JP5292778B2 - Compound and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new optical film further suppressing wavelength dependence of a phase difference value and a new compound for providing the film. <P>SOLUTION: The compound, for example, represented by formula (J-3) is exemplified. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a compound suitable for an optical film such as a polarizing plate used in a flat panel display device such as a liquid crystal display device or an organic electroluminescence display device.

Flat panel display devices (hereinafter also referred to as “FPD”) such as liquid crystal display devices (hereinafter also referred to as “LCD”) and organic electroluminescence display devices (hereinafter also referred to as “EL”) are compared with cathode ray tube display devices. Saving space and low power consumption. Therefore, in recent years, FPD has been widely used as a screen of a computer, a television, a mobile phone, a car navigation system, or a portable information terminal. In the FPD, various optical films are generally used for polarizing plates, retardation plates, and the like in order to prevent reflection and expand the viewing angle.
Optical films are required to reduce the wavelength dependence of retardation values. The degree of wavelength dependence of the phase difference value can be expressed by the value of Re (450) / Re (550), and the wavelength dependence of the phase difference value increases as the value becomes larger than 1. means. Here, Re (λ) represents a retardation value of a wavelength λ nm that is transmitted through the optical film. As a conventional optical film, an optical film obtained by coating a compound represented by the formula (II) on an alignment film Is disclosed in Patent Document 1, and the value of Re (450) / Re (550) given by the optical film is 1.065, which is not always sufficient.

JP 2006-58546 A ([Claim 2] [0115])

  The subject of this invention is providing the novel compound which can give the novel optical film which can suppress the wavelength dependence of retardation value further, and this film.

  Under such circumstances, the present inventors have found a novel optical film capable of suppressing the wavelength dependence of the retardation value and a novel compound capable of providing the film, and completed the present invention. That is, this invention is invention of the following [1]-[15] description.

（式（１）及び式（２）中、ＥＷＧは、それぞれ独立に、電子吸引基を表す。ｐ及びｑは、それぞれ独立に、０〜４のいずれかの整数を表す。但し、１≦ｐ＋ｑ≦８である。
Ａ_１及びＡ_２は、それぞれ独立に、１，４−フェニレン基を表し、該１，４−フェニレン基には、炭素数１〜４のアルキル基及び炭素数１〜４のアルコキシ基からなる群から選ばれる少なくとも１種の置換基が結合していてもよい。 [1] A compound represented by formula (1) or a compound represented by formula (2).

(In Formula (1) and Formula (2), EWG independently represents an electron-withdrawing group. P and q each independently represent an integer of 0 to 4, provided that 1 ≦ p + q ≦ 8.
A ₁ and A ₂ each independently represent a 1,4-phenylene group, and the 1,4-phenylene group is a group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. At least one substituent selected from may be bonded.

B ₁ , B ₂ and B ₃ are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, It represents —C (═O) —NR—, —NR—C (═O) —, —OCH ₂ —, —O—C (═O) —O— or a single bond. Here, R represents a C1-C4 alkyl group or a hydrogen atom.

［式（３）中、Ａ_３は、５〜２０員環の２価の環状炭化水素基又は５〜２０員環の２価の複素環基を表す。該環状炭化水素基及び該複素環基には、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、トリフルオロメチル基、トリフルオロメチルオキシ基、ニトリル基、ニトロ基又はハロゲン原子が結合していてもよい。
Ｂ_４は、−ＣＲ’Ｒ”−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＨ_２−ＣＨ_２−、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｃ（＝Ｏ）−ＮＲ’−、−ＮＲ’−Ｃ（＝Ｏ）−、−ＯＣＨ_２−、−ＮＲ’−、−ＣＨ_２Ｏ−、−ＣＨ＝ＣＨ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ＝ＣＨ−又は単結合を表す。ここで、Ｒ’及びＲ”は、それぞれ独立に、炭素数１〜４のアルキル基又は水素原子を表す。
ｎは１〜４いずれかの整数を表す。ｎが２〜４の場合には、Ａ_３及びＢ_４からなる構造単位は、互いに同一でも異なっていてもよい。］ X represents a divalent group represented by the formula (3).

[In Formula (3), A ₃ represents a 5- to 20-membered divalent cyclic hydrocarbon group or a 5- to 20-membered divalent heterocyclic group. The cyclic hydrocarbon group and the heterocyclic group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom. May be combined.
B ₄ is, -CR'R "-, - 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-, -C (= O) -NR '. -, - NR'-C (= O) -, - OCH 2 -, - NR '-, - CH 2 O -, - CH = CH-C (= O) -O -, - O-C (= O ) —CH═CH— or a single bond, wherein R ′ and R ″ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
n represents an integer of 1 to 4. When n is 2 to 4, the structural units composed of A ₃ and B ₄ may be the same as or different from each other. ]

E ₁ represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in E ₁ may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. Good.
E ₂ represents an alkyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in E ₂ may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. Good.

［式（Ｄ−１）〜（Ｄ−５）中、Ｒ_１〜Ｒ_５はそれぞれ独立に、炭素数１〜４のアルキル基又は水素原子を表す。］） P ₁ is a hydrogen atom or a group represented by (D-1) to (D-5).

[In formulas (D-1) to (D-5), R _{1 to} R ₅ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ])

［４］ 式（１）及び式（２）で表される化合物のＰ_１が、式（Ｄ−１）で表される基である［１］〜［３］のいずれか記載の化合物。 [2] The compound according to [1], wherein EWG in the formulas (1) and (2) is a nitro group, a nitrile group or a trifluoromethyl group.
[3] The compound according to [1] or [2], wherein A ₃ is any group represented by formulas (4-1) to (4-5).

[4] The compound according to any one of [1] to [3], wherein P _{1 of the} compounds represented by formula (1) and formula (2) is a group represented by formula (D-1).

[5] A composition comprising the compound according to any one of [1] to [4] and a polymerizable compound exhibiting liquid crystallinity.
[6] An optical film obtained by polymerizing the composition according to [5].
[7] An optical film containing a structural unit derived from the compound according to any one of [1] to [4].
[8] An optical film according to [6] or [7], wherein a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film is 113 to 163 nm.
[9] An optical film according to [6] or [7], wherein the retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film is 250 to 300 nm.
[10] A polarizing plate comprising the optical film and polarizing film according to any one of [6] to [9].

[11] A flat panel display comprising the polarizing plate and the liquid crystal panel according to [10].
[12] An organic electroluminescence display device comprising the polarizing plate according to [10] and an organic electroluminescence panel.

[13] A method for producing an unpolymerized film, wherein a solution containing the composition according to [5] is applied to a supporting substrate and dried.
[14] A method for producing an unpolymerized film, in which a solution containing the composition according to [5] is applied on an alignment film formed on a supporting substrate and dried.
[15] A method for producing an optical film in which an unpolymerized film obtained by the production method according to [13] or [14] is cured by polymerization.

  The present invention can provide a novel optical film that can further suppress the wavelength dependence of the retardation value and a novel compound that can provide the film.

