JP5754078B2 - Compound - Google Patents

Description

  The present invention relates to a compound useful for producing a film.

A flat panel display (FPD) includes members using films such as a polarizing plate and a retardation plate. For example, Patent Document 1 discloses a retardation obtained by polymerizing a solution obtained by dissolving a polymerizable compound represented by the formula (III-1-1) in a solvent and then applying the solution to a support substrate. A plate is disclosed.

JP 2003-287623 A

  The surface condition and stability over time of a film obtained from a conventional polymerizable compound are not always satisfactory.

As a result of intensive studies under these circumstances, the present inventors have reached the present invention.
That is, the present invention is the following invention.
[1] A compound represented by formula (1).

[In the formula (1), X represents an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a monovalent aromatic carbon atom having 6 to 20 carbon atoms which may have a substituent. Represents a hydrogen group.
E ¹ and E ² each independently represents a single bond or a divalent linking group.
A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group which may have a substituent.
B ¹ , B ² , B ³ and B ⁴ each independently represents a single bond or a divalent linking group.
F ¹ and F ² each independently represents an optionally substituted alkanediyl group having 1 to 12 carbon atoms, and —CH ₂ — contained in the alkanediyl group having 1 to 12 carbon atoms is , -O- may be substituted.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

［式（Ｐ−１）中、Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、炭素数１〜６のアルキル基又は水素原子を表す。］ [2] The above compound, wherein P ¹ and P ² are each independently a group represented by the formula (P-1).

[In Formula (P-1), R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]

[3] A composition comprising 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 comprising the film according to [4].

[7] A method for producing a film comprising a step of applying the compound according to [1] or [2] on a substrate or an alignment film formed on the substrate.

  According to the compound of the present invention, a film excellent in surface condition and stability over time can be produced.

It is the schematic which shows a polarizing film. It is the schematic which shows a liquid crystal display device. It is the schematic which shows an organic electroluminescence display. It is the schematic which shows a color filter.

［式（１）中、Ｘは、炭素数２〜２０のアルキル基、炭素数３〜２０のシクロアルキル基又は置換基を有していてもよい１価の炭素数６〜２０の芳香族炭化水素基を表す。
Ｅ^１及びＥ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｂ^１、Ｂ^２、Ｂ^３及びＢ^４は、それぞれ独立に、単結合又は２価の連結基を表す。
Ｆ^１及びＦ^２は、それぞれ独立に、置換基を有していてもよい炭素数１〜１２のアルカンジイル基を表し、該炭素数１〜１２のアルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−で置き換っていてもよい。
Ｐ^１及びＰ^２は、それぞれ独立に、水素原子又は重合性基を表す。］ The present invention is a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).

[In the formula (1), X represents an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a monovalent aromatic carbon atom having 6 to 20 carbon atoms which may have a substituent. Represents a hydrogen group.
E ¹ and E ² each independently represents a single bond or a divalent linking group.
A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group which may have a substituent.
B ¹ , B ² , B ³ and B ⁴ each independently represents a single bond or a divalent linking group.
F ¹ and F ² each independently represents an optionally substituted alkanediyl group having 1 to 12 carbon atoms, and —CH ₂ — contained in the alkanediyl group having 1 to 12 carbon atoms is , -O- may be substituted.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

  Examples of the alkyl group having 2 to 20 carbon atoms represented by X include ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 3- Methylbutyl, hexyl, 1-methylpentyl, 4-methylpentyl, heptyl, 1-methylhexyl, 5-methylhexyl, octyl, 1-methylheptyl, nonyl, 1-methyloctyl , 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 cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group. Groups are preferred.

Examples of the 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. 6-14 aromatic hydrocarbon groups are preferred. Such an aromatic hydrocarbon group may have a substituent. Examples of the substituent include alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a methoxy group, an ethoxy group, a propoxy group, and the like. And an alkoxy group having 1 to 5 carbon atoms; and halogen atoms such as a fluorine atom, a chlorine atom, and a 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.
X is preferably an alkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

The divalent linking group represented by E ¹ and E ² includes a divalent organic group, and includes —O—, —S—, —CO—O—, —O—CO—, and —O—CO—O—. , —CO—NR ⁶ —, —NR ⁶ —CO—, —O—CH ₂ — and —CH ₂ —O—. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, hexyl group, etc.). Among these, * -CO-O- (* represents a bond with a cyclohexane-1,4-diyl group) is preferable.

The divalent aromatic hydrocarbon group represented by A ¹ and A ² is a group consisting of a 5-membered or 6-membered aromatic group represented by formula (g-1) to formula (g-5). Is preferred. The hydrogen atom contained in the divalent aromatic hydrocarbon group is a halogen atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, etc.) Substituted with an alkoxy group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, etc.), trifluoromethyl group, cyano group or nitro group Also good.

Examples of A ¹ and A ² include 1,4-phenylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 4,4′-biphenylene group, and fluorene-2,7-diyl group. And a 1,4-phenylene group is preferable.

The divalent linking group represented by B ¹ , B ² , B ³ and B ⁴ includes a divalent organic group, and includes —O—, —S—, —CO—O—, —O—CO—, — ^{O-CO-O -, -} CO-NR 6 -, - NR 6 -CO -, - CO- and -CS- and the like. R ⁶ represents the same meaning as described above.
Among them, B ¹ , B ² , B ³ and B ⁴ include —O—, —CO—O—, —O—CO—, —O—CO—O—, —CO—, —O—CH ₂ —. , —CH ₂ —O— and a single bond are preferred.
B ¹ and B ² are more preferably —O—, and B ³ and B ⁴ are more preferably * —O—CO— (* represents a bond with F ¹ or F ² ).

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

Examples of the alkanediyl group having 1 to 12 carbon atoms which may have a substituent represented by F ¹ and F ² include a methylene group, an ethylene group, a propane-1,2-diyl group, and propane-1,3- Diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decandiyl group A straight-chain or branched one-chain alkanediyl group such as an undecandiyl group and a dodecandiyl group is preferred, an alkanediyl group having 4-8 carbon atoms is more preferred, and an alkanediyl group having 4-6 carbon atoms. The group is particularly preferred.
—CH ₂ — contained in the alkanediyl group having 1 to 12 carbon atoms may be replaced by —O—. Examples of the alkanediyl group in which —CH ₂ — is replaced by —O— include, for example, —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 - and the like.

