KR101648041B1 - Polymerizable compound - Google Patents

Abstract

으로 표시되는 중합성 화합물을 제공하며, 당해 화합물을 구성 부재로 하는 액정 조성물, 또한, 당해 액정 조성물을 사용한 광학 이방체, 또는 액정 디바이스를 제공한다. 본원 발명의 중합성 화합물은, 다른 액정 화합물과의 뛰어난 용해성을 가지므로 중합성 조성물의 구성 부재로서 유용하다. 또한, 본원 발명의 중합성 화합물을 함유하는 중합성 조성물은, 액정상 온도 범위가 넓어 당해 중합성 조성물을 사용한 광학 이방체는, 내열성이 높고, 편향판, 위상차판 등의 용도에 유용하다.A problem to be solved by the present invention is to provide a polymerizable liquid crystal composition which has excellent solubility with other liquid crystal compounds and has excellent heat resistance and mechanical strength when the polymerizable liquid crystal composition is cured .
[MEANS FOR SOLVING PROBLEMS]

A liquid crystal composition comprising the compound as a constituent member, and an optical anisotropic member or a liquid crystal device using the liquid crystal composition. The polymerizable compound of the present invention has excellent solubility with other liquid crystal compounds, and thus is useful as a constituent member of a polymerizable composition. Further, the polymerizable composition containing the polymerizable compound of the present invention has a wide temperature range in the liquid crystal phase, and thus the optical anisotropic material using the polymerizable composition has high heat resistance and is useful for applications such as a deflection plate and a retardation plate.

Description

[0001] POLYMERIZABLE COMPOUND [0002]

The present invention relates to a polymerizable compound, a liquid crystal composition containing the compound, and an optically anisotropic or liquid crystal device which is a cured product of the liquid crystal composition.

2. Description of the Related Art In recent years, with the advancement of the information society, the importance of an optical compensation film used for a deflecting plate, a phase difference plate, and the like required for a liquid crystal display has been increasing more and more. In an optical compensation film requiring high durability and high performance, Have been reported. Optical anisotropies used in optical compensation films and the like are not only optical characteristics but also factors such as polymerization rate, solubility, melting point, glass transition point, transparency of polymer, mechanical strength, surface hardness and heat resistance.

Conventionally, as a compound constituting the polymerizable liquid crystal composition, a compound having a structure in which a 1,4-phenylene group is linked by an ester bond (see Patent Document 1) and a compound having a fluorene group (see Patent Document 2) . However, the polymerizable compound described in the cited document has problems such as low solubility. On the other hand, although a polymerizable compound having a cinnamic acid structure has been disclosed for improving solubility (see Patent Document 3), it is a target compound for disturbing alignment by photoisomerization and is easily cis-trans isomerized The heat resistance of the phase difference for the purpose and the mechanical strength such as surface hardness are not improved. Is a polymerizable compound capable of utilizing optical isomerization, and heat resistance and mechanical strength are not improved by heat and light.

Japanese Patent Publication No. 10-513457 Japanese Patent Application Laid-Open No. 2005-60373 Japanese Patent Application Laid-Open No. 2005-120091

It is an object of the present invention to provide a polymerizable liquid crystal composition which has excellent solubility with other polymerizable compounds and liquid crystal compounds when constituting a polymerizable liquid crystal composition and is excellent in heat resistance and polymerizability Compound. ≪ / RTI > And to provide a useful material for a polymer-stabilized liquid crystal display device.

The inventors of the present invention have studied various substituents in a polymerizable compound and found that a polymerizable compound having a specific structure can solve the above-mentioned problems, thereby completing the present invention.

The present invention relates to a compound represented by the general formula (I)

(Wherein R ¹ is any one of the following formulas (R-1) to (R-15)

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, A halogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group or a nitro group, S ¹ is a group in which oxygen atoms are not directly bonded to each other, -, or an alkylene group having 1 to 12 carbon atoms which may be substituted with -OCOO-, -C≡C-, or a single bond, L ¹ and L ² independently of one another are a single bond, -O-, -S- , -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -CO-NR ¹¹ - _{^{NR 11 -CO-, -SCH 2 -,}} -CH 2 S-, -CH = CH-COO-, -COO-CH = CH-, -CH = CH-OCO-, -OCO-CH = CH-, - COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -OCOCH ₂ -, -CH ₂ COO-, -CH = CH-, -, -CH = CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - I Out (in the formula, R ¹¹ represents an alkyl group of 1 to 4 carbon atoms), M ¹ and M ² are, each independently, 1,4-phenylene, 1,4-cyclohexylene group, a pyridine-2,5 each other Diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane- M ³ represents a 1,4-phenylene group, a 1,3,4-benzenetriyl group, a 1,3,5-benzenetriyl group, a 1,3,4,5-benzenetetrayl group, a pyridine- Diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group, a 1,3-dioxane-2,5-diyl group, A cyclohexanetriyl group or a 1,3,4-cyclohexanetriyl group, M ¹ , M ² and M ³ are each independently an unsubstituted or a substituted or unsubstituted alkyl group, halogenated alkyl group, An alkoxy group, a halogen group, a cyano group, or a nitro group, m represents 1, 2 or 3, n represents 0, 1 or 2, When m and n represent 2 or 3, L ¹ , L ² , M ¹ and / or M ² present in two or three groups may be the same or different and Z represents H, F, Cl, CN, SCN, OCF ₃ , or an alkyl group having 1 to 12 carbon atoms. The alkyl group is a group in which oxygen atoms are not directly bonded to each other, and the methylene group is an oxygen atom, a sulfur atom, -CO-, -COO-, -OCO-, , -CH = CH-, or -C? C-, or Z is -L ³ -S ² -R ^{2 wherein} R ² is R ¹ , S ² is S ¹ and L ³ Represents the same meaning as L < ¹ >), k represents 1, 2 or 3, and when k represents 2 or 3, Z may be the same or different) A liquid crystal composition using the liquid crystal composition, and an optical anisotropic element or a liquid crystal display element using the liquid crystal composition.