ここで、ＥＷＧは、それぞれ独立に、電子吸引基を表す。電子吸引基としては、例えば、ニトロ基、ニトリル基、トリフルオロメチル又はフルオロ基などが挙げられる。
ｐ及びｑは、それぞれ独立に、０〜４いずれかの整数を表す。但し、１≦ｐ＋ｑ≦８であり、特に、ｐ＝ｑ＝１が好ましい。 The compound of the present invention may be described as a compound represented by the formula (1) (hereinafter sometimes referred to as the compound (1)) or a compound represented by the formula (2) (hereinafter referred to as the compound (2)). ).

Here, each EWG independently represents an electron withdrawing group. Examples of the electron withdrawing group include a nitro group, a nitrile group, trifluoromethyl, or a fluoro group.
p and q each independently represent an integer of 0 to 4. However, 1 ≦ p + q ≦ 8, and in particular, p = q = 1 is preferable.

In the case of p = q = 1, as the bonding position of EWG in the benzene ring, in the case of compound (1), it is preferable to bond to the position of the carbon atom represented by “ii” in the following left formula. In the case of the compound (2), it is preferably bonded to any carbon atom position of “i” to “iii” in the right formula below, and the position represented as “ii” is particularly preferable.

A ₁ and A ₂ each independently represent a 1,4-phenylene group, and the 1,4-phenylene group has 1 carbon atom such as a methyl group, an ethyl group, an i-propyl group, or a t-butyl group. To 4 alkyl groups; at least one substituent selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group may be bonded.

B ₁ , B ₂ and B ₃ are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, It represents —C (═O) —NR—, —NR—C (═O) —, —OCH ₂ —, —O—C (═O) —O— or a single bond. Here, R represents a C1-C4 alkyl group or a hydrogen atom.

式（３）中、Ａ_３は、５〜２０員環の２価の環状炭化水素基又は５〜２０員環の２価の複素環基を表す。
該環状炭化水素基及び該複素環基には、水酸基；メチル基、エチル基、ｉ−プロピル基、ｔ−ブチル基などの炭素数１〜４のアルキル基；メトキシ基、エトキシ基などの炭素数１〜４のアルコキシ基；トリフルオロメチル基；トリフルオロメチルオキシ基；ニトリル基；ニトロ基又はフッ素原子、塩素原子、臭素原子などのハロゲン原子が結合していてもよい。 X represents a divalent group represented by the formula (3).

In formula (3), A ₃ represents a 5- to 20-membered bivalent cyclic hydrocarbon group or a 5- to 20-membered bivalent heterocyclic group.
The cyclic hydrocarbon group and the heterocyclic group include a hydroxyl group; an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, and a t-butyl group; a carbon number such as a methoxy group and an ethoxy group. 1 to 4 alkoxy groups; trifluoromethyl group; trifluoromethyloxy group; nitrile group; a nitro group or a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom may be bonded.

As this cyclic hydrocarbon group, the cyclic hydrocarbon group represented by a following formula is illustrated.

The divalent heterocyclic group is a divalent cyclic group having a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom and a carbon atom, and may or may not have aromaticity.
Examples of the divalent heterocyclic group having aromaticity include groups represented by the following formulae.

Examples of the divalent heterocyclic group having no aromaticity include groups represented by the following formula.

A ₃ is particularly preferably a group represented by the formulas (4-1) to (4-5), and particularly represented by the formulas (4-2) and (4-5) because of ease of synthesis. Are preferred.

B ₄ is, CR'R "-, - C≡C - , - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, - C (= O) —O—, —O—C (═O) —, —O—C (═O) —O—, —CH═N—, —N═CH—, —C (═O) —NR′—. , —NR′—C (═O) —, —OCH ₂ —, —NR′—, —CH ₂ O—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond, wherein R ′ and R ″ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

n represents an integer of 1 to 4. When n is 2 to 4, the structural units composed of A ₃ and B ₄ may be the same as or different from each other.
As will be described later, n is preferably an integer of 2 to 4 from the viewpoint of easy handling when casting the compound (1) or (2) and the improvement of the orientation of the compound.

E ₁ represents an alkylene group having 1 to 12 carbon atoms.
A hydrogen atom of E ₁ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group or a t-butyl group; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group; Fluoromethyl group; trifluoromethyloxy group; nitrile group; may be substituted with a nitro group or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, but is preferably not substituted.
E ₂ represents an alkyl or cycloalkyl group having 1 to 12 carbon atoms.
A hydrogen atom contained in E ₂ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group or a t-butyl group; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group Trifluoromethyl group; trifluoromethyloxy group; nitrile group; nitro group; optionally substituted by a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

式（Ｄ−１）〜（Ｄ−５）中、Ｒ_１〜Ｒ_５はそれぞれ独立に、メチル基、エチル基、ｉ−プロピル基、ｔ−ブチル基などの炭素数１〜４のアルキル基又は水素原子を表す。
Ｐ_１としては、式（Ｄ−１）〜（Ｄ−５）で表される基であると、得られる光学フィルム中に化合物（１）又は（２）に由来する構造単位を固定化しやすい傾向があることから好ましく、特に、式（Ｄ−１）で表される基が好ましい。 P ₁ is a group represented by formulas (D-1) to (D-5) or a hydrogen atom.

In formulas (D-1) to (D-5), R _{1 to} R ₅ are each independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, or a t-butyl group, or Represents a hydrogen atom.
The P _1, the formula (D-1) ~ a group represented by (D-5), tends to immobilize the structural unit derived from a compound in the resultant optical film (1) or (2) a tendency In particular, a group represented by the formula (D-1) is preferable.

The production method of the compound (1) and the compound (2) of the present invention will be described using the carbonyl compound represented by the formula (1-B) and the carbonyl compound represented by the formula (2-C) as examples. First, the carbonyl compound is reacted with a phenol containing A ₁ such as phenol, ortho-cresol, 2-methoxyphenol, and the like to formula (1-B-1), formula (1-B-2), formula ( A bisphenol derivative represented by 2-C-1) and the formula (2-C-2) is obtained.

Subsequently, for example, methyl iodide, ethyl iodide, n-propyl iodide, isopropyl iodide, n-butyl iodide, s-butyl iodide, cyclohexyl iodide, isopropyl bromide, cyclopropyl bromide, bromide Isobutyl, cyclobutyl bromide, n-amyl bromide, s-amyl bromide, n-hexyl bromide, cyclohexyl bromide, cycloheptyl bromide, n-heptyl bromide, n-octyl bromide, n-decyl bromide A monophenol intermediate is prepared by reacting a compound giving E ₂ such as n-dodecyl bromide, n-tetradecane bromide, n-hexyl chloride, n-octyl chloride. The monophenol intermediate may be purified by silica gel column chromatography or the like.

Specific examples of the monophenol intermediate that gives the compound (1) of the present invention include the formula (1-A-1) to the formula (1-A-45).

Specific examples of the monophenol intermediate that gives the compound (2) of the present invention include formula (2-A-1) to formula (2-A-45).

Mono phenol _{intermediate, B 1 -X-E1-B3} -P1 structure by reacting a compound providing the can to produce a compound of the present invention (1) and the compound (2). If B ₁ is B ₁ —OC (═O) —, the corresponding carboxylic acid, carboxylic acid chloride or carboxylic acid mesitylated as the compound giving the structure of B ₁ -X-E1-B3-P1 such as by using the compound may be mono-phenol intermediate esterification, B ₁ is, if -O-, and using the corresponding halide as a compound which gives structure of _{B 1 -X-E1-B3-} P1 What is necessary is just to etherify.
Examples of the compound giving the structure of B ₁ -X-E1-B3-P1 include carboxylic acids represented by the formulas (3-A-1) to (1-A-124) and chlorides of the carboxylic acids. Can be mentioned. In the formula, k independently represents an integer of 1 to 12.