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

［式（Ｐ−１）〜（Ｐ−５）中、Ｒ^１〜Ｒ^５はそれぞれ独立に、炭素数１〜６のアルキル基又は水素原子を表す。＊は、Ｂ^３又はＢ^４との結合位置を表す。］ Examples of the polymerizable group include groups represented by formula (P-1) to formula (P-5), and groups represented by formula (P-1) and formula (P-2) are preferable. The group represented by P-1) is more preferable.

[In formulas (P-1) to (P-5), R ^{1 to} R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. * Represents a bonding position with B ³ or B ⁴ . ]

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

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

Compound (1) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. (for example, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heartwig reaction, Friedel-Craft reaction, Heck reaction, Aldol reaction, etc. ) Can be manufactured by appropriately combining depending on the structure.

（式中、Ｅ^１、Ｅ^２、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｂ^３、Ｂ^４、Ｆ^１、Ｆ^２、Ｐ^１、Ｐ^２及びＸは上記と同一の意味を表す。）
式（１−１）で示される化合物と式（１−２）で示される化合物との反応及び式（１−３）で示される化合物と式（１−４）で示される化合物との反応は、縮合剤の存在下に実施することが好ましい。縮合剤としては、公知のものを使用することができる。 For example, the compound represented by the formula (1-1) and the compound represented by the formula (1-2) are reacted to obtain the compound represented by the formula (1-3). Compound (1) can be obtained by reacting the compound represented by 3) with the 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 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 reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) It is preferable to carry out in the presence of a condensing agent. A well-known thing can be used as a condensing agent.

The composition of this invention contains a compound (1).
The composition of the present invention may contain one type of compound (1), or may contain two or more different types of compounds (1). Further, the composition of the present invention may contain a liquid crystal compound (however, different from the compound (1)).

  Specific examples of liquid crystal compounds include: Chapter 3 of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). .3 Among compounds described in chiral rod-like liquid crystal molecules, compounds having a polymerizable group may be mentioned. As the liquid crystal compound, a plurality of different liquid crystal compounds may be used in combination.

  Examples of the liquid crystal compound include a compound containing a group represented by the formula (4) (hereinafter sometimes referred to as “compound (4)”).

^{P 11 -B 11 -E 11 -B 12} -A 11 -B 13 - (4)
(In the formula ^{(4), P 11} represents a polymerizable group.
A ¹¹ represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group. The hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
B ¹¹ is —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹⁶ —, —NR ¹⁶ —CO—, —CO—, -CS- or a single bond is represented. 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)-, -O-C (= 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—, —O—C (═O) —CH═CH— or a single bond.
E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. In addition, hydrogen atoms contained in the alkyl group and alkoxy group may be substituted with a halogen atom. —CH ₂ — contained in the alkanediyl group may be substituted with —O— or —CO—. )

［式（Ｐ−１１）〜（Ｐ−１５）中、Ｒ^１７〜Ｒ^２１はそれぞれ独立に、炭素数１〜６のアルキル基又は水素原子を表す。］ The polymerizable group represented by P ¹¹ is preferably a radically polymerizable or cationically polymerizable group in terms of high photopolymerization reactivity, and is particularly easy to handle and easy to produce a liquid crystal compound. The polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15).

[In formulas (P-11) to (P-15), R ^{17 to} R ²¹ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]

More specifically, groups represented by the following formulas (P-16) to (P-20) are exemplified.

P ¹¹ is preferably a group represented by Formulas (P-14) to (P-20), and examples thereof include a vinyl group, a p-stilbene group, an epoxy group, and an oxetanyl group.
Particularly preferably, P ¹¹ -B ¹¹ -is an acryloyloxy group or a methacryloyloxy group.

Carbon number of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A ¹¹ is, for example, 3 to 18, preferably 5 to 12, and particularly preferably 5 or 6. A ¹¹ is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

The E ^11, an alkanediyl group having 1 to 12 carbon atoms and is preferably linear. —CH ₂ — contained in the alkanediyl group may be replaced by —O—.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane -1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12- A linear alkanediyl group having 1 to 12 carbon atoms such as a diyl 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 — and the like.

Examples of compound (4) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -A ¹⁴ -B ¹⁶ -E ¹² -B ¹⁷ -P ¹² (I)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -A ¹⁴ -F ¹¹ (II)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -E ¹² -B ¹⁷ -P ¹² (III)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -F ¹¹ (IV)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -E ¹² -B ¹⁷ -P ¹² (V)
P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -F ¹¹ (VI)
^(Wherein, A 12 ^{to A 14} have ^the same meanings as ^{A 11, B} 14 ^{~B 16 has} the same meaning as ^{B 12, B 17 is B 11} in the above ^{formula, E 12 is} a ^{E 11} It is synonymous.
In the formula, 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 hydroxy group, a methylol group, or a formyl group. , A sulfo group (—SO ₃ H), a carboxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, —CH ₂ — contained in the alkyl group and alkoxy group is replaced by —O—. It may be. )

Specific examples of liquid crystal compounds include: Chapter 3 of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). .3 Among compounds described in chiral rod-like liquid crystal molecules, compounds having a polymerizable group may be mentioned.
Specific examples of the compound (4) include, for example, the following formula (I-1) to formula (I-4), formula (II-1) to formula (II-4), formula (III-1) to formula ( III-26), Formula (IV-1) to Formula (IV-19), Formula (V-1) to Formula (V-2), Formula (VI-1) to Formula (VI-6). Compounds and the like. However, k1 and k2 in the formula represent an integer of 2 to 12. These liquid crystal compounds are preferable because they are easy to synthesize and are commercially available.

  Moreover, the usage-amount of a liquid crystal compound is 90 mass parts or less with respect to a total of 100 mass parts of a liquid crystal compound and a compound (1), for example.

  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 to include an organic solvent that facilitates film formation during film formation, and it is preferable to include a polymerization initiator having a function of curing the obtained film.

(Polymerization initiator)
The polymerization initiator preferably contains a photopolymerization initiator, and the photopolymerization initiator is preferably a photopolymerization initiator that generates radicals by light irradiation.
Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts. Specifically, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all made by Ciba Japan Co., Ltd.), Sake All BZ, Sake All Z, Sake All BEE (all all Seiko) Chemical Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152, Adekaoptomer SP-170 (all above, ADEKA Corporation) Product), TAZ-A, TAZ-PP (manufactured by Nippon Siebel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

  The amount of the polymerization initiator used in the composition of the present invention is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 100 parts by mass in total of the compound (1) and the liquid crystal compound. Parts by mass to 10 parts by mass. If it is in the said range, these can be polymerized, without disturbing the orientation of a compound (1) or a liquid crystal compound.