The polymerizable compound of the present invention has excellent solubility with other polymerizable compounds and liquid crystal compounds, and therefore is useful as a constituent member of the polymerizable composition. Further, the polymerizable composition containing the polymerizable compound of the present invention has a high curing rate and a wide temperature range of the liquid crystal phase. An optically anisotropic material using such a polymerizable composition has high heat resistance and is useful for applications such as a deflection plate and a retardation plate, and is also useful for a polymer stabilized liquid crystal display device.

In the general formula (I), R ¹ and R ² independently represent a polymerizable group, but specific examples of the polymerizable group include the following structures.

These polymerization units are cured by radical polymerization, radical addition polymerization, cation polymerization, and anionic polymerization. (R-1), formula (R-2), formula (R-4), formula (R-5) (R-11), formula (R-13) or formula (R-15) R-13) is more preferable, and the formula (R-1) and the formula (R-2) are more preferable.

S ¹ and S ² independently represent a spacer group or a single bond, but the spacer group is preferably an alkylene group having 2 to 6 carbon atoms or a single bond, and the alkylene group is an organic group in which oxygen atoms are not directly bonded to each other, The atom may be substituted with an oxygen atom, -COO-, -OCO-, or -OCOO-.

L ^1, L ² and L ³ are independently of each other, a single _{bond, -OCH 2 -, -C 2 H} 4 -, -CH 2 O-, -COO-, -OCO-, -OCOOCH 2 -, -CH 2 OCOO-, -CH = CH-COO-, -OOC-CH = CH-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, it is preferable, -CH ₂ O- or more - CF ₂ O- are preferable, and in terms of ease of manufacture, and the liquid crystal alignment property, a single bond, -COO-, -OCO-, -OCH _2.

M ¹ and M ² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, -Diiyl group is preferable, M ³ is a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine- Diyl group, a tetrahydronaphthalene-2,6-diyl group, a 1,3-dioxane-2,5-diyl group, a 1,3,5-benzenetriyl group, 1,3,5-benzenetetrayl group, 1,3,5-cyclohexanetriyl group or 1,3,4-cyclohexanetriyl group are preferable, and 1,4-phenylene group, 1,4-cyclohex More preferably a silylene group, a 1,3,5-benzenetriyl group, a 1,3,4-benzenetriyl group or a naphthalene-2,6-diyl group. Z represents a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or -L ³ -S ² -R ^{2 wherein} R ² , S ² and L ³ are R ¹ , S ¹ And L < ¹ > have the same meaning). m represents 1, 2 or 3, and n represents 0, 1 or 2, particularly preferably m = 1 and q = 0 or 1. k is preferably 1 or 2.

More specifically, the compound represented by the general formula (I) is preferably a compound represented by the following general formulas (I-1) to (I-24).

(Wherein p and q each represent an integer of 0 to 12, but when p or / and q are 0 and oxygen atoms are directly connected to each other, one oxygen atom is removed)

The compound of the present invention can be synthesized by a synthesis method described below.

(Production method 1) Production of a compound represented by the general formula (I-5)

A biphenyl derivative (S-1) is obtained by a Mitsubishi-Heck reaction with a palladium catalyst of 4-bromo-4'-hydroxybiphenyl and tert-butyl acrylate, A biphenyl derivative (S-2) having an acryloyl group is obtained by an esterification reaction using a dehydrating condensing agent such as monooxyhexyloxy) benzoic acid and dicyclohexylcarbodiimide.

In addition, trifluoroacetic acid removes the tert-butyl group to obtain a biphenyl derivative (S-3) converted to a carboxyl group.

Subsequently, the objective compound (I-5) can be obtained by an esterification reaction using a dehydrating condensing agent such as 4- (2-acryloyloxy) ethylphenol and dicyclohexylcarbodiimide.

(Production Method 2) Production of a compound represented by the general formula (I-8)

Fluorobenzaldehyde, 2-fluoro-4-bromobiphenyl and acetyl chloride were subjected to a Friedel-Crafts reaction using aluminum chloride (III) to obtain fluorobiphenyl compounds substituted with fluorine atoms by formic acid prepared from formic acid and hydrogen peroxide S-4). Further, a biphenyl derivative (S-5) was obtained by a Mizoroki-hehe reaction with a palladium catalyst with tert-butyl acrylate, followed by the addition of 6- (3-acryloylpropyloxy) -2-naphthoic acid and dicyclo A biphenyl derivative (S-6) having an acryloyl group is obtained by an esterification reaction using a dehydrating condensing agent such as hexyl carbodiimide. In addition, trifluoroacetic acid removes the tert-butyl group to obtain a biphenyl derivative (S-7) converted to a carboxyl group.