As a method for producing the formula (3-A-1) ~ (3-A-124) compounds represented by _{include A 3, B 3, B 4} , B 5, each structural unit of the _{E 1} and _{P 1} Compound, for example, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heartwig reaction, Wittig reaction, It can be produced by bonding by Friedel-Craft reaction, Heck reaction or aldol reaction. Specifically, for example, the method described in JP-A-2005-208416 ([0036-0040]), the method described in JP-A-2005-289980 ([0185]), Macromolecules, 27, 6722- 6727 (1994), Advanced, Functional, Materials, Vol. 15, 1961-1972, and the like.

The optical film of the present invention is an optical film containing a structural unit derived from at least one compound selected from the group consisting of the compound (1) and the compound (2) (hereinafter sometimes referred to as the present compound). Usually, the optical film of the present invention can be obtained by polymerizing a composition containing the present compound. In addition, the composition may further contain a compound that is different from both the compound (1) and the compound (2) and exhibits liquid crystallinity (hereinafter sometimes referred to as a liquid crystal compound). An optical film containing a structural unit derived from a liquid crystal compound is preferred because the orientation is increased and the retardation value tends to increase.
The P1 polymerizable group and the liquid crystal compound polymerizable group contained in the compound are preferably polymerizable groups capable of reacting with each other so that the present compound and the liquid crystal compound are copolymerized. It is preferable that the polymerizable group is a group represented by the formula (D-1) because it can be easily photopolymerized.
Moreover, the wavelength dependence of the refractive index of the obtained optical film is controlled by changing the content of the structural unit derived from the present compound contained in the optical film and the content of the structural unit derived from the liquid crystal compound. Can do.

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 compounds represented by the following formula (I), formula (II), formula (III), or formula (IV).
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-A15-B16-E12-P12 (I)
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-E12-P12 (II)
P11-E11-B11-A11-B12-A12-B13-A13-B14-E12-P12 (III)
P11-E11-B11-A11-B12-A12-B13-A13-B14-F11 (IV)
P11-E11-B11-A11-B12-A12-B13-F11 (V)

In the above formula (I), formula (II), formula (III), formula (IV) and formula (V), A11, A12, A13, A14 and A15 are each independently a divalent cyclic hydrocarbon group, Represents a divalent heterocyclic group, aromatic hydrocarbon group, fluorenyl group or thiophenylene group. A11, A12, A13, A14 and A15 are bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a nitro group, a nitrile group, a phenyl group, a dimethylamino group or a halogen atom. Also good.
B11, B12, B13, B14, B15 and B16 are each _{independently, -CR 11 R 12 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, -C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ₁₁ >-,- NR ₁₁ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ₁₁ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O— , -OC (= O) -CH = CH- or a single bond.
R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 5 to 7 carbon atoms in which R ₁₁ and R ₁₂ are bonded.
E11 and E12 each independently represents an alkylene group having 1 to 12 carbon atoms. E11 and E12 may be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.

P11 and P12 each independently represent a polymerizable group represented by formulas (D-1) to (D-5).
F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group or a halogen atom.

Specific examples of the liquid crystal compound include, for example, the following formulas (I-1) to (I-5), (II-1) to (I-6), (III-1) to (III-19), ( IV-1) to (IV-14), compounds represented by (V-1) to (V-5), and the like. However, in formula, m represents the integer in any one of 1-12 each independently.

これらの化合物であれば、製造が容易であったり、市販されているなど、入手が容易であることから好ましい。

These compounds are preferred because they are easy to produce and are commercially available.

As an example of a method for producing an optical film, an optical film obtained by polymerizing a composition containing the present compound of the present invention and a liquid crystal compound will be described below.
First, as a composition, an additive such as an organic solvent, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a crosslinking agent, and a leveling agent is mixed with the present compound and the liquid crystal compound as necessary. Hereinafter, this composition may be referred to as a solution. In particular, the organic solvent is preferably contained at the time of film formation because the film formation becomes easy, and the polymerization initiator is preferable because it has a function of curing the obtained optical film.

(Polymerization initiator)
The present composition usually contains a liquid crystal compound and a polymerization initiator for polymerizing the present compound. As a preferable production method of the optical film, a method of photopolymerizing a liquid crystal compound or the present compound can be mentioned. Therefore, the polymerization initiator is preferably a photopolymerization initiator.
Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxy ketones, α-amino ketones, iodonium salts, or sulfonium salts, and more specifically, Irgacure. 907, IRGACURE 184, IRGACURE 651, IRGACURE 819, IRGACURE 250, and IRGACURE 369 (all manufactured by Ciba Specialty Chemicals), Seiko All BZ, Seiko All Z, Seiko All BEE (all above, all Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka optomer SP-152 or Adeka optomer SP-170 (all asahi Denka) and the like can be mentioned.
Moreover, the usage-amount of a polymerization initiator is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a liquid crystal compound and this compound, Preferably, 0.5 to 10 weight part is preferable. It is. If it is in the said range, this compound can be polymerized, without disturbing the orientation of a liquid crystal compound.

(Polymerization inhibitor)
The composition may contain a 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. Examples include radical scavengers such as -1-piperidinyloxy radical, thiophenols, β-naphthylamines or β-naphthols.
By containing a polymerization inhibitor, the polymerization of the liquid crystal compound and the present compound can be controlled, and the stability of the obtained optical film and the stability of the liquid crystal composition before coating can be improved. The amount of the polymerization inhibitor used is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the liquid crystal compound and the present compound. It is. If it is in the said range, this compound can be polymerized, without disturbing the orientation of a liquid crystal compound.

[Photosensitizer]
Moreover, the present composition may contain a photosensitizer. Examples of the photosensitizer include xanthones such as xanthone or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, or rubrene.
By using a photosensitizer, the polymerization of the liquid crystal compound and the present compound can be made highly sensitive. The photosensitizer is used in an amount of usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to a total of 100 parts by weight of the liquid crystal compound and the present compound. Part. If it is in the said range, this compound can be polymerized, without disturbing the orientation of a liquid crystal compound.

(Leveling agent)
Furthermore, you may contain a leveling agent in this composition. As a leveling agent, for example, an additive for radiation curable coatings (BYK-352, BYK-353, BYK-361N), a coating additive (manufactured by Toray Dow Corning: SH28PA, DC11PA, ST80PA), Examples thereof include paint additives (manufactured by Shin-Etsu Silicone: KP321, KP323, X22-161A, KF6001) or fluorine-based additives (manufactured by Dainippon Ink and Chemicals: F-445, F-470, F-479). .
By using a leveling agent, the optical film can be smoothed. Furthermore, in the production process of the optical film, the fluidity of the composition solution can be controlled, and the crosslinking density of the optical film obtained by polymerizing the liquid crystal compound and the compound can be adjusted. The specific value of the amount of the leveling agent used is usually 0.1 to 30 parts by weight, preferably 0.5 parts by weight with respect to 100 parts by weight of the total amount of the liquid crystal compound and the present compound. -10 parts by weight. If it is in the said range, this compound can be polymerized, without disturbing the orientation of a liquid crystal compound.