(Polymerization inhibitor)
Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone or alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl-1 -Radical scavengers such as piperidinyloxy radicals, thiophenols, β-naphthylamines or β-naphthols.

  By using a polymerization inhibitor, the polymerization of the compound (1) can be controlled, and the stability of the film obtained from the composition (1) can be improved. The amount of the polymerization inhibitor used in the composition of the present invention is, for example, 0.1 to 30 parts by mass, preferably 0.5 parts by mass with respect to 100 parts by mass in total of the compound (1) and the liquid crystal compound. Part to 10 parts by mass. If it is in the said range, these can be polymerized, without disturbing the orientation of a compound (1) or a liquid crystal compound.

[Photosensitizer]
Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone), anthracene compounds having a substituent such as anthracene or alkyl ether (for example, dibutoxyanthracene). Etc.), phenothiazine, rubrene and the like.

  By using the photosensitizer, the polymerization reaction of the compound (1) can be performed with high sensitivity, and the temporal stability of the resulting film can be improved. Moreover, as the usage-amount of a photosensitizer, it is 0.1 mass part-30 mass parts with respect to a total of 100 mass parts of a compound (1) and a liquid crystal compound, Preferably it is 0.5 mass part-10 parts. Part by mass. If it is in the said range, these can be polymerized, without disturbing the orientation of a compound (1) or a liquid crystal compound.

(Leveling agent)
As a leveling agent, for example, an additive for radiation-curing coatings (by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), coating additives (by Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA), Examples thereof include paint additives (manufactured by Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) and fluorine additives (manufactured by DIC Corporation: F-445, F-470, F-479). .

  By using a leveling agent, a smoother film can be obtained. Furthermore, the fluidity of the composition of the present invention can be controlled and the crosslinking density of the resulting film can be adjusted during the film production process. Moreover, the usage-amount of a leveling agent is 0.01 mass part-30 mass parts with respect to 100 mass parts of compounds (1) and a liquid crystal compound, for example, Preferably they are 0.05 mass part-10 mass parts. If it is in the said range, these can be polymerized, without disturbing the orientation of a compound (1) or a liquid crystal compound.

〔solvent〕
The solvent is an organic solvent that can dissolve the compound (1), the liquid crystal compound, and the like, and may be any solvent that is inert to the polymerization reaction. Specifically, water; methanol, ethanol, ethylene glycol, isopropyl alcohol Alcohols such as 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; acetone, methyl ethyl ketone Ketone solvents such as cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene and Aromatic solvents cyclohexylene and the like; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; or chloroform and non-chlorinated hydrocarbon solvents such as chlorobenzene; and the like. These organic solvents may be used alone or in combination.

  The viscosity of the composition of the present invention is preferably adjusted to, for example, 10 mPa · s or less, and 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, so that the film obtained from the composition of the present invention can be easily formed. Moreover, the usage-amount of a solvent is 10000 mass parts-10 mass parts with respect to 100 mass parts of compounds (1), for example, Preferably it is 5000 mass parts-100 mass parts. Moreover, the density | concentration of solid content in the composition of this invention is 2-50 mass%, and 5-50 mass% is preferable. Here, solid content means the sum total of the quantity remove | excluding the solvent from the composition of this invention. When the solid content concentration of the composition of the present invention is 2% by mass or more, the film obtained from the composition of the present invention does not become too thin, and a birefringence index necessary for optical compensation of a liquid crystal panel tends to be provided. is there. Moreover, since the viscosity of a solution will become low as it is 50 mass% or less, there exists a tendency for the film thickness of a film to become difficult to produce at the time of film-forming.

[Chiral agent]
As the chiral agent, a known chiral agent (for example, liquid crystal device handbook, chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989) is used. be able to.
The chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
For example, as disclosed in JP 2007-269640, JP 2007-269639, JP 2007-176870, JP 2003-137879, JP 2000-51596, JP 2007-169178, JP 9-169608. Examples thereof include, preferably, palocolor LC756 manufactured by BASF.
The usage-amount of a chiral agent is 0.1 mass part-30 mass parts with respect to a compound (1) and 100 mass parts of liquid crystal compounds, for example, Preferably it is 1.0 mass part-25 mass parts. If it is in the said range, these can be polymerized, without disturbing the orientation of a compound (1) or a liquid crystal compound.

  The film of the present invention refers to a film that can transmit light and has an optical function. The optical function means refraction, birefringence and the like. The retardation film, which is a kind of film of the present invention, converts linearly polarized light into circularly polarized light or elliptically polarized light, conversely converts circularly polarized light or elliptically polarized light into linearly polarized light, or converts the polarization direction of linearly polarized light. Used to do.

The film can be obtained by polymerizing the compound (1). One type of compound (1) may be polymerized, or two or more types of compounds (1) may be polymerized. Moreover, the film of the present invention can also be produced by polymerizing the composition of the present invention.
In terms of ease of film formation, it is preferable to use a solution in which the compound (1) is dissolved in an organic solvent, and a film can be obtained by applying the solution on a supporting substrate, drying and polymerizing. The density | concentration of the solid content in this solution is 2-50 mass%, and 5-50 mass% is preferable.

  The film of the present invention can be obtained on a supporting substrate by applying a solution containing the compound (1) to the supporting substrate, drying and polymerizing the solution.

  Examples of the application method to the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, and a spin coater, etc. are mentioned.

  It is preferable that the support substrate is capable of forming an alignment film on the support substrate. For example, glass, a plastic sheet, a plastic film, and a translucent film can be mentioned. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylic acid ester films, polyacrylic acid ester films, cellulose ester films, and polyethylene naphthalate films. , Polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film and polyphenylene oxide film.

  When the strength of the film is required, such as a bonding step using the film of the present invention, a step of carrying and storing the film, etc., it can be easily handled without tearing by using the support substrate.

