KR20100116122A - Compound - Google Patents

Abstract

PURPOSE: A compound is provided to for a film with the optical property and the excellent time-out stability of the compound after the polymerization in the low temperature. CONSTITUTION: A compound is marked with chemical formula 1. In the chemical formula 1, X is an alkyl group with 2~20 carbons, a cyclic alkyl group with 3~20 carbons, or a substituted or non-substituted aromatic hydrocarbon group with 6~20 carbons. E1 and E2 are a boning group or a single bond, respectively. A1 and A2 are a substituted or non-substituted divalent aromatic hydrocarbon group.

Description

Compound {COMPOUND}

The present invention relates to novel compounds.

The flat panel display apparatus FPD contains the member using films, such as a polarizing plate and a phase difference plate.

In Japanese Patent Laid-Open No. 2003-287623, the formula (III-1-1)

After apply | coating the solution obtained by dissolving the polymeric compound shown by the solvent to a support base material, the retardation film obtained by superposing | polymerizing this polymeric compound is disclosed.

The present invention,

[1] Formula (1)

(In formula, X represents a C2-C20 alkyl group, a C3-C20 cyclic alkyl group, or a C6-C20 substituted or unsubstituted aromatic hydrocarbon group,

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 one or more methylene groups 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)

Compound represented by;

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

(In formula, R <^1> , R <^2> and R <^3> represent a C1-C6 alkyl group or a hydrogen atom each independently.)

The compound according to [1], which is represented by a group;

[3] a composition containing the compound according to [1] or [2] and a photopolymerization initiator;

[4] a film obtained by polymerizing the compound according to [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 method for producing a film comprising the step of applying the compound according to [1] or [2] on an alignment film formed on a substrate or on a substrate; And so on.

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

The novel compound of the present invention is formula (1)

(In formula, X represents a C2-C20 alkyl group, a C3-C20 cyclic alkyl group, or a C6-C20 substituted or unsubstituted aromatic hydrocarbon group,

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 one or more methylene groups 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)

It is a compound represented by (hereinafter abbreviated as compound (1)).

Examples of the alkyl group having 2 to 20 carbon atoms represented by X include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-methylbutyl group, and 3-methylbutyl Group, hexyl group, 1-methylpentyl group, 4-methylpentyl group, heptyl group, 1-methylhexyl group, 5-methylhexyl group, octyl group, 1-methylheptyl group, nonyl group, 1-methyloctyl group, A decyl group, an undecyl group, and a dodecyl group are mentioned, A C3-C12 alkyl group 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. The cyclic alkyl group of is preferable.

Examples of the unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, and 3-fluorenyl group. The unsubstituted aromatic hydrocarbon group of 6-14 is preferable. Such an aromatic hydrocarbon group may have a substituent, As a substituent, C1-C5 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C1-C5 alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group; And halogen atoms such as fluorine atom, chlorine atom and bromine atom; . Examples of the substituted aromatic hydrocarbon group include 4-fluorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-methylphenyl group, 4-ethylphenyl group, and 3,5-dimethylphenyl group.

It is preferable that X is a C3-C12 alkyl group or a C6-C12 aromatic hydrocarbon group.

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

As a bivalent unsubstituted aromatic hydrocarbon group represented by A <^1> and A <^2> , group which consists of a 5-membered ring or 6-membered aromatic group represented by following formula (g-1)-formula (g-5) is preferable. The hydrogen atom in a bivalent aromatic hydrocarbon group is a halogen atom, a C1-C4 alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert- butyl group, etc.), and a C1-C4 The alkoxy group (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group etc.), trifluoromethyl group, cyano group, or nitro group may be substituted.

As such a bivalent substituted or unsubstituted aromatic hydrocarbon group, 1,4-phenylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 4,4'-biphenylene group, and fluorene-2 A 7-diyl group is mentioned, 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 contains a divalent organic group. Specific examples thereof include -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ^6- , -NR ⁶ -CO-, -CO- and -CS- can be mentioned. Here, R <^6> represents the same meaning as the above. Among them, -O-, -CO-0-, -0-CO-, -O-CO-0-, -C0-, -O-CH _2- , and -CH ₂ -O- single bonds are preferable.

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

B ^1, as a combination of B ^2, B ³ and B ^4, can be given to the combination shown in Table 1. In Table 1, * in column B ^{1 and} column B ² indicates a binding site with F ¹ or F ² , and * in column B ³ and B ⁴ indicates a binding 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 are methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, dene A straight or branched unsubstituted alkanediyl group of 1 to 12 carbon atoms, such as a carne group, an undecylene group, and a dodecylene group, is preferable, and an unsubstituted alkanediyl group of 4 to 8 carbon atoms is more preferable, and a carbon number 4-6 alkanediyl group is especially preferable. The alkanediyl group may have a substituent. Moreover, the 1 or more methylene group which comprises this alkanediyl group can be substituted by the 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 -may be mentioned.

At least one of P ¹ and P ² is, that the polymerizable group is preferable, more preferably in the P ¹ and P ² is a polymerizable group. The "polymerizable group" means the group which can participate in the polymerization reaction of the compound (1).

As a polymeric group, following formula (P-1)-a formula (P-5)

(In formula, R <^1> , R <^2> , R <^3> , R <^4> and R <^5> show a C1-C6 alkyl group or a hydrogen atom each independently.)

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

Specifically, a 1-methyl vinyl group, a vinyl group, a p-stilbene group, an epoxy group, a methyl epoxy group, the group represented by Formula (P-6), and a maleimide group are mentioned.

As compound (1), the compound represented by Formula (1-a1)-a formula (1-a50) is mentioned.

Compound (1) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lectures (e.g., condensation reaction, esterification reaction, Williamson reaction, Ulman) Reaction, Wittich reaction, shif base reaction, benzylation reaction, homogenization reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel Craft Tsu reaction, a hex reaction, an aldol reaction, etc.) can be manufactured by combining suitably according to the structure.