[Organic solvent]
The organic solvent contained in the present composition is an organic solvent capable of dissolving the present compound and liquid crystal compound, and specifically, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, etc. Alcohols; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone or propylene glycol methyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone An aliphatic hydrocarbon solvent such as pentane, hexane or heptane; an aromatic hydrocarbon such as toluene, xylene or chlorobenzene; Solvent, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane, ethyl lactate, chloroform or phenol. These organic solvents may be used alone or in combination. Among them, the composition of the present invention has excellent compatibility and can be dissolved in alcohol, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, etc. Even if halogenated hydrocarbons such as are not used, they can be dissolved and applied.

The wavelength dispersion characteristic of the optical film of the present invention can be arbitrarily determined by the content of structural units derived from the present compound in the optical film. When this compound is not used and only the liquid crystal compound is used, the obtained optical film is a film exhibiting positive wavelength dispersion. And by increasing the content of the structural unit derived from the present compound among the structural units in the optical film, Re (450) / Re (550) and Re (650) / Re (550) are reduced, that is, The chromatic dispersion can be shifted in the opposite direction from positive to negative.
Specifically, as a method of reducing Re (450) / Re (550) etc. and shifting the wavelength dispersion in the reverse direction from positive to negative, the composition containing this compound and a liquid crystal compound is derived from this compound. About 2 to 5 types of compositions having different content of structural units to be prepared are prepared, and retardation values of optical films obtained by producing optical films having the same film thickness are obtained as described later for each composition. In order to obtain a correlation between the content of the structural unit derived from the present compound and the retardation value of the optical film from the results, and to give a desired retardation value to the optical film at the above film thickness from the obtained correlation What is necessary is just to determine content of the structural unit derived from this compound required for this.
As a weight ratio of the present compound to the liquid crystal compound in the present composition, the total weight of the present compound is usually 1 to 50 parts by weight, preferably 1 to 100 parts by weight of the total of the present compound and the liquid crystal compound. -30 parts by weight. When the amount is 1 part by weight or more, the wavelength dispersion is preferably shifted from positive to negative in the reverse direction, and when it is 50 parts by weight or less, a liquid crystal layer of the mixture can be stably obtained. It is preferable because an optical film can be prepared at a low cost.

The viscosity of the solution of the present composition is usually adjusted to 10 Pa · s or less, preferably about 0.1 to 7 Pa · s so as to be easily applied.
Moreover, the density | concentration of solid content in this composition solution is 5 to 50 weight% normally. When the solid content is 5% or more, the optical film becomes too thin, and there is a tendency that optical anisotropy necessary for optical compensation of the liquid crystal panel is provided. Moreover, since the viscosity of the said mixed solution is low as it is 50 weight% or less, since there exists a tendency for the nonuniformity to arise in the film thickness of an optical film, it is preferable.

Then, the solution of this composition is apply | coated to a support base material, it can dry and polymerize, and the target optical film can be obtained on a support base material.
If the polymerizable group contained in P1 and the liquid crystal compound contained in the compound is photopolymerizable, the polymerization is performed by irradiation with light such as visible light, ultraviolet light, or laser light, and the polymerizable group is heated. If polymerizable, it is polymerized by heating.
From the viewpoint of film formability, photopolymerization is preferred, and from the viewpoint of handleability, polymerization by ultraviolet light is particularly preferred.

In the case of photopolymerization, the solvent is preferably dried before the photopolymerization to obtain an unpolymerized film in order to improve the film formability. In the case of thermal polymerization, the polymerization may usually proceed with drying, but the method of polymerizing after drying most of the solvent and obtaining an unpolymerized film before the polymerization is suitable for film forming. It is preferable because it tends to be excellent.
Examples of the solvent drying method include methods such as natural drying, ventilation drying, and vacuum drying. The specific heating temperature is preferably 10 to 120 ° C, more preferably 25 to 80 ° C. Further, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. As long as the heating temperature and the heating time are within the above ranges, a supporting substrate that does not necessarily have sufficient heat resistance can be used as the supporting substrate.

  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, a spin coater, etc. are mentioned.

The support substrate may be any material that can form 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, polyethylene naphthalates. Examples thereof include a phthalate film, a polycarbonate film, a polysulfone film, a polyethersulfone film, a polyetherketone film, a polyphenylene sulfide film, and a polyphenylene oxide film.
In general, an optical film obtained from a composition containing a liquid crystal compound and the present compound is a thin film, and the strength of the film is, for example, a bonding step using the film of the present invention, a step of carrying the film, storing it, and the like. Even a necessary process can be easily handled without tearing by using a supporting substrate.

In the optical film of the present invention, preferably, an alignment film is formed on a support substrate, and a solution of the present composition is applied. The alignment film has solvent resistance that does not dissolve when applied with a solution of a composition containing the present compound, etc., has heat resistance due to solvent removal or heat treatment of liquid crystal alignment, and is peeled off by rubbing friction, etc. It is necessary that the above does not occur, etc., and is a polymer or a composition for a blended film containing a polymer.
Examples of the 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, and polyoxazole which are hydrolysates thereof. And polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or 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 or deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, or ring-opening polymerization.

  Further, these polymers can be applied after being dissolved in a solvent. The solvent is not particularly limited, but specifically, alcohol such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma Ester solvents such as butyrolactone and propylene glycol methyl ether acetate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; Toluene , Aromatic hydrocarbon solvents such as xylene, chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimeth Shietan, ethyl lactate, chloroform and the 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), Optomer (registered trademark, manufactured by JSR), and the like.
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, there is an effect that it is possible to provide a large optical film that can cope with an increase in the size of the FPD on the support substrate.
As a method for forming an alignment film on the support substrate, for example, a commercially available alignment film material or a compound that becomes a material of the alignment film 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 usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, in the unpolymerized film preparation process mentioned later, the film layer which has this compound and a liquid crystal compound can be orientated on the said oriented film at a desired angle.
Moreover, these alignment films can be rubbed or irradiated with polarized UV rays as necessary. By these, the film layer which has this compound and a liquid crystal compound can be orientated in a desired direction.
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]
As an unpolymerized film preparation process, for example, when a solution of the present composition is coated on an alignment film on an arbitrary supporting substrate and dried, a film having the present compound and a liquid crystal compound (hereinafter referred to as an unpolymerized film) And a method of producing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell. In particular, a method of obtaining an unpolymerized film on an alignment film laminated on a supporting substrate. Is preferable because the production cost can be reduced and the production of a film with a roll film is possible.
When the obtained unpolymerized film exhibits a liquid crystal phase such as a nematic phase, it has birefringence due to monodomain alignment. Since this unpolymerized film is oriented at a low temperature of about 0 to 120 ° C., preferably 25 to 80 ° C., a supporting substrate that is not necessarily sufficient with respect to heat resistance as exemplified above can be used as the orientation film. After the orientation, it is not crystallized even if it is further cooled to about 30 to 10 ° C.