Subsequently, the objective compound (I-8) can be obtained by an esterification reaction using a dehydrating condensing agent such as 4- (6-acryloyloxyhexyloxy) phenol and dicyclohexylcarbodiimide.

(Production method 3) Production of a compound represented by the general formula (I-10)

a biphenylcarboxylic acid derivative (S-8) is obtained by etherification reaction with p-hydroxybiphenylcarboxylic acid ethyl ester and 6-chlorohexanol using a base such as potassium carbonate and hydrolysis with sodium hydroxide. Then, an acrylic group-containing biphenylcarboxylic acid derivative (S-9) is obtained by esterification reaction of acrylic acid and a biphenylcarboxylic acid derivative (S-8) using p-toluenesulfonic acid.

Subsequently, by an esterification reaction using a dehydrating condensation agent such as dicyclohexylcarbodiimide with the biphenyl derivative (S-1) synthesized in Production Method 1 and the biphenylcarboxylic acid derivative (S-9) having an acrylic group, To obtain a biphenyl derivative having a diaryl group, and further, a biphenyl derivative (S-10) converted to a carboxyl group by eliminating the tert-butyl group with trifluoroacetic acid is obtained. Subsequently, an objective compound (I-10) can be obtained by an esterification reaction using a dehydrating condensing agent such as 4- (3-acryloyloxypropoxy) phenol and dicyclohexylcarbodiimide.

(Production process 4) Production of a compound represented by the general formula (I-14)

Except that 6- (3-acryloylpropyloxy) -2-cyclohexanecarboxylic acid was used instead of 6- (3-acryloylpropyloxy) -2-naphthoic acid in Production Method 2 to obtain the objective compound -14) can be obtained.

(Production method 5) Production of a compound represented by the general formula (I-18)

By an esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide of biphenyl derivative (S-1) synthesized in Production Method 1 and 4- (2-acryloyloxyethoxy) benzoic acid, To obtain a biphenyl derivative having a diaryl group, and further, a biphenyl derivative (S-11) in which tert-butyl group is eliminated by trifluoroacetic acid to convert it into a carboxylic acid group is obtained.

Subsequently, a phenol compound (S-12) having a methacryl group is obtained by esterification reaction of p-hydroxyphenylpropionic acid with hydroxyethyl methacrylate using p-toluenesulfonic acid. Subsequently, an objective compound (I-18) can be obtained by an esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide with a biphenyl derivative (S-11).

(Production method 6) Production of a compound represented by the general formula (I-22)

Bromo-3-chloropropane was etherified in the presence of a base such as sodium hydroxide to obtain an oxetane derivative (S-13 (trade name, manufactured by TOAGOSEI Co., ). Subsequently, an etherification reaction with methyl p-hydroxybenzoate in the presence of a base such as potassium carbonate or the hydrolysis with sodium hydroxide yields benzoic acid (S-14) having an oxetane group. Then, an esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide with the biphenyl derivative (S-1) synthesized in Production Method 1, and an esterification reaction with a tertiary butyl group by trifluoroacetic acid by eliminating an oxetanyl group To obtain a carboxylic acid derivative (S-15).

Subsequently, hydroquinone monotetrahydropyranyl ether and oxetane derivative (S-13), which are a reaction product of hydroquinone and 3,4-dihydro-2H-pyran, are etherified in the presence of a base such as potassium carbonate, The protecting group of the phenol is removed by hydrochloric acid to obtain a phenol derivative (S-16). The target compound (I-22) can also be obtained by an esterification reaction using a dehydrating condensing agent such as dicyclohexylcarbodiimide with a carboxylic acid derivative (S-15) having an oxetanyl group.

(Production Method 7) Production of a compound represented by the general formula (I-19)

A protocatechuic acid derivative (S-17) is obtained by esterifying 4-benzyloxyphenol and protocatechuic acid using p-toluenesulfonic acid. Subsequently, the etherification of 6-chlorohexanol and protocatechioic acid derivative (S-17) in the presence of a base such as potassium carbonate and the removal of the benzyl group by a hydrogenation reaction using palladium carbon yielded a prototype having a hydroxyl group and a phenol group (S-18). ≪ / RTI > Followed by esterification reaction with acrylic acid using p-toluenesulfonic acid to obtain a compound (S-19) having two acrylic groups.

(I-22) can be obtained by an esterification reaction of a biphenyl derivative (S-3) and a compound (S-19) having two acrylic groups with a dehydrating condensation agent such as dicyclohexylcarbodiimide have.