For example, the compound represented by Formula (1-3) obtained by making the compound represented by Formula (1-1) react with the compound represented by Formula (1-2), obtaining the compound represented by Formula (1-3), and Compound (1) can be obtained by making the compound represented by Formula (1-4) react.

(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 represent the same meaning as above)

The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the compound represented by the formula (1-3) and the compound represented by the formula (1-4) are in the presence of a condensing agent. It is preferable to carry out. As a condensing agent, a well-known thing can be used.

The composition of this invention contains compound (1). The composition of this invention may contain 1 type of compound (1), and may contain 2 or more types of compound (1). The composition of this invention can contain a liquid crystal compound different from compound (1).

As a specific example of such a liquid crystal compound, the liquid crystal handbook (Liquid Crystal Handbook Editing Committee Edition, Maruzen Co., Ltd., October 30, 2003) Chapter 3 molecular structure and liquid crystalline 3.2 nonchiral rod-like liquid crystal molecule, 3.3 chiral rod The compound which has a polymeric group is mentioned in the compound described in shape liquid crystal molecule. The composition of this invention can contain 2 or more types of liquid crystal compounds.

As a liquid crystal compound, the compound (henceforth abbreviated as compound (4)) containing the group represented by Formula (4) is mentioned, for example.

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

(Wherein, P is ^11, represents a polymerizable group,

A ¹¹ represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, May have one or more substituents selected from the group consisting of a C 1-6 alkoxy group, a C 1-6 alkoxy fluoride group, a cyano group, and a nitro group,

B ¹¹ is —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹⁶ —, —NR ¹⁶ —CO—, —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 —C≡C—, —CH═CH—, —CH ₂ —CH ₂ —, —O—, —S—, —C (═O) —, —C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR ^{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 a C1-C12 alkanediyl group and this alkanediyl group is chosen from the group which consists of a C1-C5 halogenated alkyl group, a C1-C5 alkoxy group, and a C1-C5 halogenated alkoxy group May have one or more substituents, and the methylene group contained in the alkanediyl group may be substituted with -O- or -CO-)

As the polymerizable group represented by P ¹¹ , from the viewpoint of high reactivity of photopolymerization, a radical polymerizable group or a cationic polymerizable group is preferable, the handling is easy, and the production of a liquid crystal compound is also easy, and the following formula (P-11) It is preferable that it is group represented by (P-15).

(In formula, R <^17> -R <^21> represents a C1-C6 alkyl group or a hydrogen atom each independently.)

Specifically, group represented by following formula (P-16)-(P-20) is mentioned.

It is preferable that a polymeric group is group represented by Formula (P-14)-(P-20), and a vinyl group, a p-stilbene group, an epoxy group, and an oxetanyl group are mentioned.

It is especially preferable that P <^11> -B <^11> is an acryloyloxy group or a methacryloyloxy group.

Carbon number of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A <^11> is 3-18 normally, It is preferable that it is 5-12, It is especially preferable that it is 5 or 6. As A ¹¹ , a 1,4-cyclohexylene group or a 1,4-phenylene group is preferable.

Examples of E ^11, an alkanediyl group having 1 to 12 carbon atoms in the straight-chain is preferable. The methylene group contained in this alkanediyl group can be substituted by -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 -may be mentioned.

As compound (4), the compound represented by Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), and Formula (VI) is mentioned.

(A meaning of, A ¹² ~ A ¹⁴ is the same as A ¹¹ expression, B and ¹⁴ ~ B ¹⁶ has the same meaning as B ^12, B ¹⁷ is the same meaning as B ^11, E ¹² is a means, such as E ^11.

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

As a specific example of a compound (4), Formula (I-1)-a formula (I-4), a formula (II-1)-a formula (II-4), a formula (III-1)-a formula (III-26), The compound represented by a formula (IV-1)-a formula (IV-19), a formula (V-1)-a formula (V-2), and a formula (VI-1)-a formula (VI-6) is mentioned. However, in the following formula, k1 and k2 represent the integer of 2-12. Since these liquid crystal compounds are easy to synthesize | combine, or are commercially available, these liquid crystal compounds are preferable.

Content of the liquid crystal compound in the composition of this invention is 90 weight part or less with respect to a total of 100 weight part of a liquid crystal compound and a compound (1).

The composition of this invention can contain additives, such as a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, a solvent, and a chiral agent further. In particular, since it is easy to form the composition of this invention, it is preferable to contain an organic solvent, and also to contain a polymerization initiator.

[Polymerization Initiator]

It is preferable that a polymerization initiator contains a photoinitiator, and as a photoinitiator, the photoinitiator which generate | occur | produces a radical by light irradiation is preferable.

-하이드록시케톤 화합물,

-아미노케톤 화합물, 트리아진 화합물, 요오드늄염 및 술포늄염을 들 수 있다. As a photoinitiator, a benzoin compound, a benzophenone compound, a benzyl ketal compound,

Hydroxyketone compounds,

-Amino ketone compounds, triazine compounds, iodonium salts and sulfonium salts.

Specifically, Irgacure 907 (IRGACURE907; Chiba Japan Co., Ltd.), Irgacure 184 (IRGACURE184; Chiba Japan Co., Ltd.), Irgacure 651 (IRGACURE651; Chiba Japan Co., Ltd.), Irgacure 819 (IRGACURE819; Chiba Japan Co., Ltd.), Irgacure 250 (IRGACURE 250; Chiba Japan Co., Ltd.), Irgacure 369 (IRGACURE369; Chiba Japan Co., Ltd.), Seikol BZ (SEIKUOL BZ; Seiko Chemical Co., Ltd.), Seikol Z ( SEIKUOL Z; manufactured by Seiko Chemical Co., Ltd., Seikol BEE (SElKUOL BEE; manufactured by Seiko Chemical Co., Ltd.), Kayakure BP100 (KAYACURE BP100; manufactured by Nippon Gunpowder Co., Ltd.), Kayakure UVI-6992 (KAYACURE UVI-6992; manufactured by Dausa) , ADEKA OPTOMER SP-152 (ADEKA OPTOMER SP-152; ADEKA Co., Ltd.), ADEKA OPTOMER SP-170 (ADEKA OPTOMER SP-170; ADEKA Co., Ltd.), TAZ-A (made by Nippon Siebel Hegner) , TAZ-PP ( There may be mentioned the production phone Shi bell hegeu neosa), TAZ-104 (Sanwa Chemical Co., Ltd.) and the like.