[Unpolymerized film polymerization process]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the unpolymerized film preparation step is polymerized and cured. As a result, the orientation of the film layer having a structural unit derived from the present compound and a structural unit derived from the liquid crystal compound (hereinafter sometimes referred to as a liquid crystal layer) is fixed, and the liquid crystal layer, the alignment film, and the supporting substrate are fixed. It becomes an optical film formed by laminating. Therefore, an optical film having a small change in refractive index in the plane direction of the liquid crystal layer and a large change in refractive index in the normal direction of the liquid crystal layer can be produced.
The method for polymerizing the unpolymerized film is determined according to the type of the liquid crystal compound and the present compound. For example, the unpolymerized film can be polymerized by photopolymerization or thermal polymerization. In the present invention, it is particularly preferable to polymerize an unpolymerized film by photopolymerization. According to this, since an unpolymerized film can be polymerized at a low temperature, the heat resistance selection range of the support base material is expanded. Moreover, it becomes easy to manufacture industrially.
Examples of the method for photopolymerizing the unpolymerized film include a method for polymerizing the unpolymerized film by irradiating the unpolymerized film with ultraviolet rays.
The optical film thus obtained can be produced without using a liquid crystal polymer.

In the unpolymerized film polymerization step, the present compound and the liquid crystal compound can be crosslinked by photopolymerization. Therefore, there is an effect that it is not easily affected by the change in birefringence due to heat.
Moreover, it is not necessary to use surface treating agents, such as surfactant, for the optical film obtained. That is, since the alignment film used for the optical film of the present invention has good adhesion between the support substrate and the alignment film and adhesion between the alignment film and the optical film, the production of the optical film is easy.
Furthermore, the optical film of the present invention is usually a thin film as compared with a stretched film having an equivalent retardation value.

Subsequent to the above step, a step of peeling the supporting substrate may be included. By setting it as such a structure, the film obtained becomes an optical film which consists of an alignment film and a liquid-crystal layer.
Moreover, in addition to the process of peeling the said support base material, the process of peeling an alignment film may be further included. The obtained optical film does not include a support substrate or an alignment film, and is a film composed of a structural unit derived from the present compound and a structural unit derived from a liquid crystal compound, that is, an optical film composed only of a liquid crystal layer.

In addition, the film thickness of the liquid crystal layer can be adjusted so as to give a desired retardation by appropriately adjusting the amount of the composition applied and the concentration of the organic solvent. Since the retardation value (retardation value, Re (λ)) of the optical film of the present invention is determined as shown in Equation (6), the film thickness d is adjusted to obtain the desired Re (λ). do it.
Re (λ) = d × Δn (λ) (6)
(In the formula, Re (λ) represents a retardation value at a wavelength λ nm, d represents a film thickness, and Δn (λ) represents a refractive index anisotropy at a wavelength λ nm.)

The film thickness of the liquid crystal layer in the optical film of the present invention is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.
When the alignment film is used and has birefringence, the retardation value is usually about 50 to 500 nm, preferably 100 to 300 nm.
By using a film having such optical characteristics, it is possible to optically compensate for FPDs such as all liquid crystal panels and organic EL using thin films and requiring reverse wavelength dispersion.

  The optical film thus obtained is excellent in transparency and used as various display films. For example, in order to use the optical film of the present invention as a broadband λ / 4 plate or λ / 2 plate, the content of the structural unit derived from the present compound is appropriately selected, and the liquid crystal layer according to the formula (6) is selected. The film thickness may be adjusted. Specifically, in the case of a λ / 4 plate, the Re (550) of the obtained optical film may be adjusted to 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm. In the case of a λ / 2 plate, the Re (550) of the obtained optical film may be adjusted to 250 to 300 nm, preferably 273 to 277 nm, particularly preferably about 275 nm.

  In order to use the optical film of the present invention as an optical film for a VA (vertical alignment) mode, the content of the structural unit derived from the present compound is appropriately selected, and the film thickness of the liquid crystal layer is determined according to the formula (6). Adjust it. Specifically, the film thickness may be adjusted so that Re (550) is preferably about 40 to 100 nm, more preferably about 60 to 80 nm.

The optical film of the present invention can be widely used as an optical film having excellent wavelength dispersion characteristics. Examples of the optical film include an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, and an optical compensation film for compensating a viewing angle of a transmissive liquid crystal display. be able to. Moreover, although the optical film of the invention shows excellent optical properties even with one sheet, a plurality of sheets may be laminated.
Moreover, you may combine with another film. Specifically, an elliptical polarizing plate in which the optical film of the present invention is bonded to a polarizing film, a broadband circular polarizing plate in which the optical film of the present invention is further bonded as a broadband λ / 4 plate to the elliptical polarizing plate, and the like. Can be mentioned.
Furthermore, the value of Re (450) / Re (550) in an optical film can be lowered by adding a small amount of this compound, and as a result, an optical film with reduced wavelength dependence of retardation value can be easily obtained. Can be prepared by the method.
The film concerning this invention can be utilized also for the flat panel display apparatus provided with the phase difference plate of a reflection type liquid crystal display and an organic electroluminescent (EL) display, and the said phase difference plate and the said optical film. The flat panel display device is not particularly limited, and examples thereof include a liquid crystal display device (LCD) and organic electroluminescence (EL).

Thus, the film according to the present invention can be used in a wide range of applications. For example, among these, a polarizing plate formed by laminating an optical film and a polarizing film according to the present invention and a flat panel display device including the polarizing plate will be described below. The polarizing plate according to the present invention has a polarizing function. It is obtained by laminating the optical film directly on one or both sides of a film, that is, a polarizing film, or using an adhesive or a pressure-sensitive adhesive. In the following description of FIGS. 1 and 2, 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 an optical film 1 and a polarizing film layer 2 are directly bonded (FIG. 1 (a)), (2) Embodiment in which the optical film 1 and the polarizing film layer 2 are bonded together via the adhesive layer 3 (FIG. 1B), (3) directly bonded to the optical film 1 and the optical film 1 ′, and optical Embodiment (FIG. 1 (c)) in which film 1 ′ and polarizing film layer 2 are directly bonded together, (4) optical film 1 and optical film 1 ′ are bonded through adhesive layer 3, and optical Embodiment (FIG. 1 (d)) in which the polarizing film layer 2 is directly bonded onto the film 1 ′, and (5) the optical film 1 and the optical film 1 ′ are bonded through the adhesive layer 3, Optical film 1 'and polarizing film layer 2 are pasted through adhesive layer 3' The combined embodiment (FIG. 1 (e)) is exemplified.

As a polarizing plate of this invention, a polarizing film and the optical film of this invention are bonded together. As an optical film, only from a layer containing a structural unit derived from the present compound and a structural unit derived from a liquid crystal compound, that is, only a liquid crystal layer may be used, or from a support substrate, an alignment film, and a liquid crystal layer. An optical film made of an alignment film and a liquid crystal layer can also be used.
The polarizing plate of the present invention may be formed by laminating a plurality of optical films, and the plurality of optical films may be the same or may be used in combination. When it demonstrates more concretely, as a polarizing plate concerning this invention, the structure shown to Fig.2 (a)-(k) is illustrated.
2A to 2E, as the optical film 1 and the optical film 1 ′, a film composed of the liquid crystal layer 11 or the liquid crystal layer 11 ′ and the alignment film 12 or the alignment film 12 ′ is used. 2A to 2E show a configuration in which the optical film 1 and the polarizing film 2 are directly bonded to each other (FIG. 2A), and the optical film 1 and the polarizing film 2 are interposed via the adhesive layer 3. 2 (FIG. 2B), optical film 1 and optical film 1 ′ are directly bonded, and optical film 1 ′ and polarizing film layer 2 are directly bonded (FIG. 2C). ), An optical film 1 and an optical film 1 'are bonded together through an adhesive layer 3, and a polarizing film 2 is directly bonded onto the optical film 1' (FIG. 2 (d)), and an optical film 1 and the optical film 1 ′ are bonded together via the adhesive layer 3, and the optical film 1 ′ and the polarizing film 2 are bonded together via the adhesive layer 3 ′ (FIG. 2 (e)). Show.