  In the film of the present invention, preferably, after forming an alignment film on a support substrate, it is preferable to apply a solution containing the compound (1) on the alignment film. The alignment film preferably has a solvent resistance that does not dissolve when a solution containing the compound (1) is applied. Moreover, it is preferable to have heat resistance in the heat treatment for solvent removal and liquid crystal alignment. Furthermore, an alignment film that does not peel off due to friction due to rubbing or the like is preferable. Such an alignment film is preferably composed of an alignment polymer or a composition containing an alignment polymer.

  Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyacrylamide which are hydrolysates thereof. Mention may be made of polymers such as oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. These polymers may be used alone, or two or more kinds thereof may be mixed or copolymerized. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  These alignment polymers can be dissolved in a solvent and applied. The solvent is not particularly limited, and specifically, water; alcohol such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol Ester solvents such as 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; fats such as pentane, hexane and heptane Aromatic solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Tetrahydrofuran and di Chlorinated solvents or chloroform and chlorobenzene; an ether solvent such as Tokishietan like. These organic solvents may be used alone or in combination.

  In order to form the alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optmer (registered trademark, manufactured by JSR Corporation).

  If such an alignment film is used, it is not necessary to control the refractive index by stretching, so that in-plane variation in birefringence is reduced. Therefore, it is possible to provide a large film that can cope with an increase in the size of a flat panel display (FPD) on a supporting substrate.

  As a method for forming an alignment film on the support substrate, for example, a commercially available alignment film material or a compound serving as an alignment film material is applied as a solution on the support substrate, and then annealed, An alignment film can be formed on the support substrate.

  The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, a compound (1) can be orientated on a desired angle on this alignment film.

Further, these alignment films can be rubbed or irradiated with polarized UV rays as necessary. By these orientation treatments, the compound (1) can be oriented in a desired angle and direction, and the shape and inclination of the refractive index ellipsoid showing the birefringence state of the produced film can be adjusted. In addition, if masking is performed when rubbing or polarized UV irradiation is performed, an orientation pattern can be formed on the film.
As a method for rubbing the alignment film, for example, a method in which a rubbing cloth is wound and a rotating rubbing roll is placed on a stage and brought into contact with the alignment film being conveyed can be used.

[Unpolymerized film preparation process]
When an alignment film is formed on the support substrate or on the support substrate, a solution containing the compound (1) is applied onto the alignment film and dried to obtain an unpolymerized film. When this unpolymerized film exhibits a liquid crystal phase such as a nematic phase, it has birefringence due to monodomain alignment. This unpolymerized film is usually monodomain oriented by drying at 0 to 250 ° C. Since the compound (1) exhibits a liquid crystal phase at a low temperature, a monodomain alignment is obtained at a relatively low temperature. After the alignment, the monodomain alignment is maintained even when cooled to about 100 to 0 ° C.

[Unpolymerized film polymerization process]
A polymerized film is obtained by polymerizing and curing the obtained unpolymerized film. The polymerized film is a film in which the orientation of the compound (1) is fixed, and therefore is not easily affected by changes in birefringence due to heat.
The method for polymerizing the unpolymerized film may be selected according to the type of the polymerizable group of the compound (1). If the polymerizable group of the compound (1) is a photopolymerizable group, a photopolymerization method is used, and if the polymerizable group is a thermopolymerizable group, a thermal polymerization method is used. According to the photopolymerization method, it is possible to polymerize an unpolymerized film at a low temperature, and the photopolymerizable group can be produced in that the range of heat resistance of the supporting substrate is widened and the industrial production is easy. It is preferable to use the compound (1) having The photopolymerization reaction is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. In view of handling, ultraviolet light is particularly preferable.

  The removal of the solvent may be performed in parallel with the polymerization reaction, but it is preferable from the viewpoint of film formability to remove most of the solvent before the polymerization reaction. Examples of the removal method include natural drying, ventilation drying, reduced pressure drying, and heat drying. The temperature at which the solvent is removed by heating is preferably 10 to 200 ° C, more preferably 20 to 150 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. If the heating temperature and the heating time are within the above ranges, a supporting base material that does not necessarily have sufficient heat resistance can be used as the supporting base material.

  The film of the present invention can be produced by a coating method. Therefore, for example, a thin film can be manufactured on a flexible support base represented by a flexible substrate or a support base with curvature.

  By peeling the supporting substrate, a film in which the alignment film and the film of the present invention are laminated is obtained, and further, the alignment film can be peeled to obtain the film of the present invention. Also, another support base material is bonded to the film of the present invention, and the support base material previously laminated is peeled off, or the support base material and the alignment film previously laminated are peeled off. Transfer can also be performed.

  By appropriately adjusting the contents of the compound (1) and the liquid crystal compound in the composition of the present invention, the film thickness can be adjusted to give a desired retardation. Since the retardation value (retardation value, Re (λ)) of the obtained film is determined as shown in Equation (7), Δn (λ) and film thickness are used to obtain the desired Re (λ). What is necessary is just to adjust d suitably.

Re (λ) = d × Δn (λ) (7)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)

  The film thus obtained is excellent in transparency in the visible light region and used as various display films. As described above, the thickness of the layer to be formed varies depending on the retardation value of the obtained film, but the thickness is preferably 0.1 to 10 μm, and 0.2 to 5 μm in terms of reducing photoelasticity. More preferably it is.

The film of the present invention can change the optical properties by changing the orientation state of the compound (1). As a result, for example, when used as a retardation film for a liquid crystal panel, the optical characteristics can be changed so that it can be used in VA mode, IPS mode, OCB mode, TN mode, STN mode, and the like.
More specifically, the film of the present invention, the refractive index in a slow axis direction in a plane n _x, the refractive index in a direction (a fast axis direction) perpendicular to the slow axis in the plane n _y, thickness If the refractive index in the direction is defined as _{n z, n x} ≒ _{n y} film without phase difference _{≒ n z, n x> n} y ≒ n z positive a _{plate, n x ≒ n y> n} z negative of C-plate, positive C plate of the _{n x ≒ n y <n z} , n x ≠ n y ≠ n z positive O plates and negative O plates can be manufactured.

Moreover, although it is known that the thin film which fixed the orientation of the chiral nematic phase reflects selectively, 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 center wavelength of the selective reflection wavelength band λ (nm) can be expressed by λ = n · P. Here, n represents the average refractive index of the composition, and P represents the helical pitch (μm) of the chiral nematic phase. In general, as the amount of chiral agent added increases, P decreases, so the selective reflection wavelength band can be controlled by controlling the amount of chiral agent added. In these cases, the chiral helical axis is preferably oriented so as to be substantially orthogonal to the surface direction of the transparent support.
Thus, by adding a chiral agent, a twist orientation film, a selective reflection film, a brightness enhancement film, a negative C plate, and the like can be produced. 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.