Content of the polymerization initiator in the composition of this invention is 0.1 weight part-30 weight part normally with respect to 100 weight part of total of a compound (1) and a liquid crystal compound, Preferably they are 0.5 weight part-10 weight part. If it is in the said range, compound (1) and a liquid crystal compound can be polymerized, without disturbing the orientation of a compound (1) and a liquid crystal compound.

[Polymerization inhibitor]

As a polymerization inhibitor, the catechol compound which has substituents, such as a hydroquinone compound which has substituents, such as a hydroquinone and an alkoxy group, and alkyl groups, such as butyl catechol, a pyrogallol compound, 2,2,6,6- tetramethyl-1 Radical scavengers such as -piperidinyloxy radicals, thiophenol compounds, β-naphthylamine compounds, β-naphthol compounds and the like.

By using a polymerization inhibitor, control of the polymerization reaction of a compound (1) and a liquid crystal compound becomes easy, and the stability of the film obtained can be improved. Content of the polymerization inhibitor in the composition of this invention is 0.1 weight part-30 weight part normally with respect to 100 weight part of total of a compound (1) and a liquid crystal compound, Preferably they are 0.5 weight part-10 weight part. If it is in the said range, compound (1) and a liquid crystal compound can be polymerized, without disturbing the orientation of a compound (1) and a liquid crystal compound.

[Photosensitizer]

As a photosensitizer, it has xanthone compounds, such as xanthone and thioxanthone (for example, 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, etc.), substituents, such as anthracene and an alkoxy group. Anthracene compounds (eg, dibutoxyanthracene, etc.), phenothiazine, and rubrene.

By using a photosensitizer, the polymerization reaction of the compound (1) can be performed with high sensitivity, and also the time-lapse stability of the film obtained can also be improved. As content of the photosensitizer in the composition of this invention, it is 0.1 weight part-30 weight part normally with respect to a total of 100 weight part of compound (1) and a liquid crystal compound, Preferably it is 0.5 weight part-10 weight part. If it is in the said range, compound (1) and a liquid crystal compound can be polymerized, without disturbing the orientation of a compound (1) and a liquid crystal compound.

[Leveling Agent]

As a leveling agent, additives for radiation hardening paints (BIC Chemie Japan make: BYK-352, BYK-353, BYK-361N), paint additives (Toray Dow Corning Corporation make: SH28PA, DC11PA, ST80PA), paint additives (Shin-Etsu) Chemical Industry Co., Ltd. make: KP321, KP323, X22-161A, KF6001), a fluorine additive (DIC Corporation make: F-445, F-470, F-479), etc. are mentioned.

By using a leveling agent, a smoother film can be obtained. Moreover, in the manufacturing process of a film, you may control the fluidity | liquidity of the composition of this invention, or adjust the crosslinking density in the film obtained. Content of the leveling agent in the composition of this invention is 0.01-30 weight part normally with respect to 100 weight part of total of a compound (1) and a liquid crystal compound, Preferably it is 0.05-10 weight part. If it is in the said range, compound (1) and a liquid crystal compound can be polymerized, without disturbing the orientation of a compound (1) and a liquid crystal compound.

[solvent]

As a solvent, as an organic solvent which can melt | dissolve a compound (1), a liquid crystal compound, etc., what is necessary is just a solvent inactive to a polymerization reaction, 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, 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 independently or may be used in combination of plurality.

The viscosity of the composition of the present invention is preferably adjusted to, for example, 10 mPa · s or less, preferably about 0.1 to 7 mPa · s so as to be easily applied.

By changing the amount of the solvent, the fluidity of the composition of the present invention can be controlled, and it is preferable to include a solvent in that the film formation of the composition of the present invention becomes easy. Content of a solvent is 10-100,000 weight part normally with respect to 100 weight part of compounds (1), Preferably it is 100-5,000 weight part.

The density | concentration of solid content in the composition of this invention is 2-50 weight% normally, and 5-50 weight% is preferable. When the concentration of the solid content is 2% by weight or more, the film obtained does not become too thin, so that the film having the birefringence necessary for optical correction of the liquid crystal panel tends to be easily obtained. Moreover, when the density | concentration of solid content is 50 weight% or less, the viscosity of the composition of this invention does not become small too much, and there exists a tendency for the nonuniformity of the film thickness of the film obtained to not arise easily. Here, "solid content" means the component remove | excluding the solvent from the composition of this invention.

[Chiral agent]

As a chiral agent, a well-known chiral agent (for example, a liquid crystal device handbook, Chapter 3-4-3, TN, a chiral agent for STN, page 199, described in Japan Society for the Promotion of Japanese Society 142, 1989) can be used. have. Although a chiral agent generally contains a subtitle carbon atom, a layered subtitle compound or a cotton subtitle compound which does not contain a subtitle carbon atom can also be used as the chiral agent. Specific examples of the layered subtitle compound or the cotton subtitle compound include vinaphthyl, hexane, paracyclophane and these dielectrics.

As a chiral agent, Unexamined-Japanese-Patent No. 2007-269640, Unexamined-Japanese-Patent No. 2007-269639, Unexamined-Japanese-Patent No. 2007-176870, Unexamined-Japanese-Patent No. 2003-137887, Unexamined-Japanese-Patent No. 2000-515496, Japan The chiral agent disclosed by Unexamined-Japanese-Patent No. 2007-169178 and Unexamined-Japanese-Patent No. 9-506088 is mentioned, paliocolor LC756 by Biesf Co., Ltd. is preferable.

Content of a chiral agent is 0.1 weight part-30 weight part normally with respect to 100 weight part of total of a compound (1) and a liquid crystal compound, Preferably they are 1 weight part-25 weight part. If it is in the said range, compound (1) and a liquid crystal compound can be polymerized, without disturbing the orientation of a compound (1) and a liquid crystal compound.