2 (f) and 2 (g), as the optical film 1 and the optical film 1 ′, a film composed of the liquid crystal layer 11 or the liquid crystal layer 11 ′ is used. In the optical film 1, the alignment film layer 12 is used. Alternatively, the alignment film layer 12 ′ is not included. In FIG. 2 (f), the optical film 1 and the polarizing film layer 2 are bonded together via a pair of adhesive layers 3. On the other hand, in FIG.2 (g), the optical film 1 and optical film 1 'are bonded together through the adhesive layer 3, and also the polarizing film layer 2 is bonded outside through the adhesive layer 3'. ing.
FIG. 2 (h) shows the same structure as FIG. 2 (f). However, unlike FIG.2 (f), as the film 1, the support base material 13, the alignment film 12 formed on the surface of the support base material 13, and the liquid crystal layer formed on the surface of the alignment film 12 11 is used.
FIG. 2 (i) shows the same structure as FIG. 2 (g). However, unlike FIG. 2G, the optical film 1 and the optical film 1 ′ are formed on the surface of the support base 13 or the support base 13 ′ and the support base 13 or the support base 13 ′. A laminate (film) including the alignment film 12 or the alignment film 12 ′ and the liquid crystal layer 11 or the liquid crystal film 11 ′ formed on the surface of the alignment film 12 or the alignment film 12 ′ is used.
2 (j) and 2 (k) show the same structure as FIG. 2 (g). However, of the two films, in FIG. 1 (j), a film made of the liquid crystal layer 11 ′ is used as the optical film 1 ′, and a film made of the liquid crystal layer 11, the alignment film 12 and the support base material 13 is used as the optical film 1. Is used. In FIG. 2 (k), a film composed of the liquid crystal layer 11 ′, the alignment film 12 and the support substrate 13 is used as the optical film 1 ′, and a film composed of the liquid crystal layer 11 is used as the optical film 1.

The polarizing film 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 to obtain iodine or a dichroic dye. Examples include adsorbed films.
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, epoxy, or urethane adhesive is used.
Moreover, in a polarizing film, as shown in FIG.1 (c)-FIG.1 (e), as for an optical film, you may laminate | stack 1 layer-3 layers as needed.

The flat panel display (FPD) of the present invention includes the optical film of the present invention. For example, a liquid crystal display (LCD) including a liquid crystal panel in which the polarizing film of the present invention and a liquid crystal panel are bonded to each other is provided. An organic electroluminescence display device (EL) including an organic electroluminescence panel in which the polarizing film of the present invention and a light emitting layer are bonded can be exemplified.
As an embodiment of the FPD according to the present invention, LCD and EL will be described in detail below.

[LCD]
Examples of the LCD include an LCD having a liquid crystal panel as shown in FIG. The LCD is obtained by bonding the polarizing plate 4 of the present invention and the liquid crystal panel 6 through an adhesive layer 5. According to the above configuration, when a voltage is applied to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules are driven to produce an optical shutter effect.

[EL]
Examples of the EL include an EL provided with the organic electroluminescence panel shown in FIG. The organic electroluminescence panel is obtained by bonding the optical film 4 of the present invention and the light emitting layer 7 through an adhesive layer 5.
In the organic electroluminescence panel, the optical film 4 functions as a broadband circularly polarizing plate. The light emitting layer 7 is at least one layer made of a conductive organic compound.

Hereinafter, the present invention will be described in more detail with reference to examples.
<Production example of the present compound (J-3)>
This compound (J-3) has the following structure.

The acrylic ester derivative (PG-e) used for (J-3) etc. was synthesized according to the following route.

(Synthesis example of ethyl 4- (6-hydroxyhexyloxy) benzoate (PG-a))
169 g (1.02 mol) of ethyl 4-hydroxybenzoate, 211 g (1.53 mol) of potassium carbonate and 847 g of N, N-dimethylacetamide were added, and the temperature was raised to 80 ° C. Subsequently, 277 g (1.53 mol) of 6-bromohexanol was dropped over 2 hours, and then stirred at 80 ° C. for 2 hours. After cooling, the reaction solution was poured into ice water and extracted with ethyl acetate. After the ethyl acetate layer was washed with water, the solvent was distilled off to obtain 377 g of a colorless and transparent liquid mainly composed of ethyl 4- (6-hydroxyhexyloxy) benzoate (PG-a).

(Synthesis example of 4- (6-hydroxyhexyloxy) benzoic acid (PG-b))
377 g of methanol and 181 g of water were added to 377 g of a colorless and transparent liquid containing (PG-a) as a main component obtained in the previous section and stirred. Next, 2092 g of a methanol solution containing potassium hydroxide in a saturated state (397 g (7.08 mol) of potassium hydroxide in the solution) was added dropwise and stirred at about 70 ° C. for 5 hours. After cooling, 718 g of 35% hydrochloric acid was slowly added. The precipitated white solid was filtered off while washing with water, and dried under reduced pressure at 50 ° C. to obtain 228 g of 4- (6-hydroxyhexyloxy) benzoic acid (PG-b) as a white solid. The yield was 94% based on ethyl 4-hydroxybenzoate.

(Synthesis example of 4- (6-acryloxyhexyloxy) benzoic acid (PG-c))
The inside of the container containing 228 g (0.96 mol) of the white solid (PG-b) obtained in the previous section and 244 g (2.01 mol) of N, N-dimethylaniline was replaced with nitrogen, and 2282 g of 1,4-dioxane was used. Dissolved. The temperature of the reaction solution was raised to 70 ° C., and 173 g (1.92 mol) of acrylic acid chloride was added dropwise over 30 minutes, followed by further stirring for 2 hours. After cooling, the reaction solution was poured into ice water, and then ethyl acetate was added for liquid separation and extraction, and the organic layer was taken out. The obtained organic layer was washed with water, and the solvent was distilled off under reduced pressure to obtain 109 g (0.37 mol) of 4- (6-acryloylhexyloxy) benzoic acid (PG-c) as a white solid. The yield was 39% based on (PG-b).

(Synthesis example of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d))
166 g (1.2 mol) of 4-hydroxybenzoic acid, 121 g (1.2 mol) of triethylamine and 1193 g of chloroform were placed in a container and stirred. At room temperature, a mixed solution of 113 g (1.2 mol) of chloromethyl ethyl ether and 298 g of chloroform was added dropwise over 30 minutes, and the mixture was further stirred for 2 hours. After cooling, the reaction solution was separated and washed in the order of water, aqueous hydrochloric acid solution and aqueous sodium carbonate solution, and the organic layer was taken out. The organic layer was distilled off under reduced pressure to obtain 251 g of yellow liquid mainly composed of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d).

