KR101677764B1 - Compound - Google Patents

Abstract

(식 중, X 는 탄소수 2 ∼ 20 의 알킬기, 탄소수 3 ∼ 20 의 고리형 알킬기 또는 탄소수 6 ∼ 20 의 치환 또는 비치환의 방향족 탄화수소기를 나타내고, 그 방향족 탄화 수소기는 치환기를 가질 수 있고,
E¹ 및 E² 는 각각 독립적으로 연결기 또는 단결합을 나타내고,
A¹ 및 A² 는 각각 독립적으로 2 가의 치환 또는 비치환의 방향족 탄화수소기를 나타내고,
B¹, B², B³ 및 B⁴ 는 각각 독립적으로 연결기 또는 단결합을 나타내고,
F¹ 및 F² 는 각각 독립적으로 탄소수 1 ∼ 12 의 치환 또는 비치환의 알칸디일기를 나타내고, 그 알칸디일기를 구성하는 1 개 이상의 메틸렌기는, 산소 원자로 치환할 수 있고,
P¹ 및 P² 는 각각 독립적으로 수소 원자 또는 중합성기를 나타낸다)
로 나타내는 화합물.Equation (1)

(Wherein X represents an alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, the aromatic hydrocarbon group may have a substituent,
E ¹ and E ² each independently represent a linking group or a single bond,
A ¹ and A ² each independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,
B ¹ , B ² , B ³ and B ⁴ each independently represent a linking group or a single bond,
F ¹ and F ² each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms and at least one methylene group constituting the alkanediyl group may be substituted with an oxygen atom,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group)
≪ / RTI >

Description

Compound {COMPOUND}

The present invention relates to novel compounds.

A flat panel display (FPD) includes a member using a film such as a polarizing plate and a retardation plate.

Japanese Patent Laid-Open Publication No. 2003-287623 discloses a compound represented by the formula (III-1-1)

Discloses a retardation film obtained by applying a solution obtained by dissolving a polymerizable compound represented by the following formula in a solvent to a supporting substrate and then polymerizing the polymerizable compound.

According to the present invention,

[1] Formula (1)

(Wherein X represents an alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

E ¹ and E ² each independently represent a linking group or a single bond,

A ¹ and A ² each independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,

B ¹ , B ² , B ³ and B ⁴ each independently represent a linking group or a single bond,

F ¹ and F ² each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms and at least one methylene group constituting the alkanediyl group may be substituted with an oxygen atom,

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group)

;

[2] In formula (1), P ¹ and P ² are each independently a group represented by formula (P-1)

(Wherein R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom)

Lt; 1 >

[3] A composition containing the compound described in [1] or [2] and a photopolymerization initiator;

[4] A film obtained by polymerizing the compound described in [1] or [2];

[5] A color filter comprising the film according to [4]

[6] A flat panel display device comprising the film according to [4];

[7] A process for producing a film comprising the step of applying the compound described in [1] or [2] onto an alignment film formed on a substrate or a substrate; And the like.

1 is a schematic sectional view of an example of a polarizing film comprising a film of the present invention.
2 is a schematic sectional view of an example of a liquid crystal display device including the film of the present invention.
3 is a schematic sectional view of an example of an organic EL display device including the film of the present invention.
4 is a schematic sectional view of an example of a color filter including the film of the present invention.

The novel compounds of the present invention are compounds of formula (1)

(Wherein X represents an alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

E ¹ and E ² each independently represent a linking group or a single bond,

A ¹ and A ² each independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,

B ¹ , B ² , B ³ and B ⁴ each independently represent a linking group or a single bond,

F ¹ and F ² each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms and at least one methylene group constituting the alkanediyl group may be substituted with an oxygen atom,

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group)

(Hereinafter abbreviated as compound (1)).

Examples of the alkyl group having 2 to 20 carbon atoms represented by X include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Methylhexyl group, an octyl group, a 1-methylheptyl group, a nonyl group, a 1-methyloctyl group, a 1-methylbutyl group, a 1-methylbutyl group, A decyl group, an undecyl group and a dodecyl group, and an alkyl group having 3 to 12 carbon atoms is preferable.

Examples of the cyclic alkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group and a cyclodecyl group, Is preferred.

Examples of the unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group and a 3-fluorenyl group, An unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms is preferred. Such an aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group; An alkoxy group having 1 to 5 carbon atoms such as methoxy group, ethoxy group and propoxy group; And halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; . Examples of the substituted aromatic hydrocarbon group include a 4-fluorophenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group and a 3,5-dimethylphenyl group.

X is preferably an alkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

E ¹ and E ² each independently represent a linking group or a single bond, and the linking group includes a divalent organic group. Specific examples thereof include -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ⁶ -, -NR ⁶ -CO-, ₂ - and -CH ₂ -O-, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, , Hexyl group). Among them, * -CO-O- (* represents a bonding site with 1,4-cyclohexanediyl group) is preferable.

The divalent unsubstituted aromatic hydrocarbon group represented by A ¹ and A ² is preferably a group consisting of a five-membered ring or a six-membered aromatic group represented by the following formulas (g-1) to (g-5) The hydrogen atom in the divalent aromatic hydrocarbon group is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group or tert- An alkoxy group (e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, or tert-butoxy), trifluoromethyl, cyano or nitro.

Examples of such a divalent substituted or unsubstituted aromatic hydrocarbon group include a 1,4-phenylene group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a 4,4'-biphenylene group, , And a 7-diyl group, and a 1,4-phenylene group is preferable.

B ¹ , B ² , B ³ and B ⁴ each independently represent a linking group or a single bond, and the linking group includes a divalent organic group. Specific examples thereof include -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ⁶ -, -NR ⁶ -CO-, -CS-. ≪ / RTI > Here, R ⁶ has the same meaning as above. Among them, -O-, -CO-O-, -O-CO-, -O-CO-O-, -C0-, -O-CH ₂ - and -CH ₂ -O- bond are preferable.

More preferably, B ¹ and B ² are -O-. B ³ and B ⁴ are * -O-CO- (* represents a bonding site with F ¹ or F ² ).

Examples of combinations of B ¹ , B ² , B ³ and B ⁴ include combinations shown in Table 1 below. In Table 1, * in the columns B ¹ and B ² represents a bonding site with F ¹ or F ² , and * in the columns B ³ and B ⁴ represents a bonding site with P ¹ or P ² .

