KR102248600B1 - Polymerizable liquid crystal compound, liquid crystalline polymer, liquid crystalline composition, and single-layer-coated horizontally oriented film - Google Patents

Abstract

(식 중, p는 2∼9의 정수.)

[식 중, X는 식 [3] 또는 [4]로 표시되는 기이고, M은 식 [5]로 표시되는 기이고, m 및 n은 0≤m<100, 0<n≤100, m+n≤100을 충족시키는 수이며, p 및 q는 각각 독립적으로 2∼9의 정수이다.

(식 중, R¹은 수소 또는 메틸이다. 파선은 결합손이다.)

(식 중, s1 및 s2는 1 또는 2이다. G¹은 단결합, -COO- 또는 -OCO-이며, R²는 수소, 할로젠, 사이아노, 알킬 또는 알콕시이다. 파선은 결합손이다.)]A liquid crystal polymer containing a polymerizable liquid crystal compound represented by formula [1] and a repeating unit represented by formulas [2a] and [2b], a liquid crystal composition containing the liquid crystal polymer, and a single layer coating type obtained from the composition Provides a horizontally oriented film.

(In the formula, p is an integer of 2 to 9.)

[Wherein, X is a group represented by formula [3] or [4], M is a group represented by formula [5], m and n are 0≤m<100, 0<n≤100, m+ It is a number that satisfies n≤100, and p and q are each independently integers of 2 to 9.

(In the formula, R ¹ is hydrogen or methyl. The broken line is a bond.)

(In the formula, s1 and s2 are 1 or 2. G ¹ is a single bond, -COO- or -OCO-, and R ² is hydrogen, halogen, cyano, alkyl or alkoxy. The broken line represents a bond. )]

Description

Polymerizable liquid crystal compound, liquid crystal polymer, liquid crystal composition, and single-layer coating type horizontal alignment film {POLYMERIZABLE LIQUID CRYSTAL COMPOUND, LIQUID CRYSTALLINE POLYMER, LIQUID CRYSTALLINE COMPOSITION, AND SINGLE-LAYER-COATED HORIZONTALLY ORIENTED FILM}

The present invention relates to a polymerizable liquid crystal compound, a liquid crystal polymer, a composition containing the polymer, and a single layer coating type horizontal alignment film. Specifically, a material having optical properties suitable for applications such as display devices and recording materials, in particular, polymerizable liquid crystal compounds, liquid crystal polymers that can be suitably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal monitors, It relates to a composition containing this polymer and a single-layer coating type horizontally oriented film obtained from the composition.

Due to the demand for improvement in display quality and weight reduction of a liquid crystal display device, there is a growing demand for a polymer film in which an internal molecular alignment structure is controlled as an optical compensation film such as a polarizing plate or a retardation plate. In order to meet this demand, the development of a film using the optical anisotropy of the polymerizable liquid crystal compound has been made.

The polymerizable liquid crystal compound used herein is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural moiety (a structural moiety having a spacer moiety and a mesogenic moiety), and an acrylic group is widely used as this polymerizable group.

In general, such a polymerizable liquid crystal compound becomes a polymer (film) by a method of polymerization by irradiation with radiation such as ultraviolet rays.

For example, a method of obtaining a polymer by supporting a specific polymerizable liquid crystal compound having an acrylic group between supports and irradiating radiation while maintaining the compound in a liquid crystal state (Patent Document 1), or two kinds of polymerizable properties having an acrylic group A method of obtaining a polymer by adding a photopolymerization initiator to a mixture of liquid crystal compounds or a composition in which a chiral liquid crystal is mixed with the mixture and irradiating with ultraviolet rays (Patent Document 2) is known.

In addition, several single-layer coating types, such as alignment films using polymerizable liquid crystal compounds or polymers that do not require a liquid crystal alignment film (Patent Documents 3 and 4), and alignment films using polymers containing photo-crosslinking sites (Patent Documents 5 and 6) Oriented films have been reported. However, the polymers used in these films have low solubility, and since it is necessary to use a solvent having excellent solubility such as N-methyl-2-pyrrolidone, chloroform, and chlorobenzene as a solvent, the refractive index of the films obtained from these solutions There is a problem that characteristics such as anisotropy (Δn) and haze value may deteriorate.

