradiating polarized light, and the step of post-baking.

5. A process for producing a homogeneously layered horizontally oriented film of 4 wherein the polarized light is a linearly polarized ultraviolet ray.

It is possible to produce a single layer coating type horizontally oriented film exhibiting a high Δn by applying a liquid crystal composition of the present invention, irradiating linearly polarized light at room temperature, and performing post-baking at a low temperature.

Fig. 1 is a diagram showing the retardation value angle dependency of each film obtained in Comparative Example 1 and Examples 1 to 5. Fig.
Fig. 2 is a diagram showing the retardation value angle dependency of each film obtained in Comparative Example 1 and Examples 6 to 9. Fig.
Fig. 3 is a diagram showing the retardation value angle dependency of each of the films obtained in Comparative Examples 2 to 3 and Examples 10 to 11. Fig.

[Liquid crystal composition]

The liquid crystal composition of the present invention comprises (A) a predetermined polymer, (B) a compound which does not exhibit a predetermined liquid crystallinity, and (C) an organic solvent.

[(A) Polymer]

The polymer of the component (A) contains the repeating units represented by the following formulas [1a] and [1b], and further contains the repeating unit represented by the following formula [1c].

Among the formulas [1a] and [1c], X and Y are each independently a group represented by the following formula [2] or [3].

In the formula [3], R ¹ is a hydrogen atom or a methyl group. The dashed line is a combined hand (hereinafter the same). Among them, X and Y are preferably a group represented by the formula [3].

In the formula [1a], M ¹ is a group represented by the following formula [4]. In the formula [1b], M ² is a group represented by the following formula [5] or [6].

Equation [4] to [6] of, s1, s2, s3, s4, s5 and s6 is 1 or 2, each independently, G ¹ and G ² represents a single bond, -COO- or -OCO- are each independently . R ² and R ³ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the present invention, a fluorine atom is preferable.

The alkyl group represented by R ² and R ³ may be any of linear, branched and cyclic. In the present invention, a straight chain alkyl group having 1 to 10 carbon atoms is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec- N-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. Among these, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable. The alkyl group represented by R ⁴ may be either linear or branched. In the present invention, a straight chain alkyl group having 1 to 3 carbon atoms is preferable.

The alkoxy group may be any of linear, branched and cyclic. In the present invention, a straight chain alkoxy group having 1 to 10 carbon atoms is preferable. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, tert- A siloxane group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, and a n-decyloxy group. Of these, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable. In the alkyl group and the alkoxy group, a part or all of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.

R ² or R ³ is more preferably a hydrogen atom, a fluorine atom, a cyano group, a methyl group or a methoxy group. R ⁴ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

G ¹ is preferably -COO- or -OCO-, and G ² is preferably a single bond.

In the formula [1c], A represents an alkyl group having 2 to 15 carbon atoms, which is linear or branched. Specific examples of the alkyl group include an alkyl group such as an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Methyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-butyl group, Methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, Butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2- Butyl group, a 2-ethyl-n-butyl group, a 1,1,2- Methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- N-hexyl group, 1-methyl-n-pentyl group, 1,2-dimethyl-n-hexyl group, - pentyl group, 1,3-dimethyl-n-pentyl group, 2,2- Methyl-n-pentyl group, a 1-ethyl-n-pentyl group, a 2-ethyl-n-pentyl group, Methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, Methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl n-hexyl group, 1, 3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, Ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl- Ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n- A dodecyl group, an n-tridecyl group, an n-tetradecyl group, and an n-pentadecyl group.

Of these, an alkyl group having 4 to 15 carbon atoms, particularly 4 to 12 carbon atoms is preferable in view of the solubility of the obtained polymer in an organic solvent and the like, and an n-butyl group, a 2-ethyl-n-hexyl group, Is more preferable.