Examples of the substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms represented by F ¹ and F ² include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, An unsubstituted alkanediyl group having 1 to 12 carbon atoms and a linear or branched one having 1 to 12 carbon atoms such as a caren group, an undecarenylene group and a dodecylene group is preferable, an unsubstituted alkanediyl group having 4 to 8 carbon atoms is more preferable, An alkanediyl group of 4 to 6 is particularly preferred. The alkanediyl group may have a substituent. The at least one methylene group constituting the alkanediyl group may be substituted with an oxygen atom. Examples of the group in which at least one methylene group constituting the alkanediyl group is substituted with an oxygen atom include -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O -CH ₂ -CH ₂ - and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -

At least one of P ¹ and P ² is preferably a polymerizable group, and more preferably P ¹ and P ² are polymerizable groups. The term "polymerizable group" means a group capable of participating in the polymerization reaction of the compound (1).

Examples of the polymerizable group include groups represented by the following formulas (P-1) to (P-5)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom)

(P-1) and (P-2) are preferable, and a group represented by the formula (P-1) is more preferable. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.

Specific examples include a 1-methylvinyl group, a vinyl group, a p-stilbene group, an epoxy group, a methyl epoxy group, a group represented by the formula (P-6), and a maleimide group.

Examples of the compound (1) include compounds represented by the formulas (1-a1) to (1-a50).

The compound (1) can be synthesized by a known organic synthesis reaction (for example, a condensation reaction, an esterification reaction, a Williamson reaction, a uremia reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, The reaction conditions are as follows: reaction, wittig reaction, Schiff base production reaction, benzylation reaction, fungal reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald- Hartwig reaction, Heptane reaction, heck reaction, aldol reaction, etc.), depending on the structure thereof.

For example, a compound represented by the formula (1-1) can be reacted with a compound represented by the formula (1-2) to obtain a compound represented by the formula (1-3) Compound (1) can be obtained by reacting a compound represented by formula (1-4).

(Wherein E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , B ³ , B ⁴ , F ¹ , F ² , P ¹ , P ² and X have the same meanings as defined above)

The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) . As the condensing agent, known ones can be used.

The composition of the present invention contains compound (1). The composition of the present invention may contain one kind of compound (1) or two or more kinds of compounds (1). The composition of the present invention may contain a liquid crystal compound different from the compound (1).

Specific examples of such a liquid crystal compound include three cholesteric liquid crystal molecules, 3.2 chiral chiral rod-shaped liquid crystal molecules, 3.3 chiral rod (a liquid crystal cell), three chapters of a liquid crystal handbook (published by LCD Handbook Editorial Committee, Maruzen Co., Among the compounds described in the shape liquid crystal molecules, compounds having a polymerizable group can be mentioned. The composition of the present invention may contain two or more liquid crystal compounds.

As the liquid crystal compound, for example, a compound containing a group represented by the formula (4) (hereinafter abbreviated as the compound (4)) can be mentioned.

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ - (4)

(Wherein P < ¹¹ > represents a polymerizable group,

A ¹¹ represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, An alkoxy group having 1 to 6 carbon atoms, a fluoroalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group,

B ¹¹ is a group selected from the group consisting of -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CS- or a single bond, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

B ¹² and B ¹³ are each independently selected from the group consisting of -C≡C-, -CH═CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C (═O) -, -C -O-, -OC (= O) -, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C ^{16 -, -NR 16 -C (=} O) -, -OCH 2 -, -OCF 2 -, -CH 2 O-, -CF 2 O-, -CH = CH-C (= O) -O-, -OC (= O) -CH = CH- or a single bond,

E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group is selected from the group consisting of a halogenated alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogenated alkoxy group having 1 to 5 carbon atoms And the methylene group contained in the alkanediyl group may be substituted with -O- or -CO-)

As the polymerizable group represented by P ¹¹ , a radical polymerizable group or a cationically polymerizable group is preferable from the viewpoint of high reactivity of photopolymerization. From the viewpoint of ease of handling and easy production of a liquid crystal compound, the following formula (P-11) To (P-15).

(Wherein R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom)

Specific examples thereof include groups represented by the following formulas (P-16) to (P-20).

The polymerizable group is preferably a group represented by formulas (P-14) to (P-20), and examples thereof include vinyl group, p-stilbene group, epoxy group and oxetanyl group.

P ¹¹ -B ¹¹ -, acryloyloxy group or methacryloyloxy group is particularly preferable.

The number of carbon atoms of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A ¹¹ is usually 3 to 18, preferably 5 to 12, and particularly preferably 5 or 6. As A ¹¹ , a 1,4-cyclohexylene group or a 1,4-phenylene group is preferable.

As E ¹¹ , an alkanediyl group having 1 to 12 carbon atoms in a linear form is preferable. The methylene group contained in the alkanediyl group may be substituted with -O-.

More specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptyl group, octyl group, a nonyl group, a group having Karen, Karen undecyl group, dodecyl xylene group, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Examples of the compound (4) include compounds represented by the following formulas (I), (II), (III), (IV), (V) and (VI)

(Wherein A ¹² to A ¹⁴ have the same meanings as A ¹¹ , B ¹⁴ to B ¹⁶ have the same meanings as B ¹² , B ¹⁷ has the same meaning as B ^11, and E ¹² has the same meaning as E ¹¹ .

Wherein F ¹¹ represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a methylol group, -SO ₃ H), a carboxyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms or a halogen atom, and the alkylene group and the methylene group contained in the alkoxy group may be substituted with -O-)

Specific examples of the compound (4) include compounds represented by the following formulas (I-1) to (I-4), (II- Compounds represented by formulas (IV-1) to (IV-19), formulas (V-1) to (V-2) and formulas (VI-1) to (VI-6). In the following formulas, k1 and k2 represent an integer of 2 to 12. These liquid crystal compounds are preferable because they are easy to synthesize or commercially available.

The content of the liquid crystal compound in the composition of the present invention is 90 parts by weight or less based on 100 parts by weight of the total amount of the liquid crystal compound and the compound (1).

The composition of the present invention may further contain additives such as a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, a solvent, and a chiral agent. In particular, it is preferable that the composition of the present invention contains an organic solvent in view of easy film formation, and it is preferable that the composition contains a polymerization initiator.

[Polymerization Initiator]

The polymerization initiator preferably contains a photopolymerization initiator, and as the photopolymerization initiator, a photopolymerization initiator that generates a radical by light irradiation is preferable.

-하이드록시케톤 화합물,

-아미노케톤 화합물, 트리아진 화합물, 요오드늄염 및 술포늄염을 들 수 있다. As the photopolymerization initiator, benzoin compounds, benzophenone compounds, benzyl ketal compounds,

- hydroxy ketone compounds,

- aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts.