Further, a material capable of obtaining an oriented film exhibiting a low haze value by a simple process has not been found so far.

Japanese Patent Application Publication No. 62-70407 Japanese Unexamined Patent Application Publication No. Hei 9-208957 European Patent Application Publication No. 1090325 Specification International Publication No. 2008/031243 Japanese Unexamined Patent Application Publication No. 2008-164925 Japanese Unexamined Patent Application Publication No. Hei 11-189665

The present invention has been made in view of the above problems, and a polymerizable liquid crystal compound, a liquid crystal polymer, and a liquid crystal composition comprising the liquid crystal polymer that enable the production of a single layer coating type horizontal alignment film exhibiting a low haze value through a simpler process. And it aims at providing the single-layer coating type horizontal orientation film obtained from this composition.

The present inventors, as a result of repeated intensive studies to solve the above problems, used a liquid crystalline polymer having a cinnamic acid structure on the side chain extending from the γ position of the lactone ring while containing a γ-butyrolactone skeleton in the main chain. By doing so, since a stable network structure is formed after exposure to polarized ultraviolet rays of a low exposure amount, a horizontal alignment film having Δn is obtained without using a liquid crystal alignment film, and a horizontal alignment film having a low haze value can be produced under low temperature conditions. Found that, and completed the present invention.

That is, the present invention provides the following polymerizable liquid crystal compound, liquid crystal polymer, liquid crystal composition, and single-layer coating type horizontal alignment film.

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

(In formula, p represents the integer of 2-9.)

2. A liquid crystal polymer comprising a repeating unit represented by the following formulas [2a] and [2b].

[In the formula, X is a group represented by the following formula [3] or [4],

(In the formula, R ¹ is a hydrogen atom or a methyl group. The broken line is a bond.)

M is a group represented by the following formula [5],

(In the formula, s1 and s2 are each independently 1 or 2. G ¹ is a single bond, -COO- or -OCO-, and R ² is a hydrogen atom, a halogen atom, a cyano group, and a C 1 to C 10 It is an alkyl group or a C1-C10 alkoxy group. The broken line is a bond hand.)

m and n are numbers satisfying 0≦m<100, 0<n≦100, and m+n≦100, respectively, and p and q are each independently integers of 2 to 9.]

3. A liquid crystal composition containing the polymer of 2 and an organic solvent.

4. A single-layer coating type horizontal alignment film obtained by applying the liquid crystal composition of 3 to a substrate and then irradiating polarized light to cure.

5. The single-layer coating type horizontal alignment film of 4 in which the polarization is linearly polarized ultraviolet rays.

6. Optical member provided with 4 or 5 single-layer coating type horizontal alignment films.

The liquid crystalline polymer of the present invention contains a γ-butyrolactone skeleton in its main chain. Therefore, it is possible to produce a single-layer coating type horizontal oriented film showing a low haze value by applying a composition containing this polymer, irradiating linearly polarized light with a low exposure amount at room temperature, and performing post-baking.

[Polymerizable liquid crystal compound]

The polymerizable liquid crystal compound of the present invention is represented by the following formula [1].

In the formula, p represents the integer of 2 to 9, but 3 to 6 are preferable.

A method for synthesizing the polymerizable liquid crystal compound represented by formula [1] will be described later.

[Liquid Crystalline Polymer]

The liquid crystal polymer of the present invention contains a repeating unit represented by the following formulas [2a] and [2b].

In formula [2a], X is a group represented by the following formula [3] or [4].

(In the formula, R ¹ is a hydrogen atom or a methyl group. The broken line is a bond.)

In formula [2a], M is a group represented by the following formula [5].

(In the formula, s1 and s2 are each independently 1 or 2. G ¹ is a single bond, -COO- or -OCO-, and R ² is a hydrogen atom, a halogen atom, a cyano group, and a C 1 to C 10 It is an alkyl group or a C1-C10 alkoxy group. The broken line is a bond hand.)