(Synthesis example of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e))
To 124 g of the yellow liquid mainly composed of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d) obtained in the previous section, 147 g (0.50 mol) of white solid (PG-c) obtained in the previous section, 4- Dimethylaminopyridine 7.7 (63 mmol) and chloroform 824 g were added. Subsequently, 123 g (0.60 mol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 165 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. Then, the organic layer obtained by filtering to remove the solid was separated and washed twice with 989 g of 2N hydrochloric acid. The solvent was distilled off from the washed organic layer to obtain 237 g of a pale yellow liquid.
474 g of ethanol and 12.7 g (50 mmol) of paratoluenesulfonic acid pyridinium salt were added to the obtained liquid, and the mixture was stirred at 60 ° C. for 3 hours. When the reaction solution was cooled to room temperature, white crystals were precipitated, and thus filtered to take out a solid. The obtained solid was carefully washed with ethanol and dried to obtain 180 g of (4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e). It was 86% on the basis of (PG-c).

The structure of the fluorene derivative (J-3A) used for (J-3) etc. is as follows.

(Synthesis example of 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene)
In a container, 25.0 g (93 mmol) of 2,7-dinitro-9-fluorenone, 87 g (925 mmol) of phenol, 0.49 g (5 mmol) of 3-mercaptopropionic acid, and 4.5 g of sulfuric acid were mixed. Stir for hours. When the reaction solution was added to a container containing 35 g of methanol and 70 g of water, crystals were precipitated. The crystals were separated by filtration, and 24.1 g (55 mmol) of 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene, which is yellow crystals, was obtained on a 2,7-dinitro-9-fluorenone basis. It was 59%.

(Synthesis example of (J-3A))
2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene 15.0 g (34 mmol), N, N-dimethylacetamide 75 g, potassium carbonate 7.1 g (51 mmol), ethyl iodide 5.3 g (34 mmol) ) Was heated to 70 ° C. and aged for 3 hours. After cooling, 75 g of methyl isobutyl ketone and 105 g of 1N hydrochloric acid were added to the reaction solution and stirred to separate the layers. The obtained organic layer was separated and washed twice with 105 g of 1N hydrochloric acid, and the organic layer was taken out. The obtained organic layer was concentrated, and normal heptane was added for crystallization to obtain 15.7 g of yellow crystals. The resulting crystals were purified by silica gel column chromatography to obtain 6.5 g of yellow crystals (J-3A). The yield was 41% based on 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene.

(Synthesis example of J-3)
In a container, 5.6 g (12 mmol) of (J-3A), 5.9 g (14 mmol) 4-dimethylaminopyridine of (4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e) 0.2 g (1 mmol) and 48 g of chloroform were mixed, and then 3.3 g (16 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 12 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. After adding 59 g of 2N hydrochloric acid, the solid matter was removed by filtration, and the filtrate was separated, and the organic layer was taken out, 59 g of 2N hydrochloric acid was added to the obtained organic layer, and the liquid was washed. The compound (J-3), which is a pale yellow solid, was thoroughly washed with methanol. 4.6 g was obtained, and the yield was 44% based on 9,9-bis (4-hydroxyphenyl) fluorene.

<Production example of the present compound (J-4)>
This compound (J-4) has the following structure.

The structure of the fluorene derivative (J-4A) used for (J-4) is as follows.

(Synthesis example of 2,7-dinitro-9,9-bis (4-hydroxy-3-methyl-phenyl) fluorene)
This compound 2,7-, which is a yellow solid, is prepared in the same manner as in (Synthesis example of 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene) except that orthocresol is used instead of phenol. 37 g of dinitro-9,9-bis (4-hydroxy-3-methyl-phenyl) fluorene was obtained. The yield was 67% based on 2,7-dinitro-9-fluorenone.

(Synthesis example of (J-4A))
Except for using 2,7-dinitro-9,9-bis (4-hydroxy-3-methyl-phenyl) fluorene instead of 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene, In the same manner as in (Synthesis example of (J-3A)), 10.3 g of (J-4A) as a yellow solid was obtained. The yield was 49% based on 2,7-dinitro-9,9-bis (4-hydroxy-3-methyl-phenyl) fluorene.

(Synthesis example of J-4)
It replaced with (J-3A), and except using (J-4A), it carried out similarly to (Synthesis example of (J-3)), and obtained 7.0 g of (J-4) which is a pale yellow solid. . The yield was 79% based on (J-4A).

<Production example of the present compound (J-5)>
This compound (J-5) has the following structure. The synthesis example is shown below.

The acrylic ester derivative (PG-h) used for (J-5) was synthesized according to the following route.

(Synthesis example of (PG-f))
80 g (0.37 mol) of 4- (4-hydroxyphenyl) benzoic acid, 206 g (1.49 mol) of potassium carbonate and 400 g of N, N-dimethylacetamide were added, and the temperature was raised to 90 ° C. Subsequently, 153 g (1.12 mol) of 6-chlorohexanol was dropped over 2 hours, and then stirred at 90 ° C. for 8 hours. The reaction solution was cooled and then filtered to remove solids, and then poured into water for crystallization and filtered to take out the solids. The solid was washed with 1N hydrochloric acid to obtain 434 g of an undried (PG-f) white solid.

(Synthesis example of (PG-g))
To 434 g of undried (PG-f) white solid, 600 g of tetrahydrofuran and 300 g of ethylene glycol were added, and the temperature was raised to 65 ° C. Subsequently, 394 g of 10% sodium hydroxide (0.87 mol of sodium hydroxide) was added dropwise, and then stirred at 65 ° C. for 3 hours. After cooling the reaction solution, it was poured into water and hydrochloric acid was added until it became acidic, so that crystals were precipitated. The solid was taken out by filtration and then dried to obtain 103 g of white solid (PG-g).

(Synthesis example of (PG-h))
To 100 g (0.45 mol) of white solid of (PG-g), 1000 g of N, N-dimethylacetamide and 123 g (1.02 mol) of N, N-dimethylaniline were added and cooled to 0 ° C. Subsequently, 60.5 g (0.67 mol) of acrylic acid chloride was added dropwise, and then stirred at room temperature for 3 hours. When the reaction solution was cooled and 1N hydrochloric acid was added until it became acidic, crystals were precipitated. After filtering and taking out a solid substance, when dried, 80 g of white solid of (PG-h) was obtained. The yield was 64% based on (PG-g).

(Synthesis example of J-5)
(J-5) 7.0 g which is a pale yellow solid was obtained similarly to (Synthesis example of (J-3)) except that (PG-g) was used instead of (PG-e). . The yield was 79% based on (J-3A).

<Production example of the present compound (J-6)>
This compound (J-6) has the following structure. The synthesis example is shown below.

The acrylic ester derivative (PG-i) used for (J-6) was synthesized according to the following route.