Specifically, IRGACURE 907 (manufactured by Chiba Japan KK), IRGACURE 184 (manufactured by Chiba Japan KK), IRGACURE 651 (manufactured by Chiba Japan KK), Irgacure 819 (IRGACURE 907; SEIKUOL BZ (manufactured by Seiko Chemical Co., Ltd.), Seikol Z (manufactured by Nippon Kayaku Co., Ltd.), IRGACURE 250 (manufactured by Chiba Japan KK), IRGACURE 369 SEIKUOL Z manufactured by Seiko Chemical Co., Ltd., SEKUOL BEE (manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (KAYACURE BP100, manufactured by Nippon Yakushin KK), Kayacure UVI-6992 ADEKA OPTOMER SP-170 (manufactured by ADEKA), TAZ-A (manufactured by Nippon Shibel Hegner), ADEKA OPTOMER SP-152 (manufactured by ADEKA OPTOMER SP- , TAZ-PP ( There may be mentioned the production phone Shi bell hegeu neosa), TAZ-104 (Sanwa Chemical Co., Ltd.) and the like.

The content of the polymerization initiator in the composition of the present invention is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the compound (1) and the liquid crystal compound. Within the above range, the compound (1) or the liquid crystal compound can be polymerized without disturbing the orientation of the compound (1) or the liquid crystal compound.

[Polymerization inhibitor]

Examples of the polymerization inhibitor include a catechol compound having a substituent such as a hydroquinone compound having a substituent such as hydroquinone or an alkoxy group, an alkyl group such as butyl catechol, a pyrogallol compound, a 2,2,6,6-tetramethyl- A radical scavenger such as a piperidinyloxy radical, a thiophenol compound, a? -Naphthylamine compound, a? -Naphthol compound and the like.

By using the polymerization inhibitor, the polymerization reaction of the compound (1) or the liquid crystal compound is easily controlled, and the stability of the obtained film can be improved. The content of the polymerization inhibitor in the composition of the present invention is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the compound (1) and the liquid crystal compound. Within the above range, the compound (1) or the liquid crystal compound can be polymerized without disturbing the orientation of the compound (1) or the liquid crystal compound.

[Photosensitizer]

Examples of the photosensitizer include xanthene compounds such as xanthone and thioxanthone (e.g., 2,4-diethylthioxanthone and 2-isopropylthioxanthone), anthracene and alkoxy groups Anthracene compounds (e.g., dibutoxyanthracene and the like), phenothiazine, and rubrene.

By using a photosensitizer, the polymerization reaction of the compound (1) can be carried out with high sensitivity, and the time-course stability of the resulting film can be improved. The content of the photosensitizer in the composition of the present invention is usually 0.1 parts by weight to 30 parts by weight, preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the total amount of the compound (1) and the liquid crystal compound. Within the above range, the compound (1) or the liquid crystal compound can be polymerized without disturbing the orientation of the compound (1) or the liquid crystal compound.

[Leveling agent]

Examples of the leveling agent include additives for radiation curing paints (BYK-352, BYK-353 and BYK-361N manufactured by Big Chemie Japan), paint additives (SH28PA, DC11PA and ST80PA manufactured by Toray Dow Corning Co., Ltd.) (F-445, F-470, F-479 manufactured by DIC Co., Ltd.), and the like.

By using a leveling agent, a smoother film can be obtained. In addition, the flowability of the composition of the present invention may be controlled during the production of the film, or the cross-linking density in the obtained film may be adjusted. The content of the leveling agent in the composition of the present invention is usually 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight, per 100 parts by weight of the total amount of the compound (1) and the liquid crystal compound. Within the above range, the compound (1) or the liquid crystal compound can be polymerized without disturbing the orientation of the compound (1) or the liquid crystal compound.

[solvent]

As the solvent, an organic solvent capable of dissolving the compound (1) and a liquid crystal compound or the like can be used as long as it is a solvent inert to the polymerization reaction. Specific examples thereof include water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; . These organic solvents may be used alone or in combination of two or more.

The viscosity of the composition of the present invention is preferably adjusted to about 10 mPa · s or less, preferably about 0.1 to 7 mPa · s, for easy application.

It is preferable to include a solvent in that the fluidity of the composition of the present invention can be controlled by changing the amount of the solvent and that the film formation of the composition of the present invention is facilitated. The content of the solvent is usually 10 to 10,000 parts by weight, preferably 100 to 5,000 parts by weight, per 100 parts by weight of the compound (1).

The concentration of the solid content in the composition of the present invention is usually 2 to 50% by weight, preferably 5 to 50% by weight. If the concentration of the solid content is 2% by weight or more, the resulting film is not too thin, and a film having a birefringence required for optical correction of the liquid crystal panel tends to be easily obtained. When the concentration of the solid content is 50% by weight or less, the viscosity of the composition of the present invention is not too small, and the film thickness of the obtained film tends to be uneven. Here, the term "solid content" refers to a component in which the solvent is removed from the composition of the present invention.

[Chiral]

As the chiral agent, there can be used known chiral agents (for example, described in Liquid Crystal Device Handbook, Chapter 3, Section 4-3, Chronic Agent for TN, STN, page 199, have. The chiral agent generally contains an asymmetric carbon atom, and a condensed subcomponent or a planar subcomponent not containing an asymmetric carbon atom can also be used as the chiral agent. Specific examples of the builder subcomponent or the planar subcomponent include binaphthyl, helixene, paracyclophane, and these dielectrics.

As chiral agents, there can be mentioned, for example, JP-A-2007-269640, JP-A-2007-269639, JP-A-2007-176870, JP-A-2003-137887, JP-A-2000-515496, Japanese Patent Application Laid-Open No. 2007-169178 and Japanese Laid-Open Patent Publication No. 9-506088, and paliocolor LC756 manufactured by Bayer AG is preferable.

The content of the chiral agent is usually 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, per 100 parts by weight of the total amount of the compound (1) and the liquid crystal compound. Within the above range, the compound (1) or the liquid crystal compound can be polymerized without disturbing the orientation properties of the compound (1) or the liquid crystal compound.

The film of the present invention is a film capable of transmitting light, and refers to a film having an optical function. The optical function means refraction, birefringence, and the like. The retardation film, which is one type of the film of the present invention, is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, conversely converting circularly polarized light or elliptically polarized light into linearly polarized light, or converting polarized light of linearly polarized light do.

The film is obtained by polymerizing the compound (1). One kind of the compound (1) may be polymerized, or two or more kinds of the compounds (1) may be polymerized. The film of the present invention can also be produced by polymerizing the composition of the present invention.