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms, but in the present invention, a fluorine atom is preferable.

The alkyl group may be any linear, branched or cyclic, and the number of carbon atoms is not particularly limited. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, S-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned. Among these, a linear C1-C10 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group, an ethyl group, etc. are especially preferable.

The alkoxy group may be any linear, branched or cyclic, and the number of carbon atoms is not particularly limited. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n- Hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. are mentioned. Among these, a linear C1-C10 alkoxy group is preferable, a C1-C3 alkoxy group is more preferable, and a methoxy group, an ethoxy group, etc. are especially preferable.

Further, in the above alkyl group and alkoxy group, some or all of the hydrogen atoms may be substituted with halogen atoms such as fluorine atoms.

Particularly preferred as R ² is a hydrogen atom, a fluorine atom, a cyano group, a methyl group, a methoxy group, and the like.

As G ^1, -COO- or -OCO- is preferable.

In the formulas [2a] and [2b], m and n represent the content rate (mol%) of each repeating unit, respectively, 0≤m<100, 0<n≤100, and a number satisfying m+n≤100, respectively However, from the viewpoint of improvement of Δn or improvement of the solubility of the polymer, it is preferably a number that satisfies 0<m≤90 and 10≤n<100, respectively, and satisfies 0<m≤50 and 50≤n<100. It is more preferable that it is a number to be made.

In addition, in formulas [2a] and [2b], p and q are each independently an integer of 2 to 9, but 3 to 6 are preferable, and in particular, as q, 5 or 6 is more preferable.

The liquid crystalline polymer of the present invention preferably has a weight average molecular weight (Mw) of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. When the Mw exceeds 200,000, the solubility in the solvent is lowered and the handling property may decrease. When the Mw is less than 3,000, the curing may be insufficient during thermal curing and the solvent resistance and heat resistance may decrease.

In addition, Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).

Further, the liquid crystal polymer of the present invention may contain other repeating units other than the formulas [2a] and [2b], as long as the effect of the present invention is not impaired. Examples of the polymerizable compound providing the other repeating units include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, and styrene compounds.

The content rate of the other repeating units is preferably 0 to 10 mol% of all repeating units. If the content rate of the other repeating units is too large, the properties of the polymer of the present invention, for example, properties such as liquid crystal properties may be deteriorated.

Further, the liquid crystal polymer of the present invention may be any of a random copolymer, an alternating copolymer, and a block copolymer.

[Synthesis of liquid crystal polymer]

The liquid crystal polymer of the present invention is obtained by polymerizing a polymerizable liquid crystal compound represented by formula [1] and a polymerizable compound represented by formula [6].

[In the formula, R ² , G ¹ , p, q, s1 and s2 are as described above. X'is a polymerizable group represented by the following formula [7] or [8].

(In the formula, R ¹ is the same as above.)]

The polymerizable liquid crystal compound represented by formula [1] and the polymerizable compound represented by formula [6] can be synthesized by combining techniques in organic synthetic chemistry, and the synthesis method is not particularly limited.

For example, it can be synthesized using a method proposed by Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990)). This method is a method of reacting 2-(bromomethyl)acrylic acid and an aldehyde or ketone using _{SnCl 2} as represented by the following synthesis reaction formula A1. In addition, 2-(bromomethyl)acrylic acid can be obtained by the method suggested by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, pp. 56-59) (1983)).

(In the formula, R'represents a monovalent organic group. Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm and Haas. THF represents tetrahydrofuran. Et represents an ethyl group.)

In addition _{, in the reaction of 2-(bromomethyl)acrylic acid using SnCl 2} , an α-methylene-γ-butyrolactone structure can also be obtained by reaction with a corresponding acetal or ketal instead of an aldehyde or ketone. Examples of acetal or ketal include compounds having a dimethylacetal group, a diethylacetal group, a 1,3-dioxane group, and a 1,3-dioxolane group. In the following synthesis reaction formula A2, a synthesis method and a protecting group in the case of using acetal or ketal are shown.