In the formulas [1a] to [1c], m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0 p? 0.5 and m + n + p? M, n and p are preferably numbers satisfying 0.2? M? 0.9, 0.1? N? 0.8, and 0? P? 0.4 in view of improvement in? N and improvement in solubility of the polymer, 0.8, 0.1? N? 0.5, and 0.1? P? 0.3. In the case where M ² is a group represented by the formula [6], it is preferable that p = 0, 0 <m <1, 0 <n <1 and m + More preferably 0.1? N? 0.8, and still more preferably 0.5? M? 0.8 and 0.2? N? 0.5.

Among the formulas [1a] and [1b], q and r each independently represent an integer of 2 to 9, preferably 3 to 6, more preferably 5 or 6 as q.

The polymer of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the Mw exceeds 200,000, the solubility in a solvent may deteriorate and the handling property may deteriorate. When the Mw is less than 3,000, curing becomes insufficient at the time of thermal curing, and solvent resistance and heat resistance may be lowered. Mw is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

The polymer of the component (A) may contain other repeating units other than the formulas [1a] to [1c], so long as the effect of the present invention is not impaired. Examples of the polymerizable compound giving the above other repeating unit include an acrylate ester compound, a methacrylate ester compound, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, and a styrene compound.

The content of other repeating units is preferably 0 to 10 mol% based on 100 mol% of all repeating units. If the content of other repeating units is excessively large, the properties of the polymer, such as liquid crystallinity, may be deteriorated.

When the polymer of component (A) contains the above other repeating unit, the polymerization method may be a polymerization method in which a polymerizable compound that gives the above other repeating unit coexists during the polymerization.

The polymer of the component (A) may be a random copolymer, an alternating copolymer or a block copolymer. These polymers may be used singly or in combination of two or more.

Examples of the method for synthesizing the polymer of component (A) include, but are not limited to, those described in International Publication No. 2013/133078 or International Publication No. 2015/025794.

[(B) Compound which does not show liquid crystallinity]

(B) are compounds represented by the following formula [7a], [7b] or [7c].

In the formula [7a], R ⁵ and R ⁶ are each independently selected from _{-OH, -OCH 3, -C (=} O) OH, -C (= O) OCH 3, -C (= O) OCH 2 CH 3 or -OC (= O) is CH _3. Of these, -C (= O) OCH ₃ or _{-C (= O) OCH 2 CH} 3 are preferable, and, -C (= O) ₂ CH ₃ are preferred over OCH.

Formula [7b] of, R ⁷ and R ⁸ are each independently a hydrogen _{atom, -OH, -OCH 3, -C (} = O) OH, -C (= O) OCH 3, -C (= O) OCH 2 CH ₃ or -OC (= O) CH ₃ . Of these, -C (= O) OCH ₃ or _{-C (= O) OCH 2 CH} 3 are preferable, and, -C (= O) ₂ CH ₃ are preferred over OCH.

In formula [7b], G ³ is a single bond, -C (= O) -O- or -OC (= O) -. Of these, a single bond or -C (= O) -O- is preferable, and a single bond is more preferable.

In formula [7c], G ⁴ is a single bond, -CH = CH- or -CH ₂ CH ₂ -. Of these, a single bond or -CH = CH- is preferable, and a single bond is more preferable.

Examples of the compound represented by the formula [7a] include, but are not limited to, the following compounds.

Examples of the compound represented by the formula [7b] include, but are not limited to, the following compounds.

Examples of the compound represented by the formula [7c] include, but are not limited to, the following compounds.

The compounds represented by the formulas [7a] to [7c] can be synthesized using a known method (for example, an esterification reaction) or can be obtained as a commercial product.

The content of the component (B) is preferably from 1 to 10 parts by mass, more preferably from 1 to 5 parts by mass, per 100 parts by mass of the polymer (A). When the content of the component (B) is within the above range, the effect of improving the retardation is exhibited. The compound of component (B) may be used singly or in combination of two or more.