The film of the present invention exhibits excellent optical properties even when one sheet is used, but a plurality of films having the same function may be laminated or 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 widening film, an antireflection film, a polarizing film, a circularly polarizing film, an elliptically polarizing film, a brightness enhancement film, and the like.
Moreover, since the film of this invention can be formed by making it superpose | polymerize by application | coating and ultraviolet irradiation, a film can also be formed in a liquid crystal cell or on a color filter, without passing through processes, such as bonding. In addition, the optical function can be patterned, and can be used as a so-called in-cell retardation plate.

  In the description of the drawings below, the film may be only the film of the present invention, or may be one in which an alignment film is laminated on the film of the present invention, or the alignment film on the film of the present invention. And the support base material may be laminated. In the description of FIG. 1 below, the adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.

For example, as shown in FIGS. 1 (a) to 1 (e), (1) an embodiment in which the film 1 of the present invention and the polarizing film layer 2 are directly bonded together (FIG. 1 (a)), ( 2) Embodiment in which the film 1 of the present invention and the polarizing film layer 2 are bonded together via the adhesive layer 3 (FIG. 1B), (3) the film 1 of the present invention and the film 1 ′ of the present invention And the film 1 ′ of the present invention and the polarizing film layer 2 are directly bonded (FIG. 1 (c)), (4) the film 1 of the present invention and the film 1 ′ of the present invention. And the polarizing film layer 2 directly bonded to the film 1 ′ of the present invention (FIG. 1 (d)), and (5) the film 1 of the present invention. And the film 1 'of the present invention are bonded together via an adhesive layer 3, and the film of the present invention is further bonded. Lum 1 embodiment 'and the polarizing film layer 2 adhesive layer 3' was adhered through a (FIG. 1 (e)), and the like.

The polarizing film layer may be a film having a polarizing function, for example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film, or a film obtained by stretching a polyvinyl alcohol film, or an iodine or dichroic dye. The film etc. which adsorbed are mentioned. Moreover, the polarizing film layer may be provided with the film used as a protective film as needed.
Examples of protective films include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, polyethylene naphthalate films, polycarbonate films, and polysulfone films. , Polyethersulfone film, polyetherketone film, polyphenylene sulfide film and polyphenylene oxide film.
The adhesive used for the adhesive layer 3 and the adhesive layer 3 ′ is preferably an adhesive having high transparency and excellent heat resistance. As such an adhesive, for example, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, or the like is used.
Moreover, in a polarizing film, as shown in FIG.1 (c)-FIG.1 (e), you may bond the film of 2 or more of this invention directly or through an adhesive bond layer.

The flat panel display device of the present invention includes the film of the present invention. For example, a liquid crystal display device including a liquid crystal panel in which the polarizing film of the present invention and a liquid crystal panel are bonded, and the polarizing film of the present invention And an organic EL display device including an organic electroluminescence (hereinafter also referred to as “EL”) panel in which a light emitting layer is bonded.
As embodiments 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]
Examples of the liquid crystal display device include a liquid crystal display device including a liquid crystal panel as shown in FIGS. 2 (a) and 2 (b). The liquid crystal panel includes a member 4 and a liquid crystal panel 6 bonded together through an adhesive layer 5 as shown in FIG. 2A, and a member 4 and a member 4 ′ as shown in FIG. 2B. The liquid crystal panel 6 is bonded to both surfaces via an adhesive layer 5 and an adhesive layer 5 ′. The member 4 and the member 4 ′ are members including the film of the present invention, and examples thereof include polarizing films shown in FIGS. 1 (a) to 1 (e). According to the above configuration, by applying a voltage to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules are driven and monochrome display can be performed.

[Organic EL display device]
Examples of the organic EL display device include an organic EL display device including the organic EL panel shown in FIG. The organic EL panel is formed by bonding the member 4 and the light emitting layer 7 through the adhesive layer 5. The light emitting layer 7 is at least one layer made of a conductive organic compound.
In addition, in the said organic EL panel, when the member 4 is a polarizing film, it functions as a broadband circularly-polarizing plate. Therefore, an antireflection function can be imparted to the organic EL panel.

[Color filter]
FIG. 4 is a schematic view showing the color filter 11 of the present invention.
The color filter 11 is a color filter in which a color filter layer 13 is formed on the film 12 of the present invention.
An example of a method for manufacturing the color filter 11 will be described. First, an alignment film material is applied on a support substrate, and a rubbing process is performed to form an alignment film. Next, the obtained film is desired to have a mixed solution containing the compound (1) in which the concentration of the compound (1) is adjusted so that the obtained film exhibits a desired wavelength dispersion characteristic on the obtained alignment film. The film is formed by coating while adjusting the thickness so as to obtain a retardation value of. Next, a color filter layer 13 is formed on the obtained film 12 of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Example 1
[Synthesis Example of Compound (1-a14)]
Compound (1-a14) was synthesized according to the following scheme.

Compound (e) can be obtained by reacting compound (d) and compound (h) as described below.

（化合物（ｂ）の合成例）
モノテトラヒドロピラニル保護ヒドロキノン（ａ)１００ｇ（５１５ｍｍｏｌ）、炭酸カリウム９７ｇ（７０３ｍｍｏｌ）及び６−クロロヘキサノール６４ｇ（４６８ｍｍｏｌ）を、ジメチルアセトアミド中で窒素雰囲気下、９０℃で反応させ、その後１００℃で反応させた。その後反応溶液を室温まで冷却し、純水及びメチルイソブチルケトンを加え、有機層を回収した。回収した有機層を水酸化ナトリウム水溶液及び純水で洗浄後、脱水処理した。脱水剤を濾過により除去し、得られた濾液を、減圧濃縮した。残渣にメタノールを加えて、生成した沈殿をろ過により取り出し、真空乾燥させて、化合物（ｂ）１２６ｇ（４２８ｍｍｏｌ）得た。収率は６−クロロヘキサノール基準で９１％であった。 Compound (d) was synthesized according to the following scheme. The raw material monotetrahydropyranyl protected hydroquinone (a) was synthesized by the method described in the patent document (Japanese Patent Application Laid-Open No. 2004-262848).