(In the formula, R'is the same as above.)

The compound represented by the formula [1] can be synthesized by the method of the following synthesis scheme B to which the method of the above synthesis scheme A1 or A2 is applied.

(In the formula, p is the same as above.)

The polymerizable compound represented by formula [6] is produced, for example, by the following method.

When G ¹ is -COO-, it is produced by condensing a benzoic acid derivative and a phenol derivative represented by formula [9] in a solvent in the presence of a condensing agent, as represented by the following reaction formula.

(Wherein, R ² , X', q, s1 and s2 are the same as above. DCC is N,N'-dicyclohexylcarbodiimide, and DMAP is N,N-dimethyl-4-aminopyridine. Show.)

When G ¹ is -OCO-, it is prepared by condensing a phenol derivative and a benzoic acid derivative represented by the formula [10] in a solvent in the presence of a condensing agent, as represented by the following reaction formula.

(In the formula, R ² , X', q, s1 and s2 are the same as above.)

Compounds represented by formulas [9] and [10] can be obtained as commercial products from SYNTH0N Chemicals or Midori Chemical Co., Ltd. when X'is a group represented by formula [7].

In addition, the compound represented by formulas [9] and [10], when X'is a group represented by formula [8], by the method of the following synthesis reaction formula C or D applying the method of the synthesis reaction formula A1 or A2 , Can be synthesized.

(In the formula, q and s1 are as described above. Me represents a methyl group. PCC represents pyridinium chlorochromate.)

(In the formula, q and s1 are as described above.)

The method for synthesizing the liquid crystal polymer of the present invention is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, or the like can be employed. Among these, radical polymerization is particularly preferred, and specifically, polymerization may be performed by heating the polymerizable compound in a solvent in the presence of a polymerization initiator.

As a polymerization initiator, it can be suitably selected and used from conventionally known ones. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; Persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; And azo compounds such as azobisisobutyronitrile (AIBN), azobismethylbutyronitrile, and azobisisovaleronitrile. These can be used alone or in combination of two or more.

The amount of the polymerization initiator used is preferably about 0.01 to 0.05 mol per 1 mol of the polymerizable compound.

The reaction temperature may be suitably set from 0°C to the boiling point of the solvent to be used, but it is preferably about 20 to 100°C. The reaction time is preferably about 0.1 to 30 hours.

The solvent used in the polymerization reaction is not particularly limited, and may be appropriately selected from various solvents generally used in the polymerization reaction. Specifically, water; Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, i-pentane Alcohols such as ol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, and cyclohexanol ; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether, tetrahydrofuran, and 1,4-dioxane; Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, and carbon tetrachloride; Ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monobutyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, Aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and anisole; Acetals such as methylal and diethylacetal; Fatty acids such as formic acid, acetic acid and propionic acid; Nitropropane, nitrobenzene, dimethylamine, monoethanolamine, pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, dimethylsulfoxide, acetonitrile And the like. These can be used alone or in combination of two or more.

When the liquid crystalline polymer of the present invention contains repeating units other than formulas [2a] and [2b], as a method for synthesizing, polymerization by coexisting a polymerizable compound providing the other repeating units during the polymerization. Just do it.

[Liquid Crystalline Composition]

The liquid crystal composition of the present invention is obtained by mixing at least one kind of the liquid crystal polymer and an organic solvent.

Examples of the organic solvent include ethers such as tetrahydrofuran and dioxane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Polar solvents such as N,N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as 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; Diglycol 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, etc. are mentioned. These organic solvents can be used alone or in combination of two or more.

Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and the like are preferable.

The amount of the organic solvent to be used is preferably about 60 to 95% by mass in the composition.

Further, to the liquid crystal composition of the present invention, a surfactant may be added for the purpose of improving the affinity with the substrate. Although it does not specifically limit as surfactant, A fluorine type surfactant, a silicone type surfactant, a nonionic surfactant, etc. are mentioned. Among these, a fluorine-based surfactant having a high effect of improving affinity with a substrate is preferable.