[(C) Organic solvent]

Examples of the organic solvent of component (C) include ethers such as tetrahydrofuran and dioxane; Aromatic hydrocarbons such as benzene, toluene and xylene; Polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone (NMP); Esters such as ethyl acetate, butyl acetate, and ethyl lactate; Alkoxy esters such as methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; Dialkyl dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether; Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Diglycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; Glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; Ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These organic solvents may be used alone or in combination of two or more.

Of these, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and cyclohexanone are preferred. The amount of the organic solvent used is preferably about 60 to 95% by mass in the composition.

[Other components]

A surfactant may be added to the composition of the present invention for the purpose of improving affinity with a substrate. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant, and a fluorine-based surfactant having a high affinity for improving affinity with a substrate is preferable.

Specific examples of the fluorine-based surfactant include FFP (registered trademark) EF301, EF303 and EF352 (manufactured by Tohchem Products Corporation), Megapack (registered trademark) F171, F173, R-30 and R-30N (Registered trademark) S-382, SC101, SC102, SC103, SC104, SC104, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and the like. The surfactant may be used singly or in combination of plural species, and the amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the polymer.

The adhesion promoter may be added to the composition of the present invention for the purpose of improving adhesion with a substrate. Examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane; Alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane and the like; Silane residues such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole and the like; Vinyl trichlorosilane,? -Chloropropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane, silanes such as? - (N-piperidinyl) propyltrimethoxysilane; Benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiofulasil, mercaptoimidazole, Heterocyclic compounds such as mercaptopyrimidine; Urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; Thiourea compounds, and the like.

The adhesion promoter may be used singly or in combination of two or more, and the amount thereof is preferably 1 part by mass or less based on 100 parts by mass of the polymer.

[Horizontal Orientation Film of Single Layer Coating Type]

The composition of the present invention may be applied to substrates (e.g., silicon / silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, A spin coat, a flow coat, a roll coat, a slit coat, a spray coat, or the like is applied onto a substrate or film (e.g., a film of a resin such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, The film can be formed by applying a slit coat followed by a spin coat, an inkjet method, a printing method or the like to form a coating film, and then heating and drying the coated film with a hot plate or an oven.

As the heating and drying conditions, for example, heating temperature and heating time appropriately selected from the range of 50 to 100 ° C and 0.1 to 60 minutes are employed. The heating temperature and the heating time are preferably 50 to 80 DEG C for 0.1 to 2 minutes.

The thus formed film is irradiated with linearly polarized light and subjected to post-baking to obtain a single layer coated horizontally oriented film. As a method of irradiating linearly polarized light, ultraviolet rays or visible rays having a wavelength of usually 150 to 450 nm are used, and irradiation is performed by irradiating linearly polarized light at room temperature or in a heated state.

The postbake may be heated by a hot plate or an oven, and the temperature and time are preferably 90 to 150 DEG C for 2 to 20 minutes, more preferably 95 to 120 DEG C for 5 to 20 minutes.

The film thickness of the single-layer coating type horizontally oriented film of the present invention can be appropriately selected in consideration of the step difference of the substrate to be used and the optical and electrical properties, and for example, 0.1 to 3 탆 is suitable.

The thus obtained single-layer coating type horizontally oriented film of the present invention is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizing plate and a retarder for a liquid crystal display.

(Example)

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measurement methods and the measurement conditions of each physical property in the examples are as follows.

[NMR]

The compound was dissolved in deuterated chloroform (CDCl ₃ ), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Dior).

[Average molecular weight measurement]

Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran (THF), calibration curve: standard polystyrene) manufactured by Showa Denko K.K.

[Retardation value of film]

Retardation value dependency of the retardation value at a wavelength of 550 nm was measured using a retardation measurement apparatus (RETS-100, manufactured by Otsuka Denshi Co., Ltd.).

