JP5219583B2 - Composition, optical film and method for producing the same, optical member and display device - Google Patents

Description

  The present invention relates to a composition, an optical film, a method for producing the same, an optical member, and a display device, and more specifically, 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. The present invention relates to a composition suitable for the above, an optical film used by being attached to a liquid crystal cell, a production method thereof, an optical member using the same, and a display device.

A flat panel display (FPD) includes members using optical films such as a polarizing plate and a retardation plate. Examples of the optical film include an optical film obtained by polymerizing a solution obtained by dissolving a polymerizable compound in a solvent on a supporting substrate. It is known that the phase difference (Re (λ)) of the optical film given by the light of wavelength λnm is determined by the product of the birefringence Δn and the thickness d of the film (Re (λ) = Δn). Xd). The wavelength dispersion characteristic is usually represented by a value (Re (λ) / Re (550)) obtained by dividing the phase difference value Re (λ) at a certain wavelength λ by the phase difference value Re (550) at 550 nm. It is known that uniform polarization conversion is possible in a wavelength range where Re (λ) / Re (550)) is close to 1.
As a polymerizable compound used in this way, LC242 (manufactured by BASF) is commercially available (Non-Patent Document 1).

"Paliocolor", [online], October 20, 2004, BASF, [Searched on December 5, 2007], Internet <http://www.inorganics.basf.com/p02/CAPortal/en_GB/ portal / Displaychemikalien / content / Produktgruppen / Displaychemikalien / Palicolor / Paliocolor>

  An object of the present invention is to provide a new composition that provides an optical film capable of uniform polarization conversion in a wide wavelength range.

The composition of the present invention comprises:
It includes a compound represented by formula (1) and a compound having a substituent represented by formula (2) (however, different from the compound represented by formula (1)).

[Where:
EWG each independently represents a nitro group, a nitrile group or a trifluoromethyl group.
p and q represent the integer of 0-4 each independently. However, 1 ≦ p + q ≦ 8.
R ′ and R ″ each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
s and t each independently represent an integer of 0 to 4. When s and t are 2 to 4, R ′ and R ″ may be the same as or different from each other.
A ³ and A ¹¹ each independently represent a 5- to 20-membered bivalent cyclic hydrocarbon group or a 5- to 20-membered bivalent heterocyclic group. The cyclic hydrocarbon group and 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 substituted.
B ¹ , B ² and B ³ are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ¹ —, —NR ¹ —C (═O) —, —OCH ₂ —, —O—C (═O) —O— or a single bond is represented. Wherein, ^{R 1} represents an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.
B ^{4 is, -CR 1 R 2 -, -} 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 ^1. —, —NR ¹ —C (═O) —, —OCH ₂ —, —NR ¹ —, —CH ₂ O—, —CH═CH—C (═O) —O—, —O—C (═O ) —CH═CH— or a single bond. Here, R < ¹ > and R < ² > represent a C1-C4 alkyl group or a hydrogen atom each independently.
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. The alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
E ² represents a hydrogen atom, a linear or cyclic alkyl group having 1 to 12 carbon atoms, or an unsaturated hydrocarbon group having 2 to 12 carbon atoms. The alkyl group and the unsaturated hydrocarbon group include 1 to 1 carbon atoms. A 4 alkyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom may be substituted.
P is a hydrogen atom or a group represented by formulas (P-1) to (P-5).

Here, R < ¹ > -R < ⁵ > represents a C1-C4 alkyl group or a hydrogen atom each independently.
B ¹¹ and ^{B 12} 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—, —O—C ( = O) -CH = CH- or a single bond. Here, 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.
E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. The alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and may contain —O— or —C (═O) —. Good.
m represents an integer of 1 to 3. When m is 2 or 3, the structural units consisting of A ¹¹ and B ¹¹ may be the same as or different from each other.
P ¹¹ represents a group represented by formulas (P-1) to (P-5). ]

In this composition, the compound having a substituent represented by the formula (2) (but different from the compound represented by the formula (1)) is converted into the compound represented by the formula (2A) and the formula (2B). It is preferable that it is a compound containing the compound represented by these.
^{P 11 -E 11 - (B 11} -A 11) m -B 12 -E 12 -P 12 (2A)
^{P 11 -E 11 - (B 11} -A 11) m -B 12 -F 11 (2B)
[Wherein P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² and m represent the same meaning as described above.
E ¹² is the same meaning as ^{E 11,} P ¹² represents the same meaning as ^{P 11.}
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 nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, —COOH, or a halogen atom. ]

A ³ is preferably any group represented by formulas (A-1) to (A-5).