(Synthesis Example of Compound (b))
Monotetrahydropyranyl protected hydroquinone (a) 100 g (515 mmol), potassium carbonate 97 g (703 mmol) and 6-chlorohexanol 64 g (468 mmol) were reacted in dimethylacetamide at 90 ° C. in a nitrogen atmosphere and then at 100 ° C. I let you. Thereafter, the reaction solution was cooled to room temperature, pure water and methyl isobutyl ketone were added, and the organic layer was recovered. The collected organic layer was washed with an aqueous sodium hydroxide solution and pure water, and then dehydrated. The dehydrating agent was removed by filtration, and the resulting filtrate was concentrated under reduced pressure. Methanol was added to the residue, and the resulting precipitate was removed by filtration and vacuum dried to obtain 126 g (428 mmol) of compound (b). The yield was 91% based on 6-chlorohexanol.

(Synthesis Example of Compound (c))
Compound (b) 126 g (428 mmol), 3,5-ditertiarybutyl-4-hydroxytoluene (hereinafter sometimes referred to as “BHT”) 1.4 g (6.42 mmol), N, N-dimethylaniline 117 g (963 mmol) 1 g of 1,3-dimethyl-2-imidazolidinone and chloroform were mixed. Aquiroyl chloride (58 g, 642 mmol) was added dropwise to the obtained mixed solution under a nitrogen atmosphere and ice cooling, and pure water was added to cause reaction, and then the separated organic layer was recovered. The organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate solution and pure water. A dehydrating agent was added to the washed organic layer and dried. After removing the dehydrating agent, 1 g of BHT was added to the filtered organic layer and then concentrated under reduced pressure to obtain compound (c).

(Synthesis Example of Compound (d))
After mixing the compound (c) and 200 ml of tetrahydrofuran (hereinafter sometimes referred to as “THF”), 200 ml of THF was added to the resulting mixture. Further, aqueous hydrochloric acid and concentrated aqueous hydrochloric acid were added, and the reaction was carried out under a nitrogen atmosphere at 60 ° C. To the reaction solution, 500 ml of saturated brine was added, and the organic layer was separated. The organic layer was dehydrated with a dehydrating agent, and the dehydrating agent was filtered. The obtained filtrate was concentrated under reduced pressure. Hexane was added to the resulting concentrated liquid and stirred under ice-cooling, and the precipitated powder was filtered and dried under vacuum to obtain 90 g (339 mmol) of compound (d). The yield was 79% based on the compound (c).

Compound (h) (trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester) was produced according to the following scheme.

  200 g (1.1616 mol) of trans-1,4-cyclohexanedicarboxylic acid and 1000 mL of dimethylacetamide were mixed. The temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere, and 96 g (0.6969 mol) of potassium carbonate and 10 g (0.0602 mol) of potassium iodide were added to the resulting solution, and then 140 g (1.1035 mol) of benzyl chloride. ) And the solution was reacted at 120 ° C. for 6 hours. The solution was allowed to cool to room temperature, poured into 1500 g of ice and stirred. The obtained crystals were collected by filtration and washed with water / methanol 3: 2 (v / v) and then with water. The crystal after washing was vacuum-dried to obtain 251 g of powder containing compound (f).

  251 g of powder containing compound (f) and 600 mL of chloroform were mixed. The obtained solution was ice-cooled, and 93.53 g (0.7600 mol) of ethoxychloromethane and 146.83 g (1.4515 mol) of triethylamine were added dropwise to the obtained solution under a nitrogen atmosphere. The reaction solution was reacted at room temperature under a nitrogen atmosphere for 3 hours. 600 mL of toluene was added to the reaction solution, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was collected and washed with water. The organic layer was collected, dried over anhydrous sodium sulfate and filtered, and then the solvent was removed. The obtained crude product was vacuum-dried to obtain 242 g of a liquid containing the compound (g).

  242 g of the liquid containing the compound (g) and 250 ml of THF were mixed. Under a nitrogen atmosphere, 10 g of 10% palladium-carbon (containing 50% water) was added to the resulting solution. After decompression, the atmosphere was replaced with hydrogen, and the resulting solution was reacted for 6 hours at room temperature, normal pressure, and hydrogen atmosphere. After purging with nitrogen, the resulting solution was filtered to remove the catalyst, and then the solvent was removed. The residue was dissolved in chloroform. The resulting solution was filtered through silica gel. Insoluble matter on silica gel was further extracted from silica gel with chloroform. The chloroform solution was recovered, concentrated under reduced pressure, and crystallized by adding heptane thereto. The obtained crystal was separated by filtration and vacuum-dried to obtain 106 g of compound (h). The yield was 39% based on the compound trans-1,4-cyclohexanedicarboxylic acid.

Compound (e) was produced according to the following scheme.

Compound (d) 56.8 g (215 mmol), dimethylaminopyridine 2.65 g (22 mmol), compound (h) 50 g (217 mmol) and chloroform 300 mL were mixed. The obtained mixture was ice-cooled and stirred under a nitrogen atmosphere, and a solution consisting of 48.79 g (237 mol) of dicyclohexylcarbodiimide and 50 mL of chloroform was added dropwise.
After completion of the dropwise addition, the resulting reaction solution was stirred at room temperature, and 200 mL of chloroform and 200 mL of heptane were added, and the precipitate was filtered. The filtrate was collected and washed with 2N aqueous hydrochloric acid. The separated organic layer was recovered, insoluble components were removed by filtration, anhydrous sodium sulfate was added, and after filtration, the solid obtained by removing the solvent was vacuum-dried to obtain 100 g of compound (e ′). .

  100 g of the compound (e ′), 3.7 g (202 mmol) of pure water, 3.8 g (20.2 mmol) of paratoluenesulfonic acid monohydrate and 200 mL of THF were mixed and reacted at 50 ° C. in a nitrogen atmosphere. The reaction solution was allowed to cool to room temperature, THF was removed under reduced pressure, and 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum dried. The obtained powder was dissolved in chloroform and filtered through silica gel. The filtrate was collected and dissolved in 400 mL of chloroform, the resulting solution was concentrated, and toluene was added. After the solution was concentrated under reduced pressure, heptane was added for crystallization, and the resulting powder was collected by filtration and dried in vacuo to obtain 64 g of compound (e). The yield was 76% based on the compound (d) in two steps.