The film of this invention is a film which can permeate | transmit light, and says the film which has an optical function. Optical function means refraction, birefringence, etc. The retardation film which is one kind of the film of this invention is used for converting linearly polarized light into circularly polarized or elliptically polarized light, conversely converting circularly or elliptically polarized light into linearly polarized light, or converting the polarization direction of linearly polarized light. do.

This film is obtained by superposing | polymerizing a compound (1). One type of compound (1) may be polymerized and two or more types of compound (1) may be polymerized. Moreover, the film of this invention can be manufactured also by superposing | polymerizing the composition of this invention.

It is preferable to use the solution which the compound (1) melt | dissolved in the organic solvent from the point of easiness of film formation, and an optical film is obtained by apply | coating this solution on a support base material, and drying and superposing | polymerizing. Concentration of solid content in such a solution is 2-50 weight% normally, and 5-50 weight% is preferable.

As a coating method to a support base material, the extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, and the die coating method are mentioned. The method of apply | coating using coaters, such as a dip coater, a bar coater, and a spin coater, is also mentioned.

As a support base material, what can form an orientation film on this support base material is preferable. Specifically, glass, a plastic sheet, a plastic film, and a translucent film are mentioned. As a translucent film, Polyolefin films, such as polyethylene, a polypropylene, and norbornene-type polymer; Polyvinyl alcohol film; Polyethylene terephthalate film; Polymethacrylic acid ester film; Polyacrylic acid ester film; Cellulose ester film; Polyethylene naphthalate film; Polycarbonate film; Polysulfone film; Polyether sulfone film; Polyether ketone film; Polyphenylene sulfide film; And polyphenylene oxide films.

Even in the process where the strength of the film such as the film bonding step, the conveying step, and the storage step is required, the support substrate can be used to easily handle the film without breaking the film.

After forming an oriented film on a support base material, it is preferable to apply the solution of a compound (1) on this oriented film. It is preferable that an orientation film has solvent tolerance which does not melt | dissolve in the solution at the time of application | coating of the solution of compound (1). Moreover, it is preferable that an orientation film has heat resistance in heat processing for removal of a solvent and orientation of a liquid crystal. Moreover, it is preferable that it is an orientation film which does not produce peeling by friction etc. at the time of rubbing. As such an oriented film, what consists of a composition containing an orientation polymer or an orientation polymer is preferable.

As said orientation polymer, the polyamide or gelatin compound which has an amide bond in a molecule | numerator, the polyimide which has an imide bond in a molecule | numerator, and the polyamic acid, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, polyoxa which are its hydrolyzate Sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid ester. These orientation polymers may be used independently, and may mix and use two or more types. Moreover, the copolymer of these orientation polymers may be sufficient. These oriented polymers can be easily obtained by polycondensation such as dehydration polycondensation and deamine polycondensation, radical polymerization, anion polymerization, chain polymerization such as cationic polymerization, coordination polymerization, ring-opening polymerization and the like.

These oriented polymers are normally dissolved in a solvent and used as a solution. Solvents are 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, γ-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; Etc. can be mentioned. These solvents may be used independently and may be used in combination of 2 or more type.

A commercially available alignment film material may be used as it is to form an alignment film. Examples of commercially available alignment film materials include San Eva (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optimer (registered trademark, manufactured by JSR Corporation).

When such an alignment film is used, it is not necessary to perform refractive index control by stretching, so that the in-plane variation of birefringence is small, and a large film that can cope with the enlargement of a flat panel display device (FPD) on a supporting substrate can be provided. Can be.

As a method of forming an oriented film on a support base material, the method of apply | coating on the support base material the compound used as a material of a oriented film or an oriented film as a solution, and apply | coating after that is mentioned.

The thickness of the alignment film is usually 10 to 10,000 nm, preferably 10 to 1,000 nm. When it is in the said range, a compound (1) can be orientated at a desired angle on the alignment film. If necessary, the alignment film may be subjected to a rubbing treatment, the alignment film may be subjected to polarized UV irradiation, and the treatment may cause the compound (1) to be oriented at a desired angle and direction, and the refractive index ellipsoid exhibiting the birefringent state of the produced film. You can adjust the shape and tilt of Moreover, when performing a rubbing process, or when performing polarization UV irradiation to an oriented film, when masking is performed, an orientation pattern can be manufactured to a film.

As a method of rubbing an oriented film, the method in which a rubbing cloth is wound and the rotating rubbing roll is made to contact the oriented film carried on the stage and conveyed is mentioned.

[Unpolymerized Film Preparation Process]

An unpolymerized film is obtained by apply | coating and drying the solution of compound (1) on a support base material or the orientation film formed on the support base material. When an unpolymerized film shows liquid crystal phases, such as a nematic phase, it has birefringence by monodomain orientation. Unpolymerized film is orientated mono domain by drying at 0-250 degreeC normally. Since compound (1) expresses a liquid crystal phase at low temperature, monodomain orientation is obtained at comparatively low temperature, and monodomain orientation is maintained even if it cools to about 0-100 degreeC after orientation.

[Unpolymerized Film Polymerization Process]

A polymerized film is obtained by superposing | polymerizing and hardening the obtained unpolymerized film. Since a polymeric film is a film in which the orientation of the compound (1) is immobilized, it is hardly affected by the change of birefringence due to heat.

The method of superposing | polymerizing an unpolymerized film is suitably determined according to the kind of polymeric group of compound (1). If the polymerizable group of the compound (1) is a photopolymerizable group, a photopolymerization method is used. If the polymerizable group is a thermopolymerizable group, a thermal polymerization method is used. According to the photopolymerization method, the unpolymerized film can be polymerized at a low temperature, and the compound (1) having a photopolymerizable group is used in that the selection range of the heat resistance of the supporting substrate becomes wider and the industrial production is easy. It is preferable. The photopolymerization reaction is performed by irradiating the unpolymerized film with visible light, ultraviolet light or laser light. In terms of handling, ultraviolet light is particularly preferred.