[1] Synthesis of Compound

[Synthesis Example 1] Synthesis of polymerizable compound (M1)

(100 mmol) of 4- (6-acryloyloxy-1-hexyloxy) benzoic acid (SYNTHON Chemicals), 17.0 g (100 mmol) of 4-hydroxybiphenyl, 4-dimethylaminopyridine g and a small amount of dibutylhydroxytoluene (BHT) were suspended in 200 mL of methylene chloride while stirring at room temperature. To the solution was added dropwise 24.0 g (116 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) And the mixture was stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 150 ml of 0.5 mol / L hydrochloric acid, 150 ml of a saturated sodium hydrogencarbonate aqueous solution and 150 ml of saturated brine, and dried with magnesium sulfate. The solvent was distilled off, To obtain 39.6 g of a desired polymerizable compound (M1) (yield: 89%). The measurement results of NMR are shown below.

[Synthesis Example 2] Synthesis of polymerizable compound (M2)

(1) Synthesis of intermediate compound (Q2)

(100 mmol) of biphenol, 10.0 g (48 mmol) of 2- (4-bromo-1-butyl) -1,3-dioxolane, 13.8 g (100 mmol) of potassium carbonate, And the mixture was reacted at 64 占 폚 for 24 hours with stirring. After 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 methanol, filtered, and the solvent was distilled off to obtain a white solid. This solid was then mixed with chloroform, filtered, and the solvent was distilled off to obtain 7.2 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the intermediate compound (Q2) (yield: 48%).

(2) Synthesis of intermediate compound (Z2)

Subsequently, 7.2 g (23 mmol) of the intermediate compound (Q2), 4.1 g (25 mmol) of 2- (bromomethyl) acrylic acid, 60 ml of THF, 4.7 g (25 mmol) of tin chloride (II) And 19 ml of hydrochloric acid was added to the mixture, followed by stirring at 70 캜 for 5 hours to effect reaction. After 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 result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the intermediate compound (Z2) (yield: 78%).

(3) Synthesis of polymerizable compound (M2)

3.4 g (10 mmol) of the intermediate compound (Z2), 1.8 g (10 mmol) of 4-methoxycinnamic acid, 0.08 g of DMAP and a small amount of BHT are suspended in 30 ml of methylene chloride under stirring at room temperature. To this, 13 mmol) was added, and the mixture was stirred overnight. The precipitated DCC urea was separated and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of a saturated sodium hydrogencarbonate aqueous solution and 50 mL of saturated brine successively, and dried with magnesium sulfate. The solvent was distilled off, To obtain 4.3 g of a desired polymerizable compound (M2) (yield: 86%). The measurement results of NMR are shown below.

[Synthesis Example 3] Synthesis of polymerizable compound (M3)

(1) Synthesis of intermediate compound (A3)

7.00 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 to a 200 mL eggplant- And the mixture was reacted at 64 ° C for 24 hours with stirring. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck Co., eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the obtained solution to obtain 11.3 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the intermediate compound (A3) (yield: 90%).

(2) Synthesis of intermediate compound (B3)

Then, 2.2 g (10.0 mmol) of pyridinium chlorochromate and 15.0 mL of methylene chloride were added to a 100 mL three-necked flask equipped with a cooling tube and 2.5 g (10.0 mmol) of the intermediate compound (A3) was dissolved in 15.0 mL of methylene chloride And the mixture was further stirred at room temperature for 6 hours. Subsequently, 90 ml of diethyl ether was added to the solution from which oily water adhered to the wall of the flask was removed, and the mixture was filtered under reduced pressure. The solvent was distilled off under reduced pressure to obtain a wet green solid.

This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck Co., eluent: hexane / ethyl acetate = 2/1). The solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the colorless solid was the intermediate compound (B3) (yield: 50%).