From the viewpoint of easy film formation, it is preferable to use a solution in which the compound (1) is dissolved in an organic solvent, and the solution is coated on a support substrate, followed by drying and polymerization to obtain an optical film. The concentration of the solid content in such a solution is usually from 2 to 50% by weight, and preferably from 5 to 50% by weight.

Examples of the application method for the support substrate include extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method and die coating method. A dip coater, a bar coater, a spin coater, or the like.

As the supporting substrate, it is preferable that an alignment film can be formed on the supporting substrate. Specifically, glass, a plastic sheet, a plastic film, and a light-transmitting film can be given. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers; Polyvinyl alcohol film; Polyethylene terephthalate film; Polymethacrylic acid ester film; Polyacrylate film; Cellulose ester film; Polyethylene naphthalate film; Polycarbonate film; Polysulfone film; Polyethersulfone film; Polyether ketone films; Polyphenylene sulfide films; And polyphenylene oxide films.

Even in a process in which the strength of a film such as a film adhering step, a conveying step, and a storage step is required, the support substrate can be easily handled without destroying the film.

It is preferable to apply the solution of the compound (1) on the alignment film after forming the alignment film on the supporting substrate. It is preferable that the alignment film has a solvent resistance that is not dissolved in the solution when the solution of the compound (1) is applied. It is preferable that the alignment film has heat resistance in a heat treatment for removing a solvent or aligning a liquid crystal. Further, it is preferable that it is an alignment film which does not cause peeling or the like due to friction or the like at the time of rubbing. Such an orientation film is preferably composed of a composition containing an orienting polymer or an orienting polymer.

Examples of the oriented polymer include a polyamide or gelatin compound having an amide bond in a molecule, a polyimide having an imide bond in a molecule and a hydrolyzate thereof, polyamic acid, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, Sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid ester. These oriented polymers may be used alone or in combination of two or more kinds. Also, a copolymer of these orienting polymers may be used. These oriented polymers can be easily obtained by chain polymerization, coordination polymerization, ring-opening polymerization, and the like, such as polycondensation such as dehydration polycondensation and deamine polycondensation, radical polymerization, anionic polymerization, cationic polymerization and the like.

These oriented polymers are usually dissolved in a solvent and used as a solution. The solvent is not limited. Specifically, water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; And the like. These solvents may be used alone, or two or more solvents may be used in combination.

An alignment film may be formed using a commercially available alignment film material as it is. Commercially available alignment film materials include SANEVA (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optimer (registered trademark, manufactured by JSR Corporation).

By using such an orientation film, it is not necessary to control the refractive index by stretching, so that the in-plane deviation of the birefringence becomes small, and a large film capable of coping with the enlargement of the flat panel display (FPD) .

As a method of forming the alignment film on the supporting substrate, there can be mentioned a method in which a compound which becomes a material of a commercially available alignment film material or alignment film is applied as a solution on the supporting substrate, and then the substrate is annealed.

The thickness of the alignment film is usually 10 to 10,000 nm, preferably 10 to 1,000 nm. Within the above range, the compound (1) can be oriented at a desired angle on the alignment film. The alignment film may be subjected to rubbing treatment or polarizing UV irradiation may be applied to the alignment film as required. By this treatment, the compound (1) can be oriented in a desired angle and direction, and the refractive index ellipsoid It is possible to adjust the shape and tilt of the lens. When masking is performed when rubbing treatment or polarized UV irradiation is applied to the alignment film, an alignment pattern can be produced on the film.

As a method of rubbing the alignment film, there is a method in which a rubbing roll wound around a rubbing cloth is brought into contact with an alignment film conveyed on a stage.

[Unpolymerized Film Preparation Step]

A solution of the compound (1) is coated on an alignment film formed on or on the supporting substrate to dry the film to obtain an unpolymerized film. When the unpolymerized film shows a liquid crystal phase such as a nematic phase, it has birefringence due to monodomain orientation. The unpolymerized film is ordinarily mono-domain-oriented by drying at 0 to 250 ° C. Since the compound (1) exhibits a liquid crystal phase at a low temperature, monodomain orientation is obtained at a relatively low temperature, and the monodomain orientation is maintained even after cooling to about 0-100 deg.

[Non-polymerized film polymerization step]

The obtained non-polymerized film is polymerized and cured to obtain a polymerized film. Since the polymerized film is a film in which the orientation property of the compound (1) is fixed, it is not easily affected by the change in birefringence due to heat.

The method of polymerizing the unpolymerized film is appropriately determined depending on the kind of the polymerizable group of the compound (1). When the polymerizable group of the compound (1) is a photopolymerizable group, a photopolymerization method is used, and when the polymerizable group is a thermo-polymerizable group, a thermal polymerization method is used. According to the photopolymerization method, the compound (1) having a photopolymerizable group is used because it can polymerize an unpolymerized film at a low temperature, broaden the selection range of the heat resistance of the support substrate, and industrially, . The photopolymerization reaction is carried out by irradiating visible light, ultraviolet light or laser light to the unpolymerized film. In terms of handling, ultraviolet light is particularly preferable.

The removal of the solvent may be carried out in parallel with the polymerization reaction. It is preferable to remove most of the solvent before the polymerization reaction in view of the film formability. Examples of the removing method include natural drying, air drying, vacuum drying, and heat drying. The temperature at the time of removing the solvent by heating is usually 10 to 200 占 폚, preferably 20 to 150 占 폚. The heating time is usually 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes. If the heating temperature and the heating time are within the above range, a supporting substrate having insufficient heat resistance may be used as the supporting substrate.

The film of the present invention can be produced by a coating method. It is possible to manufacture a thin film on a flexible supporting substrate typified by a flexible substrate or a supporting substrate having a curvature.

By peeling the supporting substrate, a film in which the orientation film and the film of the present invention are laminated is obtained, and the orientation film is peeled off to obtain the film of the present invention. Alternatively, a separate supporting substrate may be adhered to the film of the present invention formed on the supporting substrate or the alignment film, and the supporting substrate on which the film of the present invention is formed may be peeled off, or the supporting substrate and the alignment film may be peeled off, .

By properly adjusting the content of the compound (1) and the liquid crystal compound in the composition of the present invention, the film thickness can be adjusted so as to give a desired retardation. Since the retardation value (retardation value, Re ()) of the obtained film is determined as shown by the formula (7), it is possible to appropriately adjust the film thickness d and the retardation value n .