As specific examples of the fluorine-based surfactant (hereinafter, brand name), FTOP (registered trademark) EF301, EF303, EF352 (Mitsubishima Terrial Denshi Kasei Co., Ltd.), Megapac (registered trademark) F171, F173, R-30 (DIC Co., Ltd.), FLU0RAD (registered trademark) FC430, FC431 (manufactured by 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Suflon (registered trademark) S-382, SC101, SC102, Although SC103, SCl04, SCl05, and SCl06 (manufactured by AGC Semichemical Co., Ltd.) etc. are mentioned, it is not limited to these. Further, the surfactant may be used alone or in combination of two or more, and the amount of the surfactant is preferably 5 parts by mass or less based on 100 parts by mass of the polymer.

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

Examples of the adhesion promoter include chlorosilane compounds such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; Alkoxysilane compounds such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane ; Silazane compounds such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; Vinyltrichlorosilane, 3-chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glysideoxypropyltrimethoxysilane Silane compounds such as 3-(N-piperidinyl)propyltrimethoxysilane; Benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, urasol, uracil, mercaptoimidazole, mercapto Heterocyclic compounds such as pyrimidine; Urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; Thiourea compounds, etc. are mentioned.

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

[Single layer coating type horizontal orientation film]

The liquid crystal composition of the present invention described above is used as a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, Quartz substrate, ITO substrate, etc.) or film (e.g., triacetylcellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coating, spin coating, flow coating , Roll coating, slit coating, slit coating followed by spin coating, inkjet method, printing method, or the like, to form a coating film, followed by heating and drying with a hot plate or an oven to form a film.

As the conditions for heating and drying, for example, a heating temperature and a heating time appropriately selected within the range of 40 to 100°C and 0.1 to 60 minutes are adopted. The heating temperature and heating time are preferably 40 to 80°C for 0.1 to 2 minutes.

With respect to the film formed in this way, linearly polarized light irradiation is performed and post-baking is performed to obtain a single-layer coating type horizontally oriented film.

As a method of irradiating linearly polarized light, ultraviolet to visible light having a wavelength of 150 to 450 nm is usually used, and it is performed by irradiating linearly polarized light at room temperature or in a heated state. The irradiation dose varies depending on the light to be used, but is preferably ^{approximately 1 to 500 mJ/cm 2.}

In addition, the post-baking may be heated by a hot plate or an oven, and the temperature and time are preferably 90 to 200°C for 2 to 20 minutes, more preferably 90 to 150°C for 5 to 20 minutes.

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

The single-layer coating type horizontal alignment film of the present invention thus obtained is a material having optical properties suitable for use such as a display device or a recording material, and is particularly suitable as an optical compensation film such as a polarizing plate for a liquid crystal monitor and a retardation plate.

Example

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

[1] ¹ H-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 Geol).

[2] Measurement of average molecular weight

Using Showa Denko Corporation Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene), the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured.

[3] Haze value

(Y) The haze value of the film was measured using a Spectral Haze Meter (TC-1800H) manufactured by Tokyo Denshoku.

[4] Film retardation value (△nd)

Using a retardation measuring device (RETS-100, manufactured by Otsuka Denshi Co., Ltd.), Δnd at a wavelength of 550 nm was measured.

[5] observation under a polarization microscope

The identification of the liquid crystal phase was performed by heating a sample on a hot stage (MATS-2002S, manufactured by Tokai Hitto), and observing it with a polarizing microscope (E600-Pol, manufactured by Nikon, Inc.).

[Synthesis Example 1] Synthesis of Polymerizable Compound (M2)

4-(6-acryloyloxy-1-hexyloxy)benzoic acid (manufactured by SYNTH0N Chemicals) 29.2 g (100 mmol), 4-hydroxybiphenyl 17.0 g (100 mmol), DMAP 0.6 g and a small amount of BHT at room temperature. Under stirring, it was suspended in 200 mL of methylene chloride, and a solution in which 24.0 g (116 mmol) of DCC was dissolved in 100 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice in sequence with 0.5 mol/L hydrochloric acid 150 mL, saturated sodium hydrogen carbonate aqueous solution 150 mL, and saturated brine 150 mL, dried over magnesium sulfate, and the solvent was distilled off. Purified by recrystallization with ethanol, 39.6 g of the target polymerizable compound (M2) was obtained (yield 89%). The measurement results of NMR are shown below.