The compounds of the present invention can be used in nematic liquid crystal, smectic liquid crystal, chiral nematic, chiral masked, and cholesteric liquid crystal compositions. In addition to using at least one compound of the present invention, the liquid crystal composition of the present invention may be added with any other polymerizable compound in an arbitrary range. The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is particularly preferably an acryloyloxy group or methacryloyloxy group as the polymerizable functional group. The polymerizable liquid crystal compound preferably has two or more polymerizable functional groups in the molecule. When the liquid crystal composition of the present invention is a cholesteric liquid crystal, addition of a chiral compound is preferred. A liquid crystal composition having no polymerizable group may also be added, and the liquid crystal composition thus obtained is particularly useful for a polymer-stabilized liquid crystal display device.

Specific examples of the polymerizable compound other than the present invention include, but not limited to, compounds containing a compound represented by the general formula (I), and as the polymerizable liquid crystal compound used in combination, acryloyloxy group (R-1) or Methacryloyloxy group (R-2) is preferable, and it is more preferable to have two or more polymerizable functional groups in the molecule.

Specific examples of the polymerizable liquid crystal compound used in combination include compounds represented by the general formula (II)

(Wherein A is an alkyl group having 1 to 12 carbon atoms, H, F, Cl, CN, SCN, OCF ₃ and oxygen atoms not directly bonded to each other, -, may be substituted by -COO-, -OCO-, -OCOO, -CH = CH-, -C≡C-, or A is an -L ⁶ -S ⁴ -R ^4, R ³ and R ^4, S ³ and S ⁴ independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, wherein at least one -CH ₂ - is a bond in which oxygen atoms are not bonded directly to each other, L ⁴ , L ⁵ and L ⁶ independently of one another are a single bond, -O-, -S-, -OCH ₂ -, -OCH ₂ -, -OCH ₂ -, or -OCH ₂ - -CH ₂ O-, -CO-, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, SCH ₂ -, -CH ₂ S-, -CH═CH-COO-, -OOC-CH═CH-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -OCOCH ₂ -, -CH ₂ COO-, -CH = CH-, -C ₂ H ₄ -, -CF = CH-, -CH = CF-, -CF ₂ - -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - or -C≡C-, wherein R ¹¹ represents a carbon atom 1 M ⁴ and M ⁵ are, independently of each other, 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5 Diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, but M ⁴ and M ⁵ are independently 1, 2 or 3, provided that 1 is 2 or 3, and R < 3 > is hydrogen, , Two or three L ⁵ and M ⁵ present may be the same or different).

In particular, L ⁴ , L ⁵ and L ⁶ independently of one another represent a single bond, -O-, -COO- or -OCO-, M ³ and M ⁴ independently of one another are 1,4-phenylene , A 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, and a naphthalene-2,6-diyl group.

Specifically, the compound represented by the general formula (II) is preferably a compound represented by the general formula (II-1) to the general formula (II-22).

(Wherein a and b represent an integer of 0 to 12, but when a or / and b are 0 and oxygen atoms are directly connected to each other, one oxygen atom is removed)

The polymerizable liquid crystal compound used in the liquid crystal composition of the present invention is preferably blended with the general formulas (II-23) to (II-33) for the purpose of controlling the liquid crystal temperature range, birefringence, and viscosity reduction Do.

(Wherein a and b represent an integer of 0 to 12, but when a or / and b are 0 and oxygen atoms are directly connected to each other, one oxygen atom is removed)

In the case where the liquid crystal composition of the present invention is a cholesteric liquid crystal, a chiral compound is generally added, but specific compounds are represented by the general formulas (III-1) to (III-8). The blending amount of the chiral compound is preferably from 0.5 to 30% by weight, and more preferably from 2 to 20% by weight, based on the liquid crystal composition.

(Wherein p and q each represent an integer of 0 to 12, but when p or / and q are 0 and oxygen atoms are directly connected to each other, one oxygen atom is removed)

Further, the liquid crystal composition of the present invention may be added to a liquid crystal composition having no polymerizable group, or may be added to a liquid crystal device such as a conventional liquid crystal device such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) (Thin film transistor) liquid crystal and the like, ferroelectric liquid crystal compositions, and the like.

As the compound having a polymerizable functional group, a compound that does not exhibit liquid crystallinity may be added. Such a compound is not particularly limited as long as it is generally recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field, but the amount thereof to be added needs to be adjusted so as to exhibit liquid crystallinity as a composition.

Since the liquid crystal composition of the present invention has a biphenyl skeleton in which? Electrons are widely conjugated, polymerization by heat and light is possible without adding a polymerization initiator, but addition of a photopolymerization initiator is preferable. The concentration of the photopolymerization initiator to be added is preferably from 0.1 to 10 mass%, more preferably from 0.2 to 10 mass%, and particularly preferably from 0.4 to 5 mass%. Examples of the photoinitiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.

In order to improve the storage stability of the liquid crystal composition of the present invention, a stabilizer may be added. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tertiary butyl catechol, pyrogallol, thiophenols, nitro compounds,? -Naphthyl amines,? -Naphthols, And the like. When the stabilizer is used, the addition amount is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and particularly preferably 0.03 to 0.1% by mass with respect to the liquid crystal composition.

When the liquid crystal composition of the present invention is used as a raw material for a retardation film, a polarizing film or an orientation film, a printing ink, a coating material, a protective film, etc., a metal, a metal complex, a dye, a pigment, , A phosphorescent material, a surfactant, a leveling agent, a thixotropic agent, a gelling agent, a polysaccharide, an ultraviolet absorber, an infrared absorber, an antioxidant, an ion exchange resin and titanium oxide.