(3) Synthesis of intermediate compound (C3)

Subsequently, 1.25 g (5.0 mmol) of the intermediate compound (B3), 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, 0.8 g of Amberlyst (registered trademark) 15 (manufactured by Rohm and Haas) 8.0 g of THF, 0.95 g (5.0 mmol) of tin (II) chloride and 2.0 mL of pure water were added to the mixture, and the mixture was reacted at 70 DEG C for 5 hours with stirring. After completion of the reaction, the reaction mixture was filtered under reduced pressure, mixed with 40 mL of pure water, and 50 mL of diethyl ether was added to the mixture. Extraction was carried out three times.

The organic layer after the extraction was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.5 g of a colorless solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the colorless solid was the intermediate compound (C3) (yield: 94%).

(4) Synthesis of intermediate compound (D3)

35 ml of ethanol, 1.5 g (4.7 mmol) of the intermediate compound (C3) and 5 ml of a 10 mass% sodium hydroxide aqueous solution were added to a 100 ml eggplant-shaped flask equipped with a cooling tube, and the mixture was reacted at 85 ° C for 3 hours with stirring. After completion of the reaction, 300 mL of water and a reaction solution were added to 500 mL of the beaker, and the mixture was stirred at room temperature for 30 minutes. Then, 5 mL of 10% by mass hydrochloric acid was added dropwise and then filtered to obtain 1.3 g of a white solid.

Subsequently, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 (Rohmandhasse) and 20.0 mL of THF were added to a 50 mL branched flask equipped with a cooling tube, and the mixture was reacted by stirring at a temperature of 70 캜 for 5 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off from the solution to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1) to obtain 0.9 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the intermediate compound (D3) (yield: 71%).

(5) Synthesis of polymerizable compound (M3)

3.0 g (10.0 mmol) of the intermediate compound (D3), 1.8 g (10.0 mmol) of methyl 4-hydroxycinnamate, 0.05 g of DMAP and a small amount of BHT were suspended in 60 mL of methylene chloride under stirring at room temperature, to which 2.7 g 13.0 mmol) was added thereto, and the mixture was stirred overnight. The precipitated DCC urea was separated and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of a saturated sodium hydrogencarbonate aqueous solution and 100 mL of saturated brine successively, dried with magnesium sulfate, and the solvent was distilled off under reduced pressure, A yellow solid was obtained. This solid was purified by recrystallization (ethanol). 2.6 g of a desired polymerizable compound (M3) was obtained (yield: 56%).

[Synthesis Example 4] Synthesis of polymer (P1)

2.16 g (4.8 mmol) of a polymerizable compound (M1), 1.80 g (3.6 mmol) of a polymerizable compound (M2), 0.84 g (3.6 mmol) of n-dodecyl acrylate, 48.0 g And 0.10 g of azobisisobutyronitrile (AIBN) were introduced. After the inside of the flask was purged with nitrogen, the reaction was carried out at 60 DEG C for 20 hours with stirring. The resulting reaction solution was poured into 400 mL of methanol, and a white powder was precipitated. The white powder was filtered, and then vacuum-dried at room temperature to obtain 3.60 g of polymer (P1) (yield: 75%). The Mn of the polymer (P1) was 13,258 (Mw / Mn = 2.0).

[Synthesis Example 5] Synthesis of polymer (P2)

0.36 g (0.8 mmol) of the polymerizable compound (M1), 0.60 g (1.2 mmol) of the polymerizable compound (M2), 0.48 g (2.0 mmol) of n-dodecyl acrylate, 0.034 g of AIBN was introduced, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The resulting reaction solution was poured into 200 mL of methanol, and a white powder was precipitated. The white powder was filtered and vacuum-dried at room temperature to obtain 0.95 g of polymer (P3) (yield: 66%). The Mn of the polymer (P2) was 13,647 (Mw / Mn = 2.0).