[Synthesis Example 2] Synthesis of Polymerizable Compound (M3)

(1) Synthesis of intermediate compound (P2)

In a 500 mL eggplant flask with a cooling tube, biphenol 18.6 g (100 mmol), 2-(4-bromo-1-butyl)-1,3-dioxolane 10.0 g (48 mmol), potassium carbonate 13.8 g (100 mmol) and 200 mL of acetone was added to obtain a mixture, and the mixture was reacted with stirring at 64° C. for 24 hours. 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, and a white solid was obtained. Next, this solid was mixed with chloroform, filtered, and the solvent was distilled off to obtain 7.2 g of a white solid. The result of measuring this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P2) (yield 48%).

(2) Synthesis of intermediate compound (Q2)

Next, in a 300 mL eggplant flask with a cooling tube, 7.2 g (23 mmol) of the intermediate compound (P2), 4.1 g (25 mmol) of 2-(bromomethyl) acrylic acid, 60 mL of THF, 4.7 g (25 mmol) of tin (II) and 10 19 mL of an aqueous solution of HCl by mass was added to obtain a mixture, followed by stirring at 70° C. for 5 hours to react. 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 measuring this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (Q2) (yield 78%).

(3) Synthesis of polymerizable compound (M3)

Intermediate compound (Q2) 3.4 g (10 mmol), 4-methoxycinnamic acid 1.8 g (10 mmol), DMAP 0.08 g and a small amount of BHT were suspended in 30 mL of methylene chloride under stirring at room temperature, and DCC 2.6 in 15 mL of methylene chloride. A solution in which g (13 mmol) was dissolved was added and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice in sequence with 0.5 mol/L hydrochloric acid 50 mL, saturated sodium hydrogen carbonate aqueous solution 50 mL, and saturated brine 50 mL, dried over magnesium sulfate, and the solvent was distilled off. Purified by recrystallization with ethanol to obtain 4.3 g of the target polymerizable compound (M3) (yield 86%). The measurement results of NMR are shown below.

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

(1) Synthesis of intermediate compound (P1)

In a 100 mL eggplant flask with a cooling tube, methyl 4-hydroxycinnamate 3.6 g (20.0 mmol), 2-(4-bromo-1-butyl)-1,3-dioxolane 4.2 g (20.0 mmol), carbonic acid 5.5 g (40 mmol) of potassium and 50 mL of acetone were added to form a mixture, and the mixture was reacted with stirring at 64° C. for 24 hours. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain 6.0 g of a white solid. The result of measuring this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P1) (yield 98%).

(2) Synthesis of intermediate compound (Q1)

Next, in a 200 mL eggplant flask with a cooling tube, intermediate compound (P1) 6.0 g (20 mmol), 2-(bromomethyl) acrylic acid 3.3 g (20 mmol), THF 55.0 mL, tin (II) 4.3 g (23 mmol) and 17.0 mL of 10% by mass HCl aqueous solution was added to obtain a mixture, followed by stirring at 70°C for 20 hours to react. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 40 mL of pure water, and 50 mL of chloroform was added thereto for extraction. Extraction was performed 3 times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 4.3 g of a viscous liquid. The results of measuring this viscous liquid by NMR are shown below. From this result, it was confirmed that this viscous liquid was an intermediate compound (Q1) (yield 65%).

(3) Synthesis of polymerizable liquid crystal compound (M1)

To a 200 mL eggplant flask with a cooling tube, 60 mL of ethanol, 4.3 g (13 mmol) of the intermediate compound (Q1), and 15 mL of a 10 mass% aqueous sodium hydroxide solution were added to form a mixture, followed by reaction at 85° C. for 5 hours while stirring. After completion of the reaction, 300 mL of water and the reaction solution were added to a 500 mL beaker, stirred at room temperature for 30 minutes, and 15 mL of a 10% by mass HCl aqueous solution was added dropwise, followed by filtration to obtain a white solid.