Next, the optical anisotropic medium of the present invention will be described. The optically anisotropic material produced by polymerizing the liquid crystal composition of the present invention can be used for various purposes. For example, when the polymerizable liquid crystal composition of the present invention is polymerized in a state in which it is not oriented, it can be used as a light scattering plate, a polarizing plate, and a Moire pattern prevention plate. The optically anisotropic material produced by polymerization in the state in which the polymerizable liquid crystal composition of the present invention is oriented is useful because it has optical anisotropy in physical properties. Such optically anisotropic medium is, for example, to the rubbing of the polymerizable liquid crystal composition of the surface of the invention, the rubbing-treated substrate, or a substrate surface to form an organic thin film with a cloth such as a cloth-treated substrate, or SiO ₂ everywhere The liquid crystal of the present invention can be produced by, for example, carrying on a substrate having a deposited alignment film or sandwiching the substrate between substrates, and then polymerizing the liquid crystal of the present invention.

Examples of the method for carrying the polymerizable liquid crystal composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping and printing. In the coating, an organic solvent may be added even if the polymerizable liquid crystal composition is used as it is. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, Methoxy-2-ethoxyethane, propylene glycol monomethyl acetate, and N-methylpyrrolidone. These may be used singly or in combination, and may be suitably selected in consideration of the vapor pressure thereof and the solubility of the polymerizable liquid crystal composition. The addition amount thereof is preferably 90% by weight or less. As a method of volatilizing the added organic solvent, natural drying, heat drying, vacuum drying, and vacuum drying can be used. In order to further improve the coatability of the polymerizable liquid crystal material, it is effective to provide an intermediate layer such as a polyimide thin film on the substrate, or to add a leveling agent to the polymerizable liquid crystal material. The provision of the intermediate layer such as the polyimide thin film on the substrate is also effective as a means for improving the adhesion property when the adhesion between the optical anisotropy obtained by polymerizing the polymerizable liquid crystal material and the substrate is poor.

As a method of sandwiching the liquid crystal composition between the substrates, an injection method using a capillary phenomenon can be mentioned. Means for reducing the space formed between the substrates and then injecting the liquid crystal material is also effective.

Examples of the orientation treatment other than the rubbing treatment or the SiO ₂ sidewall deposition include the use of the flow alignment of the liquid crystal material and the use of electric fields or magnetic fields. These alignment means may be used alone or in combination. As an alignment treatment method instead of rubbing, a photo alignment method may also be used. This method can be carried out by, for example, an organic thin film having a functional group capable of photo-dimerizing (photodimerizing) reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group capable of isomerizing into light, An alignment film is formed by irradiating a thin film with polarized light, preferably polarized ultraviolet light. By applying a photomask to this photo-alignment method, patterning of the orientation can be easily achieved, so that it becomes possible to precisely control the molecular orientation in the optical anisotropic body.

As for the shape of the substrate, it may have a curved surface as a constituent part in addition to a flat plate. The material constituting the substrate can be used regardless of whether it is an organic material or an inorganic material. Examples of the organic material to be used as the material of the substrate include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethylmethacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene , Polyarylate, polysulfone, triacetylcellulose, cellulose, polyetheretherketone and the like. Examples of the inorganic material include silicon, glass, calcite and the like.

When appropriate orientation can not be obtained by rubbing these substrates with cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film may be formed on the substrate surface by rubbing with cloth or the like by a known method. The polyimide thin film which gives a pretilt angle which is used in a normal TN liquid crystal device or STN liquid crystal device is particularly preferable because it can more precisely control the molecular alignment structure inside the optical anisotropic body.

When the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the above-mentioned polyimide thin film on the electrode.

As a method for polymerizing the liquid crystal composition of the present invention, it is preferable to proceed with rapid polymerization, and therefore, a method of polymerizing by irradiation with active energy rays such as ultraviolet rays or electron beams is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out while the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy ray. In addition, a means for changing the alignment state of the non-polymerized portion by changing the conditions such as the electric field, the magnetic field, or the temperature after polymerizing only a specific portion by using a mask at the time of light irradiation, May be used. The temperature at the time of irradiation is preferably within the temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, when an optically anisotropic substance is to be produced by photopolymerization, it is preferable to polymerize at a temperature as close as possible to the room temperature, that is, at a temperature of typically 25 ° C, as far as possible in order to avoid unintentional induction of thermal polymerization. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the strength is 0.1 mW / cm ² or less, a long time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is ² W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition may be deteriorated .

The optically anisotropic material of the present invention obtained by polymerization can also be subjected to heat treatment in order to alleviate initial characteristic changes and to exhibit stable characteristics. The temperature of the heat treatment is preferably in the range of 50 to 250 占 폚, and the heat treatment time is preferably in the range of 30 seconds to 12 hours. The optically anisotropic material of the present invention produced by such a method may be used singly or in combination without peeling from the substrate. The obtained optical anisotropic material may be laminated or may be used by being attached to another substrate.