Re (?) = D x? N (?) (7)

(Wherein, Re (?) Represents a retardation value at a wavelength? Nm, d represents a film thickness, and? N (?) Represents a birefringence at a wavelength? Nm)

The film thus obtained is excellent in transparency and is used as various display films. The thickness of the layer to be formed differs depending on the retardation value of the resulting film as described above. The thickness is preferably 0.1 to 10 mu m, more preferably 0.2 to 5 mu m in terms of reducing the photoelasticity.

The film of the present invention can change optical properties in various ways by changing the orientation state of the compound (1). As a result, when used as a retardation film for a liquid crystal panel, the optical characteristics can be changed for use in a VA mode, an IPS mode, an OCB mode, a TN mode, and an STN mode.

More specifically, when the refractive index in the in-plane slow axis direction is n _x , the refractive index in the direction perpendicular to the in-plane slow axis (fast axis direction) is n _y , the refractive index in the thickness direction is n _z If defined, n _x Of ≒ n _y ≒ n film, n _x there is no phase difference between the _Z> n _y ≒ n _z of the opposite Syktyvkar A plate, n _{x ≒} n _y> n the negative C plate, n _x ≒ n _y <n _z of _z Forge Syktyvkar C plate, Positive O plate with n _x ≠ n _y ≠ n _z , and Negative O plate can be manufactured.

Thin films fixed in the chiral nematic phase orientation are known to be selectively reflected, and selective reflection is also confirmed in the film of the present invention. The selective reflection wavelength band can be selected according to the intended use of the film. The central wavelength of the selective reflection wavelength band? (Nm) is represented by? = N? P, n represents the average refractive index of the composition, and P represents the spiral pitch (占 퐉) on the chiral nematic phase. In general, when the content of the chiral agent increases, P becomes small, so that the selective reflection wavelength band can be controlled by controlling the content of the chiral agent. In these cases, it is preferable that the chiral helical axis is oriented so as to be almost orthogonal to the plane direction of the transparent support.

By using the chiral agent in this way, a twist orientation film, a selective reflection film, a brightness enhancement film, and a negative C plate can be produced. When the film is used as a film of a negative C plate, it is preferable that the ultraviolet region has a selective reflection wavelength band.

The film of the present invention exhibits excellent optical characteristics even with one sheet. A plurality of films having the same function may be laminated, or may be used in combination with other films. Therefore, the film of the present invention can be used for a retardation film, a viewing angle compensation film, a viewing angle expansion film, an antireflection film, a polarizing film, a circularly polarizing film, an elliptically polarizing film,

Further, since the film of the present invention can be formed by polymerization and polymerization by irradiation and ultraviolet irradiation, the film can be formed in the liquid crystal cell or on the color filter without passing through a process such as adhesion. In addition, patterning of an optical function is also possible, and it is optimal for use as a so-called in-cell retardation plate.

Fig. 1 is a schematic cross-sectional view showing an example of a polarizing film including a film of the present invention, Fig. 2 is a schematic cross-sectional view showing an example of a liquid crystal display device including the film of the present invention, 4 is a schematic cross-sectional view showing an example of a color filter including the film of the present invention. In these drawings, the film may be only the film of the present invention, the orientation film may be laminated on the film of the present invention, or the orientation film and the supporting substrate may be laminated on the film of the present invention. The adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.

Fig. 1 shows an embodiment of a polarizing film comprising the film of the present invention. 1 (a) shows an embodiment in which the film 1 of the present invention and the polarizing film layer 2 are directly bonded. Fig. 1 (b) 2) are adhered via the adhesive layer (3). 1 (c) shows an embodiment in which the film 1 of the present invention is directly bonded to the film 1 'of the present invention and the film 1' of the present invention is directly bonded to the polarizing film layer 2 1 (d) shows a case where the film 1 of the present invention and the film 1 'of the present invention are bonded via the adhesive layer 3 and the polarizing film layer 1' (2) are directly bonded. Fig. 1 (e) is a plan view of a film 1 'of the present invention and a film 1' of the present invention bonded together via an adhesive layer 3, ) Are adhered via the adhesive layer 3 '.

The polarizing film layer may be a film having a polarizing function. Specifically, a film obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol film or a polyvinyl alcohol film is stretched to adsorb iodine or a dichroic dye And the like. The polarizing film layer may be provided with a film to be a protective film, if necessary. Examples of the protective film include polyolefin films such as polyethylene, polypropylene and norbornene polymers; Polyethylene terephthalate film; Polymethacrylic acid ester film; Polyacrylate film; Cellulose ester film; Polyethylene naphthalate film; Polycarbonate film; Polysulfone film; Polyethersulfone film; Polyether ketone films; Polyphenylene sulfide films; And polyphenylene oxide films; And the like.

The adhesive used for the adhesive layer 3 and the adhesive layer 3 'is preferably an adhesive having high transparency and excellent heat resistance. Examples of the adhesive include acrylic adhesives, epoxy adhesives, and urethane adhesives.

As shown in Fig. 1 (c) to Fig. 1 (e), two or more films of the present invention may be bonded directly or via an adhesive layer.

The flat panel display device of the present invention includes the film of the present invention and specifically includes a polarizing film including the film of the present invention and a liquid crystal display device having a liquid crystal panel bonded with the liquid crystal panel, An organic EL display device including a polarizing film including a film and an organic electroluminescence (hereinafter also referred to as &quot; EL &quot;) panel to which a light emitting layer is bonded.

A liquid crystal display device and an organic EL display device as embodiments of the flat panel display device of the present invention will be described below in detail.

[Liquid crystal display device]

Specific examples of the liquid crystal display device include a liquid crystal display device having a liquid crystal panel as shown in Figs. 2A and 2B. The liquid crystal panel is formed by bonding a member 4 including the film of the present invention and a liquid crystal panel 6 with an adhesive layer 5 interposed therebetween as shown in FIG. The member 4 including the inventive film and the member 4 'including the film of the present invention are bonded to both sides of the liquid crystal panel 6 with the adhesive layer 5 and the adhesive layer 5' interposed therebetween. According to the above configuration, by applying a voltage to the liquid crystal panel using an electrode (not shown), liquid crystal molecules can be driven to perform black and white display.

[Organic EL display device]

As a specific example of the organic EL display device, an organic EL display device including the organic EL panel shown in Fig. 3 and the like can be given. The organic EL panel is formed by bonding a member 4 including the film of the present invention and a light emitting layer 7 with an adhesive layer 5 interposed therebetween. The light emitting layer 7 is at least one layer made of a conductive organic compound.

Further, in the above organic EL panel, when the member 4 including the film of the present invention is a polarizing film, it functions as a broadband circularly polarizing plate. Therefore, it is possible to impart an antireflection function to the organic EL panel.