Next, to a 50 mL eggplant flask equipped with a condenser, the obtained white solid, 15 mL of 10% by mass HCl aqueous solution, and 60.0 mL of tetrahydrofuran were added to form a mixture, followed by stirring at 70 DEG C for 5 hours to react. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain a white solid. This white solid was purified by recrystallization (hexane/tetrahydrofuran = 2/1), and then 3.0 g of a white solid was obtained. The result of measuring this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target polymerizable liquid crystal compound (M1) (yield 73%).

Further, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (M1), at the time of heating, the phase transition was carried out at 85°C to a nematic phase (thermal polymerization at 113°C).

[Example 2] Synthesis of Polymer (1)

To a flask equipped with a cooling tube, 0.64 g (2.0 mmol) of the polymerizable liquid crystal compound (M1) obtained in Example 1, 6.0 g of NMP, and 4 mg of AIBN were charged, and the flask was purged with nitrogen, and then at 60° C. for 20 hours. It was stirred and reacted. The obtained reaction solution was poured into 300 mL of methanol, and white powder was precipitated. After filtering this white powder, it vacuum-dried at room temperature and obtained 0.35g of polymer (1) (yield 55%).

Mn of the obtained polymer (1) was 18,640 and Mw was 35,975 (Mw/Mn=1.93).

[Example 3] Synthesis of Polymer (2)

In a flask equipped with a cooling tube, 0.50 g (1.6 mmol) of the polymerizable liquid crystal compound (M1) obtained in Example 1, 0.369 (0.8 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 1, 9.0 g of NMP and 4 mg of AIBN After equipping the flask with nitrogen, the mixture was stirred at 60° C. for 20 hours to react. The obtained reaction solution was poured into 600 mL of methanol, and white powder was precipitated. After filtering this white powder, it vacuum-dried at room temperature, and obtained 0.65 g of a polymer (2) (yield 76%).

Mn of the obtained polymer (2) was 10,162 and Mw was 30,786 (Mw/Mn=3.0).

[Example 4] Synthesis of Polymer (3)

In a flask equipped with a cooling tube, 0.32 g (1.0 mmol) of the polymerizable liquid crystal compound (M1) obtained in Example 1, 0.44 g (1.0 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 1, NMP 8.0 g and AIBN 3 mg was charged, the flask was purged with nitrogen, and then stirred at 60° C. for 20 hours to react. The obtained reaction solution was poured into 600 mL of methanol, and white powder was precipitated. After filtering this white powder, it vacuum-dried at room temperature and obtained 0.6 g of polymer (3) (yield 79%).

Mn of the obtained polymer (3) was 3,271 and Mw was 4,907 (Mw/Mn=1.5).

[Example 5] Synthesis of Polymer (4)

In a flask equipped with a cooling tube, 0.30 g (0.95 mmol) of the polymerizable liquid crystal compound (M1) obtained in Example 1, 0.98 g (2.2 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 1, NMP 12.0 g and AIBN 5 mg was charged, the flask was purged with nitrogen, and then stirred at 60° C. for 20 hours to react. The obtained reaction solution was poured into 600 mL of methanol, and white powder was precipitated. After filtering this white powder, it vacuum-dried at room temperature and obtained 1.1 g of polymer (4) (yield 86%).

Mn of the obtained polymer (4) was 7,539, and Mw was 16,586 (Mw/Mn=2.2).

[Comparative Example 1] Synthesis of Polymer (5)

In a flask equipped with a cooling tube, 0.62 g (1.4 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 1, 0.30 g (0.6 mmol) of the polymerizable compound (M3) obtained in Synthesis Example 2, 8.3 g of NMP and 17 mg of AIBN Was charged, the flask was purged with nitrogen, and then stirred at 60° C. for 20 hours to halve. The obtained reaction solution was poured into 200 mL of methanol, and white powder was precipitated. After filtering this white powder, it vacuum-dried at room temperature, and obtained 0.65 g of a polymer (5) (yield 71%).