Although removal of a solvent may be performed in parallel with a polymerization reaction, it is preferable at the point of film formability to remove most solvents before performing a polymerization reaction. As the removal method, methods, such as natural drying, ventilation drying, reduced pressure drying, and heat drying, are mentioned. The temperature at the time of heating and removing a solvent is 10-200 degreeC normally, and it is preferable that it is 20-150 degreeC. The heating time is usually 10 seconds to 60 minutes, and preferably 30 seconds to 30 minutes. If heating temperature and a heat time exist in the said range, the support base material in which heat resistance is not necessarily enough as a support base material can be used.

The film of this invention can be manufactured by a coating method. A thin film can be manufactured on the flexible support substrate or curvature-supported substrate represented by a flexible substrate.

By peeling a support base material, the film in which the orientation film and the film of this invention were laminated | stacked is obtained, Furthermore, the orientation film is peeled off and the film of this invention can be obtained. In addition, another supporting substrate is bonded to the film of the present invention formed on the supporting substrate or the alignment film, and the transfer is performed by peeling off the supporting substrate on which the film of the present invention is formed or peeling the supporting substrate and the alignment film. You can also carry out.

By adjusting content of the compound (1) and liquid crystal compound in the composition of this invention suitably, a film thickness can be adjusted so that a desired phase difference may be provided. Since the phase difference value (retardation value, Re ((lambda))) of the film obtained is determined like Formula (7), in order to obtain desired Re ((lambda)), what is necessary is just to adjust (DELTA) n ((lambda)) and film thickness (d) suitably. .

Re (λ) = d × Δn (λ) (7)

(Wherein Re (λ) represents a phase difference value at a wavelength λ nm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λ nm)

The film thus obtained is excellent in transparency and used as various display films. Although the thickness of the layer formed differs according to the phase difference value of the film obtained as mentioned above, it is preferable that it is 0.1-10 micrometers, and it is more preferable that it is 0.2-5 micrometers in the point which makes photoelasticity small.

The film of this invention can change an optical characteristic in various ways by changing the orientation state of a compound (1). As a result, when used as a retardation film for liquid crystal panels, optical characteristics can be changed so that it can be used for VA mode, IPS mode, OCB mode, TN mode, STN mode, etc.

More specifically, in the film of the present invention, n _x is the refractive index in the in-plane slow axis direction, n _y is the refractive index in the direction orthogonal to the slow axis in the plane, and n _z is the refractive index in the thickness direction. 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 A C plate, a positive O plate and a negative O plate of n _x ≠ n _y ≠ n _z can be produced.

Moreover, although the thin film which fixed the orientation of a chiral nematic phase is known to be selectively reflected, the selective reflection is confirmed also in the film of this 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 λ (nm) is represented by λ = n · P, n represents the average refractive index of the composition, and P represents the spiral pitch (μm) of the chiral nematic phase. In general, when the content of the chiral agent increases, P decreases, 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 spiral axis is oriented so as to be substantially orthogonal from the plane direction of the transparent support.

By using a chiral agent in this way, a torsion-oriented film, a selective reflection film, a brightness improving film, a negative C plate, etc. can be made. Moreover, when using as a film of a negative C plate, it is preferable that there exists a selective reflection wavelength band in an ultraviolet region.

Although one film of this invention shows the outstanding optical characteristic, you may laminate | stack two or more films of the same function, and may use it in combination with another film. Therefore, the film of this invention can be used for retardation film, a viewing angle compensation film, a viewing angle expansion film, an antireflection film, a polarizing film, a circularly polarizing film, an elliptical polarizing film, a brightness improving film, etc.

Moreover, since the film of this invention can be formed by superposing | polymerizing by application | coating and ultraviolet irradiation, it can also form a film in a liquid crystal cell or a color filter, without going through the process of adhesion | attachment. In addition, patterning of optical functions is also possible, and is also optimal for use as a so-called in-cell retardation plate.

1 is a schematic cross-sectional view showing an example of a polarizing film containing a film of the present invention, FIG. 2 is a schematic cross-sectional view showing an example of a liquid crystal display device including a film of the present invention, and FIG. It is a schematic sectional drawing which shows an example of the organic electroluminescence display containing a film, and FIG. 4 is a schematic sectional drawing which shows an example of the color filter containing the film of this invention. In such a figure, the film may be only the film of the present invention, the alignment film may be laminated on the film of the present invention, or the alignment film and the supporting substrate may be laminated on the film of the present invention. In addition, an adhesive agent and an adhesive may be generically called an adhesive agent.

In FIG. 1, embodiment of the polarizing film containing the film of this invention is shown. FIG.1 (a) is embodiment to which the film 1 of this invention and the polarizing film layer 2 were directly bonded, and FIG.1 (b) is the film 1 and polarizing film layer of this invention ( 2) This is embodiment bonded together via the adhesive bond layer 3. FIG. 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' and the polarizing film layer 2 of the present invention are directly bonded. 1 (d) is a film 1 of the present invention and a film 1 'of the present invention are adhered through an adhesive layer 3, and a polarizing film layer on the film 1' of the present invention. This is an embodiment in which (2) is directly bonded. FIG.1 (e) adheres the film 1 of this invention and the film 1 'of this invention through the adhesive bond layer 3, and also the film 1' and polarizing film layer 2 of this invention. ) Is an embodiment in which an adhesive layer is bonded through an adhesive layer 3 '.

The polarizing film layer may be a film having a polarizing function, and specifically, a film and a polyvinyl alcohol-based film drawn by adsorbing an iodine or a dichroic dye on a polyvinyl alcohol-based film and stretched to adsorb iodine or a dichroic dye. The film etc. which were made are mentioned. Moreover, the polarizing film layer may be equipped with the film used as a protective film as needed. As a protective film, Polyolefin films, such as polyethylene, a polypropylene, and norbornene-type polymer; Polyethylene terephthalate film; Polymethacrylic acid ester film; Polyacrylic acid ester film; Cellulose ester film; Polyethylene naphthalate film; Polycarbonate film; Polysulfone film; Polyether sulfone film; Polyether ketone film; Polyphenylene sulfide film; And polyphenylene oxide films; Etc. can be mentioned.