[Color Filter]

4 is a schematic cross-sectional view showing an example of the color filter 11 including the film of the present invention.

The color filter 11 is a color filter formed by forming a color filter layer 13 on the film 12 of the present invention.

An example of a method of manufacturing the color filter 11 will be described. First, an alignment film material is coated on a supporting substrate and rubbed to form an alignment film. Then, a solution containing the compound (1) whose concentration or the like is adjusted so that the resulting film exhibits a desired wavelength dispersion property is applied onto the resulting alignment film while adjusting the thickness so that the obtained film exhibits a desired retardation value To form a film. Then, the color filter layer 13 is formed on the obtained film 12 of the present invention.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, &quot;% &quot; and &quot; part (s) &quot;

Example 1 [Synthesis Example of Compound (1-a14)] [

(1) Synthesis of Compound (e)

Compound (e) was obtained by reacting compound (d) and compound (h) as shown in the following scheme.

(Synthesis Example of Compound (d)) [

The compound (a) was synthesized by the method described in JP-A-2004-262884.

100 g of the compound (a), 97 g of potassium carbonate and 64 g of 6-chlorohexanol were reacted by heating in N, N-dimethylacetamide at 90 占 폚 under a nitrogen atmosphere. Further, the reaction was conducted by heating at 100 占 폚. The obtained reaction mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added, and the organic layer was separated. The organic layer was washed with an aqueous solution of sodium hydroxide and pure water, followed by dehydration treatment. The dehydrating agent was removed by filtration, and the obtained filtrate was concentrated under reduced pressure. Methanol was added to the obtained residue, and the resulting precipitate was taken out by filtration and vacuum drying to obtain 126 g of the compound (b). Yield: 91% (based on 6-chlorohexanol).

126 g of the compound (b), 1.4 g of 3,5-di-tert-butyl-4-hydroxytoluene, 117 g of N, N-dimethylaniline, 1 g of 1,3- . To the resultant mixture, 58 g of acryloyl chloride was dropwise added under ice-cooling in a nitrogen atmosphere, and further pure water was added to react. The organic layer was separated from the obtained reaction mixture. The organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate solution and pure water. The organic layer was dried by adding a dehydrating agent. After removing the dehydrating agent, 1 g of 3,5-di-tert-butyl-4-hydroxytoluene was added to the obtained filtrate, and the filtrate was concentrated under reduced pressure to obtain a compound (c).

Compound (c) and 200 ml of tetrahydrofuran were mixed. To the obtained mixture, 200 ml of tetrahydrofuran was further added, and then hydrochloric acid and concentrated hydrochloric acid were added, and the reaction was carried out at 60 占 폚 in a nitrogen atmosphere. The reaction mixture was washed with 500 ml of a saturated saline solution and dehydrated with a dehydrating agent. The dehydrating agent was filtered, and the obtained filtrate was concentrated under reduced pressure. Hexane was added to the obtained concentrate, and the mixture was stirred under ice-cooling. The precipitated solid was taken out by filtration and vacuum dried to obtain 90 g of a compound (d). Yield: 79% (based on compound (c)).

(Synthesis Example of Compound (h)) [

200 g of trans-1,4-cyclohexanedicarboxylic acid and 1000 ml of N, N-dimethylacetamide were mixed. The resulting mixture was heated to 80 DEG C under stirring in a nitrogen atmosphere, and then 96 g of potassium carbonate and 10 g of potassium iodide were added. Further, 140 g of benzyl chloride was added, and the resulting solution was reacted at 120 DEG C for 6 hours. The resulting reaction solution was cooled to room temperature, poured into 1500 g of ice and stirred. The obtained crystals were taken out by filtration, washed with water / methanol 3: 2 (v / v), and then with water. The crystals after washing were vacuum-dried to obtain 251 g of a powder containing the compound (f).

251 g of the powder containing the compound (f) and 600 ml of chloroform were mixed. The obtained solution was ice-cooled, and 93.53 g of ethoxychloromethane and 146.83 g of triethylamine were added dropwise in a nitrogen atmosphere. The resulting solution was allowed to react at room temperature for 3 hours under a nitrogen atmosphere. To the reaction solution obtained, 600 ml of toluene was added, and the hydrochloride of precipitated triethylamine was removed by filtration. The obtained filtrate was washed with water and then dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the solvent was removed from the obtained filtrate. The obtained concentrated residue was vacuum dried to obtain 242 g of a liquid containing the compound (g).

242 g of a liquid containing the compound (g) and 250 ml of tetrahydrofuran were mixed. 10 g of 10% palladium-carbon (50% strength) was added to the obtained solution in a nitrogen atmosphere, and the resulting mixture was allowed to react at room temperature and normal pressure in a hydrogen atmosphere for 6 hours. The resulting reaction mixture was filtered to remove the catalyst, and then the solvent was removed. The residue was dissolved in chloroform and the resulting solution was filtered using silica gel. The insoluble product on silica gel was extracted with chloroform, and the resulting chloroform solution was concentrated under reduced pressure. Heptane was added to the residue to crystallize. The obtained crystals were taken out by filtration and vacuum dried to obtain 106 g of a compound (h). Yield: 39% (based on trans-1,4-cyclohexanedicarboxylic acid).

(Synthesis Example of Compound (e)) [

56.8 g of the compound (d), 2.65 g of N, N-dimethylaminopyridine, 50 g of the compound (h) and 300 ml of chloroform were mixed. The obtained mixed solution was stirred under ice-cooling in a nitrogen atmosphere, and a solution obtained by dissolving 48.79 g of dicyclohexylcarbodiimide in 50 ml of chloroform was added dropwise. After completion of the dropwise addition, the resulting mixture was stirred at room temperature. To the obtained reaction mixture, 200 ml of chloroform and 200 ml of heptane were added, and the precipitate was removed by filtration. After the filtrate was washed with 2 N hydrochloric acid, insoluble matter was removed by filtration. The obtained filtrate was dried over anhydrous sodium sulfate, and then sodium sulfate was removed by filtration. The solvent was removed from the resulting filtrate, and the obtained solid was vacuum-dried to obtain 100 g of the compound (e ').

100 g of the compound (e '), 3.7 g of pure water, 3.8 g of p-toluenesulfonic acid monohydrate and 200 mL of tetrahydrofuran were mixed and reacted at 50 DEG C under a nitrogen atmosphere. The obtained reaction solution was allowed to cool to room temperature, and then tetrahydrofuran was removed under reduced pressure. 200 ml of heptane was added to the obtained residue. The precipitated precipitate was taken out by filtration, washed with pure water, and then vacuum-dried. The resulting powder was dissolved in chloroform and filtered through silica gel. The filtrate was mixed with 400 ml of chloroform, and the resulting solution was concentrated. Toluene was added to the concentrated residue, and the resulting solution was concentrated under reduced pressure. The concentrate residue was crystallized by adding heptane, and the obtained crystals were taken out by filtration. The crystals taken out were vacuum-dried to obtain 64 g of a compound (e). Yield: 76% (based on compound (d)).