(Synthesis example of (PG-i))
To 19.6 g of the yellow liquid mainly composed of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d) obtained in the previous section, 30.9 g (75 mmol) of the white solid of (PG-e) obtained in the previous section, 4-Dimethylaminopyridine 1.2 (10 mmol) and 245 g of chloroform were added. Subsequently, 20.6 g (100 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 49 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. Then, the organic layer obtained by filtering to remove the solid was separated and washed twice with 989 g of 2N hydrochloric acid. In the washed organic layer, the solvent was distilled off to obtain 88 g of a pale yellow liquid.
To the obtained liquid were added 88 g of tetrahydrofuran, 1.9 g (8 mmol) of paratoluenesulfonic acid pyridinium salt and 88 g of ethanol, and the mixture was stirred at 60 ° C. for 3 hours. When the reaction solution was cooled to room temperature, white crystals were precipitated, and thus filtered to take out a solid. The obtained solid was carefully washed with ethanol and then dried to obtain 19.2 g of (PG-i). The yield was 48% based on (PG-e).

(Synthesis example of J-6)
7.3 g of a light yellow solid (J-5) was obtained in the same manner as in (Synthesis example of (J-3)) except that (PG-i) was used instead of (PG-e). . The yield was 83% based on (J-3A).

Example 1
<Example of optical 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 after heating and drying, a 89 nm thick film was obtained. Subsequently, after rubbing the surface, a coating solution (mixed solution) having the composition of Example 1 in Table 1 was applied to the surface subjected to the rubbing treatment by spin coating, and dried at 45 ° C. for 1 minute. . Subsequently, after leaving at room temperature for 1 minute, 1200 mJ / cm ² ultraviolet rays were irradiated to prepare an optical film.
In Table 1, LC242 is a liquid crystal compound obtained from BASF, the photopolymerization initiator is Irgacure 907 (manufactured by Ciba Specialty Chemicals), the leveling agent is BYK361N (manufactured by Big Chemie Japan), and the solvent is cyclo Pentanone was used. Moreover, the weight% in the tables other than the solvent means the weight% of the solid content with the coating solution being 100% by weight.

<Measurement of wavelength dispersion characteristics>
In the wavelength range of 450 nm to 700 nm, the retardation value of the created optical film is measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments), and the retardation value Re (450) at a wavelength of 450 nm is measured with the program attached to the apparatus. The retardation value Re (550) at a wavelength of 550 nm and the retardation value Re (650) at a wavelength of 650 nm were calculated. The results are shown in Table 2. In the table, d represents the film thickness of the liquid crystal layer, β represents the tilt angle that is an index of birefringence, and the smaller the value of β, the more horizontally aligned.
It can be seen that the value of Re (450) / Re (550) is close to 1, and the wavelength dependence of the phase difference value is reduced.

(Example 2)
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used. About the obtained optical film, the phase difference value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2. It can be seen that the value of Re (450) / Re (550) is close to 1, and the wavelength dependence of the phase difference value is reduced.

(Example 3)
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used. About the obtained optical film, the phase difference value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2. It can be seen that the value of Re (450) / Re (550) is close to 1, and the wavelength dependence of the phase difference value is reduced.

Example 4
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used. About the obtained optical film, the phase difference value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2. It can be seen that the value of Re (450) / Re (550) is close to 1, and the wavelength dependence of the phase difference value is reduced.

(Comparative Example 1)
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used. About the obtained optical film, the phase difference value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2.

(Comparative Example 2)
Table 2 shows the Re (450) / Re (550) values of the optical film obtained by coating the alignment film with the compound represented by the formula (II) disclosed in Patent Document 1.

The present invention can provide a novel optical film that can further suppress the wavelength dependence of the retardation value and a novel compound that can provide the film.

A polarizing plate in which an optical film and a polarizing film are bonded directly or via an adhesive A polarizing plate in which a plurality of optical films and a polarizing film are bonded directly or via an adhesive layer Bonded product of polarizing plate and liquid crystal panel used in liquid crystal display devices Organic electroluminescence panel used for organic electroluminescence display device

Explanation of symbols

1, 1 ′ optical film 2 polarizing film 3, 3 ′, 3 ″ adhesive 11, 11 ′ liquid crystal layer (including structural units derived from compound (1) or (2)
Layer consisting only of film)
12, 12 ′ Alignment film 13, 13 ″ Support substrate 4 Polarizing plate 5 Adhesive layer 6 Liquid crystal panel 7 Light emitting layer

Claims (15)

The compound represented by Formula (1) or the compound represented by Formula (2).

(In Formula (1) and Formula (2), EWG independently represents an electron withdrawing group, and the electron withdrawing group is a nitro group, a nitrile group, a trifluoromethyl group, or a fluoro group. P and q Each independently represents an integer of 0 to 4, provided that 1 ≦ p + q ≦ 8.
A ₁ and A ₂ each independently represent a 1,4-phenylene group, and the 1,4-phenylene group is a group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. At least one substituent selected from may be bonded.
B ₁ , B ₂ and B ₃ are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, It represents —C (═O) —NR—, —NR—C (═O) —, —OCH ₂ —, —O—C (═O) —O— or a single bond. Here, R represents a C1-C4 alkyl group or a hydrogen atom.
X represents a divalent group represented by the formula (3).

[In Formula (3), A ₃ represents a 5- to 20-membered divalent cyclic hydrocarbon group or a 5- to 20-membered divalent heterocyclic group. The cyclic hydrocarbon group and the heterocyclic group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom. May be combined.
B ₄ is, -CR'R "-, - 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-, -C (= O) -NR '. -, - NR'-C (= O) -, - OCH 2 -, - NR '-, - CH 2 O -, - CH = CH-C (= O) -O -, - O-C (= O ) —CH═CH— or a single bond, wherein R ′ and R ″ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
n represents an integer of 1 to 4. When n is 2 to 4, the structural units composed of A ₃ and B ₄ may be the same as or different from each other. ]
E ₁ represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in E ₁ may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. Good.
E ₂ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group, and a hydrogen atom contained in E ₂ is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. May be.
P ₁ is a group represented by (D-1) to (D-5).

[In formulas (D-1) to (D-5), R _{1 to} R ₅ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ]) The compound according to claim 1, wherein EWG in the formulas (1) and (2) is a nitro group, a nitrile group or a trifluoromethyl group. The compound according to claim 1 or 2, wherein A ₃ is any group represented by formulas (4-1) to (4-5).

The compound according to any one of claims 1 to 3, wherein P _{1 of the} compounds represented by formula (1) and formula (2) is a group represented by formula (D-1). The composition containing the compound in any one of Claims 1-4, and the polymeric compound which shows liquid crystallinity. An optical film obtained by polymerizing the composition according to claim 5. The optical film containing the structural unit derived from the compound in any one of Claims 1-4. The optical film according to claim 6 or claim 7 retardation value at a wavelength 550nm light (Re (550)) is 113～163Nm. The optical film according to claim 6 or 7, wherein a retardation value (Re (550)) at a wavelength of 550 nm of light is 250 to 300 nm. The polarizing plate containing the optical film and polarizing film in any one of Claims 6-9. A flat panel display device comprising the polarizing plate according to claim 10 and a liquid crystal panel. An organic electroluminescence display device comprising the polarizing plate according to claim 10 and an organic electroluminescence panel. The manufacturing method of the unpolymerized film which apply | coats the solution containing the composition of Claim 5 to a support base material, and makes it dry. The manufacturing method of the unpolymerized film which apply | coats the solution containing the composition of Claim 5 on the orientation film | membrane formed on the support base material, and dries. The manufacturing method of the optical film which hardens the unpolymerized film obtained by the manufacturing method of Claim 13 or 14 by superposition | polymerization.

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