It is preferable that the adhesive agent used for the adhesive bond layer 3 and the adhesive bond layer 3 'is an adhesive high in transparency and excellent in heat resistance. Examples of the adhesive include acrylic adhesives, epoxy adhesives, urethane adhesives, and the like.

Moreover, as shown to FIG. 1 (c)-FIG. 1 (e), you may adhere | attach 2 or more films of this invention directly or through an adhesive bond layer.

The flat panel display device of this invention is equipped with the film of this invention, Specifically, the liquid crystal display device provided with the polarizing film containing the film of this invention, and the liquid crystal panel to which the liquid crystal panel was bonded, of the present invention The organic electroluminescence display provided with the polarizing film containing a film, and the organic electroluminescent panel (henceforth "EL") with which the light emitting layer adhere | attached is mentioned.

As an embodiment of the flat panel display device of the present invention, a liquid crystal display device and an organic EL display device will be described in detail below.

[Liquid crystal display device]

As a specific example of a liquid crystal display device, the liquid crystal display device provided with the liquid crystal panel as shown to FIG. 2 (a) and FIG. 2 (b) is mentioned. The liquid crystal panel is formed by adhering the member 4 and the liquid crystal panel 6 including the film of the present invention through the adhesive layer 5 as shown in Fig. 2 (a) or as shown in Fig. 2 (b). The member 4 containing the film of this invention and the member 4 'containing the film of this invention are adhere | attached on both surfaces of the liquid crystal panel 6 through the contact bonding layer 5 and the contact bonding layer 5'. According to the above configuration, by applying a voltage to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules can be driven to perform monochrome display.

[Organic EL display device]

As an example of an organic electroluminescence display, the organic electroluminescence display provided with the organic electroluminescent panel shown in FIG. 3, etc. are mentioned. The organic EL panel is formed by bonding the member 4 containing the film of the present invention and the light emitting layer 7 via the adhesive layer 5. The said light emitting layer 7 is a layer of at least 1 layer which consists of electroconductive organic compounds.

Moreover, in the said organic electroluminescent panel, when the member 4 containing the film of this invention is a polarizing film, it functions as a broadband circular polarizing plate. Therefore, an antireflection function can be provided to an 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 in which the color filter layer 13 is formed on the film 12 of this invention.

An example of the manufacturing method of the color filter 11 is demonstrated. First, an alignment film material is coated on a supporting substrate, and a rubbing treatment is performed to form an alignment film. Subsequently, while adjusting the thickness so that the film obtained may show the desired phase difference value, the solution containing the compound (1) in which the density | concentration of compound (1) etc. were adjusted so that the film obtained may show desired wavelength dispersion characteristic on the obtained orientation film may be obtained. To form a film. Next, the color filter layer 13 is formed on the film 12 of this invention obtained.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are weight% and a weight part, unless there is particular notice.

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

(1) Synthesis of Compound (e)

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

(Synthesis example of compound (d))

Compound (a) was synthesize | combined by the method described in Unexamined-Japanese-Patent No. 2004-262884.

100 g of compound (a), 97 g of potassium carbonate and 64 g of 6-chlorohexanol were heated and reacted at 90 ° C. in a N, N-dimethylacetamide under a nitrogen atmosphere. Furthermore, it heated and reacted at 100 degreeC. The obtained reaction mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added to separate an organic layer. The organic layer was washed with aqueous sodium hydroxide solution and pure water, and then dehydrated. The dehydrating agent was removed by filtration, and the obtained filtrate was concentrated under reduced pressure. Methanol was added to the obtained residue, the produced precipitate was taken out by filtration and dried in vacuo to give 126 g of compound (b). Yield: 91% (based on 6-chlorohexanol).

Compound (b) 126 g, 3,5-di-tert-butyl-4-hydroxytoluene 1.4 g, N, N-dimethylaniline 117 g, 1 g of 1,3-dimethyl-2-imidazolidinone and chloroform Was mixed. To the obtained mixture, 58 g of acryloyl chloride was added dropwise under ice cooling in a nitrogen atmosphere, and further pure water was added and reacted. The organic layer was separated from the obtained reaction mixture. The organic layer was washed with hydrochloric acid, saturated aqueous sodium carbonate solution and pure water. The organic layer was dried by adding a dehydrating agent. After removing a dehydrating agent, 1 g of 3, 5- di-tert- butyl- 4-hydroxytoluenes were added to the obtained filtrate, and it concentrated under reduced pressure, and obtained the compound (c).

Compound (c) and 200 ml of tetrahydrofuran were mixed. After further adding 200 mL of tetrahydrofuran to the obtained mixture, hydrochloric acid and concentrated hydrochloric acid were added, and reaction was performed at 60 degreeC under nitrogen atmosphere. The reaction mixture was washed with 500 ml of saturated brine and then 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 stirred under ice cooling. The precipitated solid was taken out by filtration and dried in vacuo to obtain 90 g of 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. After heating up the obtained mixture to 80 degreeC, stirring in nitrogen atmosphere, 96 g of potassium carbonate and 10 g of potassium iodide were added. Furthermore, 140 g of benzyl chloride was added, and the obtained solution was reacted at 120 degreeC for 6 hours. After allowing the obtained reaction solution to cool to room temperature, it was poured into 1500 g of ice and stirred. The obtained crystals were taken out by filtration and washed with water / methanol 3: 2 (v / v) followed by water. The crystals after washing were dried in vacuo to give 251 g of a powder containing compound (f).

251 g of a powder containing 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 dripped under nitrogen atmosphere. The obtained solution was made to react at room temperature under nitrogen atmosphere for 3 hours. 600 ml of toluene was added to the obtained reaction solution, and the hydrochloride salt of triethylamine which precipitated 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 solvent was removed from the filtrate obtained. The obtained concentrated residue was dried in vacuo to give 242 g of a liquid containing a compound (g).