<Synthesis Example of Compound (1-a14)>
3.4 g (18 mmol) of phenylhydroquinone, 16 g (38 mmol) of the compound (e), 0.5 g (4 mmol) of 4-dimethylaminopyridine and 237 g of chloroform were mixed. A solution prepared by dissolving 9.4 g (45 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 9 g of chloroform was added dropwise to the mixture at room temperature, and reacted for 36 hours. 140g of 2N hydrochloric acid was added to the reaction solution, and it filtered. The obtained filtrate was washed with 140 g of 2N hydrochloric acid, and the filtrate after washing was concentrated to obtain about 50 g of a concentrated solution. After adding 0.4 g of activated carbon to the filtrate after concentration and filtering through Celite, the solvent was removed and methanol was added to obtain a solid. The obtained solid was washed with methanol to obtain 8.4 g of a compound (1-a14) as a white solid. The yield was 47% based on phenylhydroquinone.

¹ H-NMR (CDCl ₃ ) of the compound (1-a14): δ (ppm) 1.35 to 1.91 (m, 24H), 2.35 to 2.58 (m, 12H), 3.93 ( t, 4H), 4.17 (t, 4H), 5.81 (dd, 2H), 6.12 (m, 2H), 6.40 (dd, 2H), 6.84 to 6.99 (m) 8H), 7.11 (m, 3H), 7.38 (m, 5H)

  The phase transition temperature of the obtained compound (1-a14) was measured by texture observation with a polarizing microscope. Compound (1-a14) exhibited a nematic phase from 84 ° C. to 198 ° C. at the time of temperature rise, and became isotropic at 198 ° C. As the temperature was lowered from 200 ° C., a nematic phase was exhibited from 198 ° C. to 36 ° C. and crystallized at 36 ° C. Thus, the compound (1-a14) not only exhibits nematic liquid crystallinity over a wide temperature range, but also exhibits nematic liquid crystallinity at around 40 ° C.

Example 2
[Synthesis Example of Compound (1-a3)]
Compound (1-a3) was synthesized according to the following scheme.

<Synthesis Example of Compound (1-a3)>
1.0 g (6 mmol) of t-butylhydroquinone, 6.0 g (14 mmol) of the compound (e), 0.2 g (1.4 mmol) of 4-dimethylaminopyridine and 121 g of chloroform were mixed. A solution consisting of 4.5 g (22 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) and 24 g of chloroform was added dropwise to the mixed solution at room temperature and reacted for 3 hours. After adding 60 g of 2N hydrochloric acid to the reaction solution, the filtrate was taken out by filtration. The filtrate was washed with 60 g of 2N hydrochloric acid, and then concentrated to about 40 g. Activated carbon (0.3 g) was added to the filtrate after concentration and filtered through Celite, and then the solvent was distilled off, and methanol was added to obtain a solid. The obtained solid was washed with methanol to obtain 4.1 g of a compound (1-a3) as a white solid. The yield was 71% based on t-butylhydroquinone.

¹ H-NMR (CDCl ₃ ) of the compound (1-a3): δ (ppm) 1.34 (s, 9H) 1.35 to 1.91 (m, 24H), 2.35 to 2.58 (m 12H), 3.94 (t, 4H), 4.17 (t, 4H), 5.81 (dd, 2H), 6.12 (m, 2H), 6.40 (dd, 2H), 6 .84 to 7.06 (m, 11H)

The phase transition temperature of the obtained compound (1-a3) was observed by texture observation with a polarizing microscope. The compound (1-a3) exhibited a smectic phase from 66 ° C. to 96 ° C. and a nematic phase from 96 ° C. to 180 ° C. or higher when the temperature was raised. When the temperature was lowered at 180 ° C., a nematic phase was exhibited from 180 ° C. to 29 ° C. or less, and no crystallization occurred.
The compound (1-a3) not only exhibits nematic liquid crystal properties in a wide temperature range, but also exhibits nematic liquid crystal properties at around 30 ° C.

Comparative Example 1
<Synthesis Example of Compound (III-1-1)>
Compound (III-1-1) was synthesized according to the following scheme.

(Synthesis Example of Compound (i))
84.5 g (509 mmol) of ethyl 4-hydroxybenzoate, 84.2 g (559 mmol) of 4-chlorobutyl acetate, 105 g (763 mmol) of potassium carbonate, and 254 g of N, N-dimethylacetamide were added, and the mixture was heated to 100 ° C. and stirred. . After cooling, methyl isobutyl ketone was added, washed with water, and the solvent was distilled off to obtain 126 g of an oily substance mainly composed of compound (i). The yield was 88% based on ethyl 4-hydroxybenzoate.

(Synthesis Example of Compound (j))
126 g of an oily substance containing compound (i) as a main component, 378 g of methanol, 252 g of water and 54 g (1348 mmol) of sodium hydroxide were mixed and reacted at 65 ° C. The reaction solution was cooled, poured into 756 g of ice, and 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. The yield was 97% based on the compound (i).

(Synthesis Example of Compound (k))
Under a nitrogen atmosphere, 90.0 g (428 mmol) of a solid mainly composed of the compound (j) and 77.8 g (642 mmol) of N, N-dimethylaniline were dissolved in 720 g of N, N-dimethylacetamide. The solution was ice-cooled to 0 ° C., and 58.1 g (642 mmol) of acrylic acid chloride was added dropwise and reacted at room temperature. 1N hydrochloric acid was added to the reaction solution. The precipitated solid was taken out, dissolved in ethyl acetate, washed with water, and the solvent was removed to obtain 102 g of a solid containing compound (k) as a main component. The yield was 90% based on the compound (j).

(Synthesis Example of Compound (III-1-1))
Hydroquinone 3 g (30 mmol), solid 16 g (60 mmol) containing compound (k) as a main component, 4-dimethylaminopyridine 0.7 g (6 mmol), and chloroform 127 g were mixed. A solution prepared by dissolving 12 g (60 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 32 g of chloroform was added dropwise to the mixed solution at room temperature and reacted for 3 hours. The reaction solution was filtered after adding 159 g of 2N hydrochloric acid. The obtained filtrate was washed with 159 g of 2N hydrochloric acid, the solvent was distilled off from the filtrate after washing, and methanol was added to obtain a solid. The obtained solid was washed with methanol to obtain 12.0 g of compound (III-1-1) as a white solid. The yield was 66% based on hydroquinone.