[Synthesis Example 6] Synthesis of polymer (P3)

(0.4 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.44 g (1.0 mmol) of the polymerizable compound (M3) obtained in Synthesis Example 3, 5.8 g of NMP and 12 mg of AIBN were charged in a flask equipped with a cooling tube , The flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The resulting reaction solution was poured into 200 mL of methanol, and a white powder was precipitated. The white powder was filtered and vacuum-dried at room temperature to obtain 0.5 g of polymer (P3) (yield: 78%). The Mn of the obtained polymer (P3) was 15,877 (Mw / Mn = 3.26).

[2] Preparation of liquid crystal composition, film production and evaluation

The structures of the compounds (1) to (9) used in the following examples are shown below.

Compound (2) was synthesized from an esterification reaction using 4- (4-hydroxyphenyl) benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and sulfuric acid with ethanol.

Compound (6) was synthesized from an esterification reaction using p-anisic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and compound (1) using DMAP.

[Example 1]

150 mg of the polymer (P1) and 7.5 mg of the compound (1) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in toluene / cyclohexanone (75 / 25, w / w) to prepare a liquid crystal composition.

The obtained composition was applied to a glass substrate by a spin coat (300 rpm / 5 seconds, 500 rpm / 20 seconds), prebaked on a hot plate at 55 캜 for 30 seconds, and then cooled to room temperature.

Subsequently, the coated film formed on the glass substrate was irradiated with linearly polarized ultraviolet rays at a rate of 100 mJ / cm ² (illuminance measured at a wavelength of 313 nm) and post baked on a hot plate at 100 캜 for 15 minutes to obtain a film. The obtained film had a film thickness of 1.8 mu m, a retardation value (DELTA d) of 212 nm and DELTA n of 0.118.

[Example 2]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that the compound (2) was used instead of the compound (1). The obtained film had a film thickness of 1.9 mu m, a retardation value of 275 nm, and an n of 0.145.

[Example 3]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that Compound (3) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of Compound (1). The obtained film had a film thickness of 1.8 占 퐉, a retardation value of 235 nm, and? N of 0.127.

[Example 4]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that 3.0 mg of the compound (4) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of 7.5 mg of the compound (1). The obtained film had a film thickness of 1.9 mu m, a retardation value of 211 nm, and a n of 0.111.

[Example 5]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that Compound (5) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of Compound (1). The obtained film had a film thickness of 2.0 占 퐉, a retardation value of 242 nm and? N of 0.120.

[Example 6]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that the compound (6) was used instead of the compound (1). The obtained film had a film thickness of 1.8 占 퐉, a retardation value of 255 nm, and? N of 0.142.

[Example 7]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that Compound (7) (manufactured by ALDRICH) was used instead of Compound (1). The obtained film had a film thickness of 1.8 占 퐉, a retardation value of 240 nm, and? N of 0.133.

[Example 8]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that Compound (8) (manufactured by ALDRICH) was used instead of Compound (1). The obtained film had a film thickness of 2.0 mu m, a retardation value of 207 nm, and DELTA n of 0.103.

[Example 9]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that Compound (9) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of Compound (1). The obtained film had a film thickness of 1.7 mu m, a retardation value of 182 nm, and a n of 0.107.

[Example 10]

150 mg of the polymer (P2) and 7.5 mg of the compound (2) were dissolved in 0.850 g of toluene / cyclohexanone (75/25, w / w) containing 0.02% by mass of a surfactant R-30 To prepare a liquid crystal composition.

The obtained composition was applied to a glass substrate by a spin coat (300 rpm / 5 seconds, 900 rpm / 20 seconds), pre-baked on a hot plate at 55 캜 for 30 seconds, and then cooled to room temperature.

Subsequently, the coated film formed on the glass substrate was irradiated with linearly polarized ultraviolet rays at a rate of 100 mJ / cm ² (illuminance measured at a wavelength of 313 nm) and post baked on a hot plate at 100 캜 for 15 minutes to obtain a film. The obtained film had a film thickness of 1.7 mu m, a retardation value (DELTA d) of 110 nm, and DELTA n of 0.065.