242 g of liquid containing compound (g) and 250 ml of tetrahydrofuran were mixed. After adding 10 g of 10% palladium-carbon (50% hydrous) to the obtained solution under nitrogen atmosphere, the mixture obtained at room temperature and atmospheric pressure was reacted under hydrogen atmosphere for 6 hours. The obtained 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. Insoluble matter on silica gel was extracted with chloroform, and the resulting chloroform solution was concentrated under reduced pressure. Heptane was added to the obtained residue for crystallization. The obtained crystal was taken out by filtration and dried in vacuo to obtain 106 g of compound (h). Yield: 39% (based on trans-1,4-cyclohexanedicarboxylic acid).

(Synthesis example of compound (e))

56.8 g of compound (d), 2.65 g of N, N-dimethylaminopyridine, 50 g of compound (h) and 300 ml of chloroform were mixed. The obtained liquid mixture was ice-cooled and stirred in nitrogen atmosphere, and the solution obtained by dissolving 48.79 g of dicyclohexyl carbodiimide in 50 ml of chloroform was dripped. After completion of dropping, the obtained 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. The filtrate was washed with 2N hydrochloric acid, and then the insolubles were removed by filtration. After drying the obtained filtrate with anhydrous sodium sulfate, sodium sulfate was removed by filtration. From the obtained filtrate, the solvent was removed and the obtained solid was vacuum dried to obtain 100 g of the compound (e ').

100 g of 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 ° C under a nitrogen atmosphere. After allowing the obtained reaction solution to cool to room temperature, 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 dried in vacuo. The obtained 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 obtained solution was concentrated under reduced pressure. Heptane was added to the concentrated residue to crystallize, and the obtained crystals were taken out by filtration. The taken crystal was dried in vacuo to give 64 g of compound (e). Yield: 76% (based on compound (d)).

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

3.4 g of phenylhydroquinone, 16 g of compound (e), 0.5 g of 4-dimethylaminopyridine and 237 g of chloroform were mixed. The solution obtained by dissolving 9.4 g of N, N'- dicyclohexylcarbodiimide in 9 g of chloroform was dripped at the obtained mixture at room temperature, and it was made to react for 36 hours. 140 g of 2N hydrochloric acid was added to the obtained reaction mixture, and the obtained mixture was filtered. 140g of 2N hydrochloric acid was added to the obtained filtrate, and it wash | cleaned, and it concentrated, and obtained about 50g of concentrate. 0.4 g of activated carbon was added to the concentrate, and the mixture was filtered through celite. After the obtained filtrate was concentrated, methanol was added to the concentrated residue to obtain a solid. The obtained solid was wash | cleaned with methanol, and 8.4g of compound (1-a14) which is a white solid was obtained. Yield: 47% (based on phenylhydroquinone)

The phase transition temperature of the obtained compound (1-a14) was confirmed by texture observation with a polarization microscope. The compound (1-a14) showed a nematic phase from 84 degreeC to 198 degreeC at the time of temperature rising, and became isotropic at 198 degreeC. When temperature was lowered at 200 degreeC, the nematic phase was shown from 198 degreeC to 36 degreeC, and it crystallized at 36 degreeC. Thus, the compound (1-a14) not only shows nematic liquid crystallinity in a wide temperature range, but also shows nematic liquid crystallinity in the vicinity of 40 degreeC.

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

1.0 g of tert-butylhydroquinone, 6.0 g of compound (e), 0.2 g of 4-dimethylaminopyridine and 121 g of chloroform were mixed. The solution obtained by dissolving 4.5 g of N, N'- dicyclohexylcarbodiimide in 24 g of chloroform was dripped at the obtained mixture at room temperature, and it was made to react for 3 hours. After 60 g of 2N hydrochloric acid was added to the obtained reaction solution, the obtained mixture was filtered. The obtained filtrate was washed with 60 g of 2N hydrochloric acid, and then concentrated to give about 40 g of concentrated solution. 0.3 g of activated carbon was added to the concentrate, and the mixture was 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 wash | cleaned with methanol, and 4.1g of compound (1-a3) which is a white solid was obtained. Yield: 71% (based on tert-butylhydroxy).

The phase transition temperature of the obtained compound (1-a3) was confirmed by texture observation with a polarization microscope. It confirmed that the compound (1-a3) showed the smectic phase from 66 degreeC to 96 degreeC at the time of temperature rising, and showed the nematic phase from 96 degreeC to at least 180 degreeC. As a result of lowering the temperature at 180 ° C., it was confirmed that the nematic phase was exhibited from 180 ° C. to at least 29 ° C., and crystallization was not performed. The compound (1-a3) not only shows nematic liquid crystallinity in a wide temperature range, but also shows 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 ° C and stirred. After cooling, methylisobutylketone was added to the reaction mixture and the mixture was washed with water, and then the solvent was removed to obtain 126 g of an oily substance having compound (i) as a main component. Yield: 88% (based on ethyl 4-hydroxybenzoate).

(Synthesis example of compound (j))

126 g of an oily substance having 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 ° C. After cooling the reaction mixture, it was poured into 756 g of ice and further hydrochloric acid was added. The precipitated solid was taken out, washed with water and heptane, and dried to obtain 91 g of a solid containing compound (j) as a main component. Yield: 97% (based on compound (i)).

(Synthesis example of compound (k))

Under a nitrogen atmosphere, 90.0 g of solid having Compound (i) and 77.8 g of N, N-dimethylaniline were dissolved in 720 g of N, N-dimethylacetamide. After cooling the obtained solution to 0 degreeC, 58.1 g of acrylic acid chlorides were dripped and reacted at room temperature. 1N hydrochloric acid was added to the obtained reaction mixture, and the precipitated solid was taken out. The solid taken out was dissolved in ethyl acetate. After wash | cleaning the obtained solution with water, the solvent was removed and the solid 102g which has a compound (k) as a main component was obtained. Yield: 90% (based on compound (j)).