The phase transition temperature of compound (III-1-1) was measured by texture observation with a polarizing microscope. As the temperature was raised, the crystal phase changed to a nematic phase around 107 ° C, and further changed to an isotropic liquid phase around 167 ° C. When the temperature was lowered from the isotropic liquid phase, it changed to a nematic phase around 167 ° C., and when the temperature was further lowered to around 74 ° C., it returned to the crystalline phase.
That is, it was found that the compound (III-1-1) exhibits a nematic phase between 107 ° C. and 167 ° C. when the temperature is raised and between 167 ° C. and 107 ° C. when the temperature is lowered.

<Adjustment of composition>
(Examples 3 to 6, Comparative Example 2)
A composition having the composition shown in Table 2 was prepared. % In Table 2 means mass% when the total mass of the composition is 100 mass%.

光重合開始剤：イルガキュア８１９(チバ・ジャパン社製)（アシルホスフィンオキサイド化合物）
レベリング剤：ＢＹＫ３６１Ｎ（ビックケミージャパン製）
溶剤：シクロペンタノン

Photopolymerization initiator: Irgacure 819 (manufactured by Ciba Japan) (acylphosphine oxide compound)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Thermal behavior 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. The composition described in Table 3 was applied to the surface subjected to the rubbing treatment by a spin coating method. While heating the coated substrate with a hot stage polarizing microscope (hot stage: LTS350, manufactured by Linkam Co., Ltd., polarizing microscope: BX-51, manufactured by Olympus Co., Ltd.) at a temperature rising rate of 30 ° C./min. The behavior of the composition was observed. When the temperature dropped, the behavior was observed by natural cooling. The results are shown in Table 3.

(Examples 7 to 10, Comparative Example 3)
<Example of film production>
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. The composition described in Table 4 was applied to the surface subjected to the rubbing treatment by a spin coat method, and dried at a temperature (T _c ) described in Table 4 for 1 minute. After leaving for 1 minute at the temperature (T _d ) shown in Table 4, an ultraviolet ray with an integrated light amount of 2400 mJ / cm ² was irradiated to form a film.

<Surface observation>
The surface state of the film was observed with a polarizing microscope at a magnification of 400 times. If it is a monodomain, it is marked as ◯, and if a defect is present, it is marked as x. The results are shown in Table 4.
<Stability over time>
The film was left in the atmosphere at room temperature for 2 weeks, and then the surface state of the film was observed with a polarizing microscope. If no alignment defect is found, the mark is ◯, and if an alignment defect is observed, the mark is ×. The results are shown in Table 4.

＜光学特性の測定＞
フィルムの位相差値を測定機（ＫＯＢＲＡ−ＷＲ、王子計測機器社製）により測定した。位相差値（ｎｍ）の測定は、ガラス基板、配向膜及びフィルムを含む積層体について行ったが、ガラス基板及び配向膜は複屈折性を有さない（配向膜及びガラス基板については、Ｒｅ（４４７）＝Ｒｅ（５４７）＝Ｒｅ（６２８）＝０）ので、測定された位相差値をフィルムの位相差値とすることができる。位相差値Ｒｅ（λ）は、波長（λ）４４７ｎｍ、５４７ｎｍ及び６２８ｎｍにおいて測定した。フィルムの膜厚ｄ（μｍ）は、レーザー顕微鏡（ＬＥＸＴ３０００、オリンパス社製）を用いて測定した。結果を表５に示す。

<Measurement of optical properties>
The retardation value of the film was measured with a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments). The retardation value (nm) was measured for a laminate including a glass substrate, an alignment film, and a film. However, the glass substrate and the alignment film do not have birefringence (for the alignment film and the glass substrate, Re ( 447) = Re (547) = Re (628) = 0), the measured retardation value can be used as the retardation value of the film. The phase difference value Re (λ) was measured at wavelengths (λ) of 447 nm, 547 nm, and 628 nm. The film thickness d (μm) of the film was measured using a laser microscope (LEXT 3000, manufactured by Olympus). The results are shown in Table 5.

  In the examples, a film could be produced at a low temperature of 30 ° C. or 50 ° C.

  By polymerizing the compound of the present invention, it is possible to produce a film having excellent surface conditions and stability over time and having optical properties at a low temperature.

1, 1 ′ film 2, 2 ′ polarizing film layer 3, 3 ′, 3 ″ adhesive layer 4, 4 ′ member 5, 5 ′ adhesive layer 6 liquid crystal panel 7 light emitting layer 11 color filter 12 film 13 color filter layer

Claims (7)

The compound represented by Formula (1).

[In the formula (1), X represents an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a monovalent aromatic carbon atom having 6 to 20 carbon atoms which may have a substituent. Represents a hydrogen group.
E ¹ and E ² are each independently a single bond , —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ⁶ —, — NR ⁶ —CO—, —O —CH ₂ — or —CH ₂ —O— is represented, and 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 aromatic hydrocarbon group which may have a substituent .
B ¹ , B ² , B ³ and B ⁴ are each independently a single bond , —O—, —S—, —CO—O—, —O—CO—, —O—CO—O— or —CO. ^{-NR 6 -, - NR 6 -CO} -, - represents a CO- or -CS-.
F ¹ and F ² each independently represents an optionally substituted alkanediyl group having 1 to 12 carbon atoms, and —CH ₂ — contained in the alkanediyl group having 1 to 12 carbon atoms is , -O- may be substituted.
P ¹ and P ² each independently represent a hydrogen atom or a group represented by any one of formulas (P-1) to (P-5), and at least one of P ¹ and P ² Is a group represented by any one of formulas (P-1) to (P-5).

[In formulas (P-1) to (P-5), R ^{1 to} R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. * Represents a bonding position with B ³ or B ⁴ . ]] The compound according to claim ^1, wherein P ¹ and P ² are each independently a group represented by the formula (P-1).

[In Formula (P-1), R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]   A composition comprising the compound according to claim 1 or 2 and a photopolymerization initiator.   A film obtained by polymerizing the compound according to claim 1.   A color filter comprising the film according to claim 4.   A flat panel display comprising the film according to claim 4.   The manufacturing method of the film including the process of apply | coating the compound of Claim 1 or 2 on the base material or the oriented film formed on the base material.

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