Mn of the obtained polymer (5) was 10,975 and Mw was 19,206 (Mw/Mn=1.75).

[Preparation of composition and evaluation of film production]

A composition was prepared using the polymer obtained in the above Examples and Comparative Examples, and a film was produced according to the following conditions, and its properties were examined.

Film production conditions:

Spin coating: 300rpm/5sec, 1000rpm/20sec

Pre-baking: 55℃/30sec (hot plate)

Exposure: linearly polarized ultraviolet rays, vertical irradiation, wavelength 313 nm

[Example 6]

150 mg of polymer (2) and 0.3 mg of R-30 (a surfactant manufactured by DIC Corporation, as follows.) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (2).

This solution was applied to a glass substrate by spin coating, prebaked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

Next, the coating film formed on the glass substrate ^{was exposed to light at an irradiation dose of 5 mJ/cm 2} , and then post-baked at 140° C./15 minutes (on a hot plate). The film thickness of the obtained film was 1.0 µm, and when it was observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the ?nd was 36 nm, and the haze value was 0.07%.

[Example 7]

150 mg of polymer (3) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (3).

This solution was applied to a glass substrate by spin coating, prebaked, and then allowed to cool to room temperature. At this time, the film obtained on the substrate was transparent.

Next, the coating film formed on the glass substrate ^{was exposed to light at an irradiation dose of 5 mJ/cm 2} , and then post-baked at 110° C./15 minutes (on a hot plate). The film thickness of the obtained film was 0.8 µm, and when it was observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the ?nd was 58 nm, and the haze value was 0.06%.

[Example 8]

150 mg of polymer (4) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (4).

This solution was applied to a glass substrate by spin coating, prebaked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

Next, the coating film formed on the glass substrate ^{was exposed to light at an irradiation dose of 5 mJ/cm 2} , and then post-baked at 110° C./15 minutes (on a hot plate). The film thickness of the obtained film was 0.8 µm, and when it was observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the ?nd was 33 nm, and the haze value was 0.34%.

[Comparative Example 2]

150 mg of polymer (5) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (5).

This solution was applied to a glass substrate by spin coating, prebaked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

Next, the coating film formed on the glass substrate ^{was exposed to light at an irradiation dose of 500 mJ/cm 2} , and then post-baked at 100°C for 10 minutes (on a hot plate). The film thickness of the obtained film was 0.8 µm, and when it was observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the ?nd was 62 nm, and the haze value was 2.1%.

The above results are put together and shown in Table 1 below.

polymer Film thickness △nd (nm) Haze value (%) Example 6 (2) 1.0 36 0.07 Example 7 (3) 0.8 58 0.06 Example 8 (4) 0.8 33 0.34 Comparative Example 2 (5) 0.8 62 2.1

Claims (6)

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

(In formula, p represents the integer of 2-9.) A liquid crystalline polymer comprising a repeating unit represented by the following formulas [2a] and [2b].

[In the formula, X is a group represented by the following formula [3] or [4],

(In the formula, R ¹ is a hydrogen atom or a methyl group. The broken line is a bond.)
M is a group represented by the following formula [5],

(In the formula, s1 and s2 are each independently 1 or 2. G ¹ is a single bond, -COO- or -OCO-, and R ² is a hydrogen atom, a halogen atom, a cyano group, and a C 1 to C 10 It is an alkyl group or a C1-C10 alkoxy group. The broken line is a bond hand.)
m and n are numbers satisfying 0≤m<100, 0<n≤100, and m+n≤100, respectively,
p and q are each independently an integer of 2 to 9.] A liquid crystal composition containing the polymer according to claim 2 and an organic solvent. A single-layer coating type horizontal alignment film obtained by applying the liquid crystal composition according to claim 3 to a substrate and then irradiating polarized light to cure. The single layer coating type horizontal alignment film according to claim 4, wherein the polarized light is linearly polarized ultraviolet rays. An optical member comprising the single-layer coating type horizontal alignment film according to claim 4 or 5.