Further, the polymerizable compound of the present invention may be added to the non-polymerizable liquid crystal composition. In the case of a liquid crystal display element, an example has been reported in which a polymerizable compound is added to a liquid crystal medium to improve display characteristics. In order to control the orientation of liquid crystal molecules in the liquid crystal cell, the present compound may also be used. Specific liquid crystal compositions include nematic liquid crystal compositions used in conventional liquid crystal display devices such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, TFT (thin film transistor) liquid crystal, And the like.

As the compound having a polymerizable functional group, a compound that does not exhibit liquid crystallinity may be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field. The amount thereof to be added needs to be adjusted so as to exhibit liquid crystallinity as a composition. ), But it is preferable that the polymerizable compound contains 1 to 5 kinds, particularly preferably 1 to 3 kinds. If the content of the compound represented by the general formula (I) is too small, the alignment regulating force against the non-polymerizable liquid crystal compound becomes weak. If the content is too high, the required energy at the time of polymerization increases and the amount of the polymerizable compound The lower limit value is preferably 0.01% by mass, more preferably 0.03% by mass, and the upper limit value is preferably 2.0% by mass, more preferably 1.0% by mass.

[Example]

Hereinafter, the present invention will be described in further detail with reference to Examples. However, the present invention is not limited to these Examples. In the compositions of the following Examples and Comparative Examples, "%" means "% by mass".

(Example 1)

12.8 g (96 mmol) of aluminum (III) chloride and 100 ml of dichloromethane were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer and stirred. Subsequently, 8.4 g (110 mmol) of acetyl chloride was slowly added dropwise over 90 minutes, and 80 ml of a dichloromethane solution of 20 g (80 mmol) of 4-bromo-2-fluorobiphenyl was slowly added dropwise over 2 hours. After completion of the dropwise addition, stirring was further continued for 2 hours to terminate the reaction. The reaction solution was slowly poured into 500 ml of ice water, extracted with dichloromethane, and the organic layer was washed with pure water and saturated brine. After the solvent was distilled off, drying was performed to obtain 23 g of an acetyl group-introduced compound. Then, 23 g of the acetyl group-introduced compound and 300 ml of formic acid were charged into a reaction vessel equipped with a stirrer, a condenser and a thermometer, 20 ml of 34.5% aqueous hydrogen peroxide was added, and the mixture was heated to reflux for 6 hours. After completion of the reaction, 450 ml of a 10% sodium hydrogen sulfite aqueous solution was added to decompose the peroxide. The precipitated solid was filtered and dissolved in ethyl acetate, and the organic layer was washed with water and saturated brine. After the solvent was distilled off, purification was carried out on a silica gel column twice (weight ratio) to obtain 18 g of a compound represented by the formula (1).

10 g (37.4 mmol) of 4-bromo-3-fluorobiphenyl, 5.7 g (44.8 mmol) of tert-butyl acrylate, 5.6 g (56 mmol) of triethylamine, 410 mg of palladium acetate and 300 ml of dimethylformamide were charged and reacted by heating the reactor at 100 占 폚 under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with a 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was carried out with a 2-fold (weight ratio) silica gel column to obtain 10.5 g of a compound represented by the formula (2).

Subsequently, 10 g (31 mmol) of the compound represented by the above formula (2), 7.7 g (31 mmol) of 4- (3-acryloyloxypropyloxy) benzoic acid and 30 ml of dimethylaminopyridine were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer And 100 ml of methylene chloride are charged, and the reaction vessel is maintained at 5 캜 or lower in the ice-cooled bath. 4.6 g (37 mmol) of diisopropylcarbodiimide was slowly added dropwise in an atmosphere of nitrogen gas. After completion of dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, followed by washing with a 10% aqueous hydrochloric acid solution, washing with saturated brine, and drying the organic layer with anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out by using a silica gel column twice in weight (weight ratio) and recrystallization from methylene chloride / methanol gave 11 g of the aimed compound represented by formula (3).

In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 11 g of the compound represented by the formula (3) was dissolved in 15 ml of methylene chloride, 15 ml of trifluoroacetic acid was added dropwise, and the mixture was stirred at room temperature for 30 minutes. Thereafter, pure water was added to precipitate a solid. The solid was dissolved in 150 ml of ethyl acetate and 150 ml of tetrahydrofuran, and the organic layer was washed with saturated brine. The solvent was distilled off to obtain 8 g of a compound represented by the formula (4).

Subsequently, 8 g (15.5 mmol) of the compound shown in the above formula (4), 3 g (15.5 mmol) of acrylic acid 2- (4-hydroxyphenyl) ethyl, and 15 g of dimethylaminopyridine were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer And 100 ml of methylene chloride are charged, and the reaction vessel is maintained at 5 캜 or lower in a ice-cooled bath. 2.3 g (18.6 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, followed by washing with a 10% aqueous hydrochloric acid solution, washing with saturated brine, and drying the organic layer with anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 2-fold (weight ratio) silica gel column, and recrystallization from methylene chloride / methanol gave 3 g of the target compound shown in the formula (5). This compound exhibited a nematic liquid crystal phase at a wide temperature ranging from 114 ° C to 180 ° C or higher.