(2) Synthesis Example of Compound (1-a14)

3.4 g of phenylhydroquinone, 16 g of the compound (e), 0.5 g of 4-dimethylaminopyridine and 237 g of chloroform were mixed. A solution obtained by dissolving 9.4 g of N, N'-dicyclohexylcarbodiimide in 9 g of chloroform was added dropwise to the resulting mixture at room temperature, followed by reaction for 36 hours. To the obtained reaction mixture, 140 g of 2 N hydrochloric acid was added, and the resultant mixture was filtered. To the resulting filtrate was added 140 g of 2 N hydrochloric acid, followed by washing and concentration to obtain about 50 g of a concentrated solution. 0.4 g of activated carbon was added to the concentrate, and the mixture was filtered through celite. The resulting filtrate was concentrated, and methanol was added to the concentrated residue to obtain a solid. The obtained solid was washed with methanol to obtain 8.4 g of a white solid compound (1-a14). Yield: 47% (based on phenyl hydroquinone)

The phase transition temperature of the obtained compound (1-a14) was confirmed by a texture observation by a polarizing microscope. Compound (1-a14) exhibited a nematic phase at 84 DEG C to 198 DEG C and an isotropic phase at 198 DEG C at the time of elevated temperature. When the temperature was lowered at 200 占 폚, it exhibited a nematic phase from 198 占 폚 to 36 占 폚 and crystallized at 36 占 폚. Thus, the compound (1-a14) not only exhibits nematic liquid crystallinity in a wide temperature range, but also exhibits nematic liquid crystallinity in the vicinity of 40 ° C.

Example 2 [Synthesis Example of Compound (1-a3)] [

1.0 g of tert-butylhydroquinone, 6.0 g of the compound (e), 0.2 g of 4-dimethylaminopyridine and 121 g of chloroform were mixed. To the obtained mixture, a solution obtained by dissolving 4.5 g of N, N'-dicyclohexylcarbodiimide in 24 g of chloroform was added dropwise at room temperature, and the mixture was allowed to react for 3 hours. 60 g of 2 N hydrochloric acid was added to the obtained reaction solution, and the resulting mixture was filtered. The obtained filtrate was washed with 60 g of 2N hydrochloric acid and then concentrated to obtain about 40 g of a concentrated solution. 0.3 g of activated carbon was added to the concentrate and filtered through celite. The solvent was distilled off from the obtained filtrate. Methanol was added to the obtained concentrated residue to obtain a solid. The obtained solid was washed with methanol to obtain 4.1 g of a white solid compound (1-a3). Yield: 71% (on tert-butylhydroxy).

The phase transition temperature of the obtained compound (1-a3) was confirmed by a texture observation by a polarizing microscope. Compound (1-a3) exhibited a smectic phase from 66 ° C to 96 ° C at the time of heating, and a nematic phase at 96 ° C until at least 180 ° C. As a result of lowering the temperature at 180 占 폚, it was confirmed that the product exhibited a nematic phase from 180 占 폚 to at least 29 占 폚 and was not crystallized. Compound (1-a3) not only exhibits nematic liquid crystallinity in a wide temperature range, but also exhibits nematic liquid crystallinity in the vicinity of 30 ° C.

Comparative Example 1 [Synthesis Example of Compound (III-1-1)] [

(Synthesis Example of Compound (i)) [

84.5 g of ethyl 4-hydroxybenzoate, 84.2 g of 4-chlorobutyl acetate, 105 g of potassium carbonate and 254 g of N, N-dimethylacetamide were mixed, and the resulting mixture was heated to 100 캜 and stirred. After cooling, methyl isobutyl ketone was added to the reaction mixture, the mixture was washed with water, and the solvent was removed to obtain 126 g of an oily substance containing the compound (i) as a main component. Yield: 88% (based on ethyl 4-hydroxybenzoate).

(Synthesis Example of Compound (j)) [

126 g of an oily substance containing the compound (i) as a main component, 378 g of methanol, 252 g of water and 54 g of sodium hydroxide were mixed and reacted at 65 캜. The reaction mixture was cooled and then poured into 756 g of ice and further hydrochloric acid was added. The precipitated solid was taken out, washed with water and heptane, and then dried to obtain 91 g of a solid containing the compound (j) as a main component. Yield: 97% (based on compound (i)).

(Synthesis Example of Compound (k)) [

In a nitrogen atmosphere, 90.0 g of a solid containing the compound (i) as a main component and 77.8 g of N, N-dimethylaniline were dissolved in 720 g of N, N-dimethylacetamide. After the obtained solution was cooled to 0 deg. C, 58.1 g of acrylic acid chloride was added dropwise and the reaction was allowed to proceed at room temperature. To the obtained reaction mixture was added 1 N hydrochloric acid, and the precipitated solid was taken out. The extracted solid was dissolved in ethyl acetate. The obtained solution was washed with water and then the solvent was removed to obtain 102 g of a solid containing the compound (k) as a main component. Yield: 90% (based on compound (j)).

(Synthesis Example of Compound (III-1-1)

3 g of hydroquinone, 16 g of a solid containing the compound (k) as a main component, 0.7 g of 4-dimethylaminopyridine and 127 g of chloroform were mixed. To the obtained mixture, a solution obtained by dissolving 12 g of N, N'-dicyclohexylcarbodiimide in 32 g of chloroform was added dropwise at room temperature, and the mixture was allowed to react for 3 hours. To the reaction mixture was added 159 g of 2N hydrochloric acid, followed by filtration. 159 g of 2 N hydrochloric acid was added to the obtained filtrate, followed by washing. The solvent was distilled off, and methanol was added to obtain a solid. The obtained solid was washed with methanol to obtain 12.0 g of a white solid compound (III-1-1). Yield: 66% (based on hydroquinone).

The phase transition temperature of the compound (III-1-1) was confirmed by a texture observation by a polarizing microscope. When the temperature was raised, the crystal phase was changed to a nematic phase at about 107 ° C, and the isotropic liquid phase was changed to about 167 ° C. When the temperature is lowered, the isotropic liquid phase changes to a nematic phase at about 167 ° C, and when the temperature is lowered to about 74 ° C, it returns to the crystalline phase. That is, it was found that the compound (III-1-1) exhibits a nematic phase at a temperature between 107 ° C and 167 ° C at a heating temperature and between 167 ° C and 107 ° C at a temperature lowering.