[Example 11]

150 mg of the polymer (P3) and 7.5 mg of the compound (2) were dissolved in 0.850 g of cyclohexanone containing 0.02% by mass of a surfactant R-30 (manufactured by DIC) to prepare a liquid crystal composition.

The obtained composition was applied to a glass substrate by a spin coat (300 rpm / 5 seconds, 500 rpm / 20 seconds), prebaked on a hot plate at 55 캜 for 30 seconds, and then cooled to room temperature.

Subsequently, the coated film formed on the glass substrate was irradiated with linearly polarized ultraviolet rays at a rate of 100 mJ / cm ² (illuminance measured at a wavelength of 313 nm) and post baked on a hot plate at 100 캜 for 15 minutes to obtain a film. The obtained film had a film thickness of 1.5 占 퐉, a retardation value? Nd of 35 nm, and? N of 0.023.

[Comparative Example 1]

A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that the compound (1) was not used. The obtained film had a film thickness of 1.8 占 퐉, a retardation value of 175 nm, and? N of 0.099.

[Comparative Example 2]

A liquid crystal composition and a film were obtained in the same manner as in Example 10 except that the compound (2) was not used. The obtained film had a film thickness of 1.6 占 퐉, a retardation value of 87 nm, and? N of 0.054.

[Comparative Example 3]

A liquid crystal composition and a film were obtained in the same manner as in Example 11 except that the compound (2) was not used. The obtained film had a film thickness of 1.5 占 퐉, a retardation value of 26 nm and? N of 0.018.

The above results are summarized in Table 1.

Figs. 1 to 3 show the angular dependence of the retardation values of the films of Examples 1 to 11 and Comparative Examples 1 to 3. As a result, it was found that a horizontally oriented film was obtained.

Claims (5)

(A) a polymer comprising a repeating unit represented by the following formula [1a], [1b] and [1c]
(B) a compound which does not exhibit liquid crystallinity, represented by the following formula [7a], [7b] or [7c]
(C) an organic solvent
&Lt; / RTI &gt;

[Wherein X and Y are each independently a group represented by the following formula [2] or [3]

(Wherein R < ¹ &gt; is a hydrogen atom or a methyl group, and the broken line is a bonding hand).
M ¹ is a group represented by the following formula [4], M ² is a group represented by the following formula [5] or [6]

(Wherein, s1, s2, s3, s4, s5 and s6 is 1 or 2, each independently, and G ¹ and G ² represents a single bond, -COO- or -OCO-, each independently, R ² and R ³ A halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and the broken line indicates a bonded bond.
A is a linear or branched alkyl group having 2 to 15 carbon atoms,
m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0? p? 0.5 and m + n + p?
q and r each independently represent an integer of 2 to 9.]

(Wherein, R ⁵ and R ⁶ are each independently selected from _{-OH, -OCH 3, -C (=} O) OH, -C (= O) OCH 3, -C (= O) OCH 2 CH 3 or -OC (= O) is CH _3, R ⁷ and R ⁸ are each independently a hydrogen _{atom, -OH, -OCH 3, -C (} = O) OH, -C (= O) OCH 3, -C (= O) OCH ₂ CH ₃ or -OC (═O) CH ₃ , G ³ is a single bond, -C (═O) -O- or -OC (═O) -, G ⁴ is a single bond, -CH═CH - or -CH ₂ CH ₂ -. A single-layer coating type horizontally oriented film produced by using the liquid crystal composition according to claim 1. An optical member comprising the single-layer coating type horizontally oriented film according to claim 2. A process for producing a single-layer coating type horizontally oriented film comprising the step of applying the liquid crystal composition according to claim 1 to a substrate, the step of irradiating polarized light, and the step of post-baking. The method for producing a single-layer coating type horizontally oriented film according to claim 4, wherein the polarized light is linearly polarized ultraviolet light.

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