(Physical property value)

≪ ¹ > H-NMR (solvent: deuterated chloroform)

(m, 2H), 4.00 (t, 2H), 4.36 (m, 2H) 2H), 7.37-7.45 (m, 2H), 6.63 (d, 1H), 6.98 (dd, 2H), 7.13 2H), 7.82 (d, 1H), 8.16-8.18 (m, 2H), 7.62 (d,

≪ ¹³ > C-NMR (solvent: chloroform in chloroform):

?: 28.4, 34.4, 61.1, 64.6, 64.8, 114.3, 115.2, 115.5, 118.5, 121.5, 121.7, 122.0, 124.5, 128.3, 129.9, 130.0, 130.3, 130.9, 131.1, 132.3, 135.4, 144.7, 158.6, 161.0, 163.1, 164.7, 165.0, 166.0

Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ^-1

Melting point: 114 占 폚

(Example 2)

30 g (120 mmol) of 4-bromo-2-fluorobiphenyl and 120 ml of dichloromethane were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer and stirred. The reaction vessel was cooled to 0 캜, 18 g of aluminum chloride (III) was added, and 17 g of oxalyl chloride was slowly added dropwise over 30 minutes.

After completion of dropwise addition, the reaction vessel was returned to room temperature and stirred for 2 hours to terminate the reaction. The reaction solution was slowly poured into 500 ml of ice water, extracted with dichloromethane, and the organic layer was dried with sodium sulfate. After the solvent is distilled off, the reaction product is dissolved in 200 ml of toluene, 7 ml of ethanol is added, and the reaction vessel is cooled to 0 占 폚. Thereafter, 15 g (150 mmol) of triethylamine was slowly added dropwise. After completion of dropwise addition, the reaction vessel was returned to room temperature and stirred for 2 hours to terminate the reaction. After completion of the reaction, the hydrochloride of triethylamine was separated by filtration, and the organic layer was washed with 10% hydrochloric acid, pure water and saturated brine. The solvent was distilled off to obtain 35 g of a compound represented by the formula (6).

Subsequently, 35 g (108 mmol) of the compound represented by the formula (6), 13 g (130 mmol) of ethyl acrylate, 13 g (130 mmol) of triethylamine, 800 mg of palladium acetate, Amide were charged, and the reactor was heated to 100 占 폚 under a nitrogen gas atmosphere for reaction. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with a 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was carried out with a 2-fold (weight ratio) silica gel column to obtain 33 g of a compound represented by the formula (7).

Further, 33 g (96 mmol) of the compound represented by the above formula (7) and 200 ml of ethanol were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer, and dissolved by heating at 60 캜. Subsequently, 50 ml of an aqueous solution in which 10 g of sodium hydroxide was dissolved was slowly added dropwise. After completion of dropwise addition, the mixture was allowed to react at the same temperature for 2 hours. After completion of the reaction, 100 ml of a 10% hydrochloric acid aqueous solution was added to precipitate a solid. The solid was filtered off, washed with acetone, and dried to obtain 26 g of a compound represented by the formula (8).

Subsequently, 26 g (91 mmol) of the compound represented by the formula (8), 35 g (181 mmol) of acrylic acid 2- (4-hydroxyphenyl) ethyl and 2.2 g of dimethylaminopyridine were placed in a reaction vessel equipped with a stirrer, a condenser and a thermometer , And 300 ml of methylene chloride are charged, and the reaction vessel is kept at 5 캜 or lower in a ice-cooled bath. 27.3 g (210 mmol) of diisopropylcarbodiimide was slowly added dropwise in an atmosphere of nitrogen gas. After completion of dropwise addition, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 400 ml of methylene chloride was added to the filtrate, and the mixture was washed with a 10% hydrochloric acid aqueous solution and then with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 2-fold (weight ratio) silica gel column, and recrystallization from methylene chloride / methanol gave 45 g of the aimed compound represented by the formula (9). This compound exhibited a nematic liquid crystal phase at a wide temperature ranging from 106 ° C to 180 ° C or more.

(Physical property value)

≪ ¹ > H-NMR (solvent: deuterated chloroform)

(m, 2H), 6.36 (m, 2H), 6.66 (d, 1H), 6.40 (t, 2H) 1H), 7.71 (d, 2H), 7.83 (d, 1H), 7.71-7.19 (m, 4H), 7.26-7.32 8.28-8.30 (m, 2H)

≪ ¹³ > C-NMR (solvent: chloroform in chloroform):

?: 34.4, 64.8, 115.4, 115.6, 119.1, 121.5, 121.6, 124.6, 128.3, 129.1, 129.9, 130.4, 130.8, 131.1, 135.5, 144.4, 149.3, 149.5, 164.8, 164.9, 166.0

Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ^-1

Melting point: 106 DEG C

(Example 3)

To prepare a polymerizable liquid crystal composition (composition 1) having the following composition.

The polymerizable liquid crystal composition exhibited good phase stability and had a nematic liquid crystal phase. To this composition, 3% of a photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) was added to prepare a polymerizable liquid crystal composition (Composition 2). The cyclohexanone solution of the composition 2 was spin-coated on a polyimide-attached glass, and irradiated with ultraviolet rays of ⁴ mW / cm ² using a high-pressure mercury lamp for 120 seconds. As a result, the composition 2 was maintained in a uniformly oriented state Then, an optically anisotropic material was obtained. The surface hardness of this optically anisotropic material (according to JIS-SK-5400) was H. When the retardation of the obtained optical anisotropy before heating was 100%, the retardation after heating at 240 占 폚 for 1 hour was 90%, and the retardation reduction rate was 10%.