Examples 3 to 6 and Comparative Example 2

&Lt; Preparation of composition >

A composition having the composition shown in Table 2 was prepared. % In Table 2 means weight% when the total weight of the composition is taken as 100% by weight.

Photopolymerization initiator: Irgacure 819 (acylphosphine oxide compound, manufactured by Chiba Japan KK)

Leveling agent: BYK361N (manufactured by Big Chemie Japan)

Solvent: Cyclopentanone

<Numerical observation>

A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate and dried by heating to form a film having a thickness of 89 nm. The surface of the film was rubbed to form an alignment film. On the rubbed surface, the composition shown in Table 2 was applied by a spin coat method. The resulting substrate was heated at a heating rate of 30 占 폚 / min at a heating temperature using a polarizing microscope (hot stage: LTS350, manufactured by Linkam, polarimeter microscope: BX-51, Olympus) equipped with a hot stage, The behavior was observed. During cooling, the behavior was observed by natural cooling. The results are shown in Table 3.

Observation result Example 3 When the temperature was raised, the phase transition to a nematic phase at 78 ° C was started to form a monodomain structure, and it was confirmed that the monodomain structure was maintained at at least 150 ° C. As a result of lowering the temperature at 150 캜, it showed a nematic phase up to 38 캜 and formed a monodomain structure, and crystallized at 38 캜. Example 4 When the temperature was raised, phase transition to a nematic phase at 20 캜 was initiated to form a monodomain structure, and it was confirmed that the monodomain structure was maintained at at least 150 캜. As a result of lowering the temperature at 150 캜, it showed a nematic phase up to 40 캜, formed a monodomain structure, and crystallized at 40 캜. Example 5 When the temperature was raised, phase transition to a nematic phase at 84 占 폚 was initiated to form a monodomain structure, and it was confirmed that the monodomain structure was maintained at at least 150 占 폚. As a result of lowering the temperature at 150 캜, it showed a nematic phase up to 40 캜 and formed a mono-domain structure and crystallized at 40 캜. Example 6 When the temperature was raised, phase transition to a nematic phase at 100 ° C was initiated to form a monodomain structure and it was confirmed that the monodomain structure was maintained at least up to 150 ° C. As a result of lowering the temperature at 150 캜, it showed a nematic phase up to 36 캜, formed a monodomain structure, and crystallized at 36 캜. Comparative Example 2 When the temperature was raised, phase transition to a nematic phase at 143 ° C was initiated to form a monodomain structure, and it was confirmed that the monodomain structure was maintained at at least 158 ° C. As a result of lowering the temperature at 160 캜, it was confirmed that a nematic phase was formed up to 80 캜 and a monodomain structure was formed.

<Production Example of Film>

A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate and dried by heating to form a film having a thickness of 89 nm. The surface of the film was rubbed to form an alignment film. On the rubbing treated surface, the composition shown in Table 2 was applied by the spin coat method and dried at the temperature (T _c ) shown in Table 4 for one minute. The film was allowed to stand at the temperature (T _d ) shown in Table 4 for one minute, and then irradiated with ultraviolet light having an accumulated light quantity of 2400 mJ / cm 2 to produce a film.

<Observation of Surface Condition>

The surface state of the film was observed with a polarization microscope at a magnification of 400 times. Indicates a mono domain, and &quot; x &quot; indicates that a defect has occurred. The results are shown in Table 4.

<Time course stability>

The film was allowed to stand in the air at room temperature for 2 weeks, and then the surface state of the film was observed with a polarizing microscope. .Largecircle. Indicates that alignment defects can not be found, and &amp; cir &amp; The results are shown in Table 4.

&Lt; Measurement of optical characteristics &

The retardation value of the film was measured by a measuring device (KOBRA-WR, Oji Instruments Co., Ltd.). The retardation value (nm) was measured for a laminate including a glass substrate, an alignment film and a film. Since the glass substrate and the alignment film do not have birefringence (Re (447) = Re 547) = Re (628) = 0), and the measured retardation value can be used as the retardation value of the film. The retardation value Re (?) Was measured at wavelengths? 447 nm, 547 nm and 628 nm. The film thickness d (占 퐉) of the film was measured using a laser microscope (LEXT 3000, manufactured by Olympus Corporation). The results are shown in Table 5.

In the examples, films could be produced at a low temperature of 30 占 폚 or 50 占 폚.

By polymerizing the compound of the present invention, a film having excellent surface state and time-course stability and having optical characteristics can be produced at a low temperature.

1, 1 'film
2, 2 'polarizing film layer
3, 3 'adhesive layer
4, 4 'member comprising the film of the invention
5, 5 'adhesive layer
6 liquid crystal panel
7 Light emitting layer
11 Color filters
12 film
13 Color filter layer

Claims (7)

Equation (1)

(Wherein X represents an alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms,
The substituent of the aromatic hydrocarbon group having 6 to 20 carbon atoms is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom,
E ¹ and E ² each independently represent a linking group or a single bond,
The linking group of E ¹ and E ² is selected from -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ⁶ -, -NR ⁶ -CO -, -O-CH ₂ - or -CH ₂ -O-, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ¹ and A ² each independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,
The substituents for A ¹ and A ² are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group, a cyano group or a nitro group,
B ¹ , B ² , B ³ and B ⁴ each independently represent a linking group or a single bond,
Wherein B ^1, B ^2, B ³ and B ⁴ is a linking group, -O-, -S-, -CO-O- , -O-CO-, -O-CO-O-, -CO-NR 6 - , -NR ⁶ -CO-, -CO- and -CS-, R ⁶ has the same meaning as defined above,
F ¹ and F ² each independently represent an unsubstituted alkanediyl group having 1 to 12 carbon atoms and at least one methylene group constituting the alkanediyl group may be substituted with an oxygen atom,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group)
&Lt; / RTI &gt; The method according to claim 1,
In the formula (1), P ¹ and P ² are each independently a group represented by the formula (P-1)

(Wherein R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom)
&Lt; / RTI &gt; A composition comprising the compound according to any one of claims 1 and 2 and a photopolymerization initiator. A film obtained by polymerizing the compound according to claim 1 or 2. A color filter comprising the film of claim 4. A flat panel display device comprising the film according to claim 4. A process for producing a film, comprising the step of applying the compound according to any one of claims 1 to 3 on an alignment film formed on a substrate or a substrate.

Images