(Synthesis example of compound (III-1-1))

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

The phase transition temperature of compound (III-1-1) was confirmed by texture observation with a polarization microscope. When the temperature was increased, the crystal phase was changed from the crystal phase to the nematic phase in the vicinity of 107 ° C, and further changed to the isotropic liquid phase in the vicinity of 167 ° C. When the temperature was lowered, it changed from an isotropic liquid phase to a nematic phase near 167 ° C, and when the temperature was lowered to around 74 ° C, it returned to a crystalline phase. That is, it was found that the compound (III-1-1) exhibited a nematic phase between 107 ° C and 167 ° C at the time of elevated temperature and between 167 ° C and 107 ° C at the time of temperature decrease.

Examples 3-6 and Comparative Example 2

<Preparation of composition>

The composition of the composition of Table 2 was prepared. % In Table 2 means the weight% at the time of making the total weight of a composition into 100 weight%.

Photopolymerization initiator: Irgacure 819 (manufactured by Chiba Japan; Acylphosphine oxide compound)

Leveling agent: BYK361N (manufactured by Big Chemie Japan)

Solvent: Cyclopentanone

<Heat behavior observation>

A 2 wt% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified, 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. A rubbing treatment was performed on the surface of the film to form an alignment film. The surface of the rubbing process was apply | coated by the spin coat method of the composition of Table 2. The obtained substrate was heated using a polarizing microscope equipped with a hot stage (hot stage: LTS350, manufactured by Linkam, polarized microscope: BX-51, manufactured by Olympus) while heating at a temperature increase rate of 30 deg. The behavior was observed. At low temperature, the behavior was observed by natural cooling. The results are shown in Table 3.

Observation Example 3 Increasing the temperature, it was confirmed that the phase transition to the nematic phase at 78 ℃ to start to form a mono domain structure, maintaining the mono domain structure to at least 150 ℃. When temperature was lowered at 150 degreeC, the nematic phase was shown to 38 degreeC, the monodomain structure was formed, and it crystallized at 38 degreeC. Example 4 When the temperature was raised, it was confirmed that the phase transition to nematic phase at 20 ° C started to form a monodomain structure, and the monodomain structure was maintained up to at least 150 ° C. When temperature was lowered at 150 degreeC, the nematic phase was shown to 40 degreeC, the monodomain structure was formed, and it crystallized at 40 degreeC. Example 5 When the temperature was raised, it was confirmed that the phase transition to a nematic phase at 84 ° C. started to form a mono domain structure, and the mono domain structure was maintained up to at least 150 ° C. When temperature was lowered at 150 degreeC, the nematic phase was shown to 40 degreeC, the monodomain structure was formed, and it crystallized at 40 degreeC. Example 6 When the temperature was increased, it was confirmed that the phase shifted to a nematic phase at 100 ° C to start to form a monodomain structure, and maintained the monodomain structure up to at least 150 ° C. When temperature was lowered at 150 degreeC, the nematic phase was shown to 36 degreeC, the monodomain structure was formed, and it crystallized at 36 degreeC. Comparative Example 2 When the temperature was raised, it was confirmed that the phase shifted to a nematic phase at 143 ° C to start to form a monodomain structure, and maintained the monodomain structure up to at least 158 ° C. When the temperature was lowered at 160 degreeC, the nematic phase was shown to 80 degreeC and it confirmed that the monodomain structure was formed.

<Production example of film>

A 2 wt% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified, 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. A rubbing treatment was performed on the surface of the film to form an alignment film. The surface of the rubbing process was apply | coated by the spin coat method, and the composition of Table 2 was dried at the temperature (T _c ) of Table 4 for 1 minute. After being left for 1 minute at the temperature (T _d ) shown in Table 4, a film was prepared by irradiating ultraviolet rays with an integrated light quantity of 2400 mJ / cm 2.

<Observation of surface state>

The surface state of the film was observed at a magnification of 400 times with a polarizing microscope. (Circle) when the monodomain is shown, and when a defect has generate | occur | produced, it is set to x. The results are shown in Table 4.

<Time stability>

After leaving the film in the air at room temperature for 2 weeks, the surface state of the film was observed with a polarizing microscope. When an orientation defect is not found, it is set as x when (circle) and generation | occurence | production of an orientation defect is confirmed. The results are shown in Table 4.

Measurement of Optical Properties

The retardation value of the film was measured by the measuring device (KOBRA-WR, the Oji measuring instrument company make). 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 (for a glass substrate and an alignment film, Re (447) = Re ( 547) = Re (628) = 0) and the measured retardation value can be used as the retardation value of the film. Retardation value Re ((lambda)) was measured at wavelength ((lambda)) 447 nm, 547 nm, and 628 nm. The film thickness (d) (micrometer) of the film was measured using the laser microscope (LEXT3000, Olympus company). The results are shown in Table 5.

In the Example, the film was manufactured at low temperature of 30 degreeC or 50 degreeC.

By superposing | polymerizing the compound of this invention, the film which is excellent in surface state and time-lapse stability, and has an optical characteristic can be manufactured at 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 emitting layer
11 color filter
12 films
13 color filter layer

Claims (7)

Formula (1)

(In formula, X represents a C2-C20 alkyl group, a C3-C20 cyclic alkyl group, or a C6-C20 substituted or unsubstituted aromatic hydrocarbon group,
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 one or more methylene groups 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)
Compound represented by. The method of claim 1,
In Formula (1), P <^1> and P <^2> are respectively independently Formula (P-1)

(In formula, R <^1> , R <^2> and R <^3> represent a C1-C6 alkyl group or a hydrogen atom each independently.)
Compound which is group represented by. The composition containing the compound of Claim 1 or 2, and a photoinitiator. The film obtained by superposing | polymerizing the compound of Claim 1 or 2. The color filter containing the film of Claim 4. The flat panel display device containing the film of Claim 4. The manufacturing method of the film containing the process of apply | coating the compound of Claim 1 or 2 on the oriented film formed on the base material or the base material.

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