(Comparative Example 1)

To prepare a polymerizable liquid crystal composition (Composition 3) having the composition shown below.

The polymerizable liquid crystal composition exhibited a nematic liquid crystal phase, but crystals were precipitated at room temperature for 1 hour because of poor solubility.

(Comparative Example 2)

To prepare a polymerizable liquid crystal composition (Composition 4) having the composition shown below.

The polymerizable liquid crystal composition had good commercial stability and exhibited a nematic liquid crystal phase. To this composition, 3% of a photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) was added to prepare a polymerizable liquid crystal composition (Composition 5). A cyclohexanone solution of the composition 5 was spin-coated on a polyimide-attached glass and irradiated with ultraviolet rays of ⁴ mW / cm ² using a high-pressure mercury lamp for 120 seconds. As a result, the composition 3 was maintained in a uniform orientation Then, an optically anisotropic material was obtained. The surface hardness of this optically anisotropic material (according to JIS-SK-5400) was 2B. When the retardation of the obtained optical anisotropy before heating was 100%, the retardation after heating at 240 占 폚 for 1 hour was 75% and the retardation reduction rate was 25%.

As described above, the composition 5 of the comparative example 2 is obviously inferior in the heat resistance as compared with the composition 2 of the present invention, because the optical anisotropy which can be produced has a large retardation reduction rate. Further, the surface hardness was also insufficient as 2B.

Claims (9)

The compound of formula (I)

(Wherein R ¹ is any one of the following formulas (R-1) to (R-15)

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, A halogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group or a nitro group, S ¹ is a group in which oxygen atoms are not directly bonded to each other, -, or an alkylene group having 1 to 12 carbon atoms which may be substituted with -OCOO-, -C≡C-, or a single bond, L ¹ and L ² independently of one another are a single bond, -O-, -S- , -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -CO-NR ¹¹ - _{^{NR 11 -CO-, -SCH 2 -,}} -CH 2 S-, -CH = CH-COO-, -COO-CH = CH-, -CH = CH-OCO-, -OCO-CH = CH-, - COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -OCOCH ₂ -, -CH ₂ COO-, -CH = CH-, -, -CH = CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - I Out (in the formula, R ¹¹ represents an alkyl group of 1 to 4 carbon atoms), M ¹ and M ² are, each independently, 1,4-phenylene, 1,4-cyclohexylene group, a pyridine-2,5 each other Diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane- M ³ represents a 1,4-phenylene group, a 1,3,4-benzenetriyl group, a 1,3,5-benzenetriyl group, a 1,3,4,5-benzenetetrayl group, a pyridine- Diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group, a 1,3-dioxane-2,5-diyl group, A cyclohexanetriyl group or a 1,3,4-cyclohexanetriyl group, M ¹ , M ² and M ³ are each independently an unsubstituted or a substituted or unsubstituted alkyl group, halogenated alkyl group, An alkoxy group, a halogen group, a cyano group, or a nitro group, m represents 1, 2 or 3, n represents 0, 1 or 2, When m and n represent 2 or 3, two or three L ¹ , L ² , M ¹ and / or M ^{2 present} may be the same or different, and Z represents -L ³ -S ² -R ² ( Wherein R ² represents R ¹ , S ² represents S ¹ and L ³ represents the same as L ^1, and k represents 1, 2 or 3, and when k represents 2 or 3 Z may be the same or different). The method according to claim 1,
In formula (I), L ¹ , L ² and L ³ independently represent -O-, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -C ₂ H ₄ - , -C≡C-, or a single bond, M ¹ and M ² are each independently a 1,4-cyclohexylene group, a 1,4-phenylene group, a naphthalene-2,6-diyl group, And M ³ represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a naphthalene-2,6-diyl group, a 1,3,5-benzenetriyl group, represents a 1,3,4-benzenetricarboxylic group, M ^1, M ² and M ³ are independently each other an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a good optionally substituted by halogen, cyano or nitro, m Represents 1 and 2, and n represents 0 and 1. 3. The method according to claim 1 or 2,
In the general formula (I), M ³ is a 1,4-phenylene group which may be unsubstituted or substituted by an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen, a cyano group or a nitro group, A di-yl group, or a 1,3,4-benzenetriyl group. 3. The method according to claim 1 or 2,
In the polymerizable compound represented by formula (I), R ¹ and R ² independently represent a group represented by formula (R-1) or formula (R-2). 3. The method according to claim 1 or 2,
n is 0. 3. The method according to claim 1 or 2,
L ¹ , L ² and L ³ independently of one another represent -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, or a single bond. A liquid crystal composition containing the polymerizable compound according to any one of claims 1 to 3. An optically anisotropic composition comprising a polymer of a liquid crystal composition containing the polymerizable compound according to claim 7. A liquid crystal display element characterized by using the optical anisotropic element according to claim 8.