  Furthermore, it is preferable that P of the compound represented by Formula (1) and Formula (2) is a group represented by Formula (P-1).

Moreover, it is preferable that the film of this invention is formed from the said composition, or a thing obtained by superposing | polymerizing the said composition especially.
This film functions as a λ / 4 plate having a retardation value (Re (550)) at a wavelength of 550 nm of light passing through the film of 113 to 163 nm, or a retardation value at a wavelength of 550 nm of light passing through the film ( What functions as a (lambda) / 2 board whose Re (550)) is 250-300 nm is preferable.

Moreover, this invention provides the polarizing plate or optical member containing the said film.
Furthermore, the flat panel display device of the present invention is equipped with the polarizing plate or the optical member.

Moreover, the manufacturing method of the unpolymerized film of this invention apply | coats the solution containing the said composition on the support base material or the alignment film formed on the support base material, It is characterized by drying.
Furthermore, the film production method of the present invention is characterized in that the unpolymerized film is cured by polymerization.

  According to the composition of the present invention, a film capable of uniform polarization conversion in a wide wavelength range can be provided.

  The composition of the present invention comprises at least one compound represented by the above formula (1) (hereinafter sometimes referred to as the compound (1)) and at least one substitution represented by the above formula (2). And a compound having a group (however, different from the compound represented by the formula (1)).

In each group in Formula (1) and Formula (2), the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. Hexyl group, octyl group, 2-ethylhexyl group and the like.
Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group and the like.
Examples of the divalent cyclic hydrocarbon group include groups represented by the following formula.
A divalent heterocyclic group is a divalent cyclic group having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom and a carbon atom. Also good. For example, as the divalent heterocyclic group having aromaticity, a group represented by the following formula is exemplified.

Examples of the divalent heterocyclic group having no aromaticity include groups represented by the following formula.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As the alkylene group, methylene group, ethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group , 1-ethylethylene group, 2-ethylethylene group and the like.
Examples of the unsaturated hydrocarbon group include a vinyl group, a propynyl group, a butenyl group, a pentenyl group, a hexenyl group, a butadienyl group, a pentadienyl group, an ethynyl group, and a propynyl group.
In this specification, any chemical structural formula varies depending on the number of carbon atoms, but unless otherwise specified, an alkyl group, a cyclic alkyl group, an alkoxy group, a divalent cyclic hydrocarbon group, a divalent heterocyclic ring. Examples of the group, halogen atom, alkylene group, unsaturated hydrocarbon group and the like are the same as those described above. Moreover, the thing which can take both a linear or branched includes both.

In particular, in formula (1) and formula (2), p = q = 1 is preferable as p and q.
In the case of p = q = 1, the bonding position of EWG in the benzene ring is not particularly limited and may be different on the left and right, but it is possible that both are bonded to the position of the carbon atom at the ii position in the following formula. It is preferable from an easy point.
R ′ and R ″ are preferably a methyl group, an ethyl group or the like.
Moreover, as s and t, s = t = 0 or 1 is preferable. In particular, when s = t = 1, the bonding position of the substituent R ′ or R ″ in the benzene ring is not particularly limited and may be different from right to left. Bonding to a position is preferable from the viewpoint of easy synthesis.
As A ³ and A ¹¹ , groups represented by formulas (A-1) to (A-5) are particularly preferable, and in particular, from the ease of synthesis, formulas (A-2) and (A-5) The group represented by these is preferable.

As will be described later, n is preferably an integer of 2 to 4 from the viewpoint of easy handling when the composition containing the compound (1) is cast and the improvement of the orientation of the compound.
The alkylene group for E ¹ may be substituted, but is preferably unsubstituted.
Further, when the substituent E ¹¹ is substituted, the substituents, an alkyl group or an alkoxy group having 1 to 4 carbon atoms or is preferably a halogen atom,.
P is easily copolymerized with the compound containing the substituent of formula (2) and tends to immobilize the structural unit derived from compound (1) in the resulting optical film. The groups represented by 1) to (P-5) are preferable, and the group represented by the formula (P-1) is particularly preferable because it can be easily photopolymerized.

The B ¹¹ and ^{B 12,} from the viewpoint of liquid properties are improved, in _{particular, -C≡C -, - CH = CH} -, - CH 2 -CH 2 -, - O -, - C (= O) - O-, -O-C (= O)-, -O-C (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O)- ^{NR 11 -, - NR 11 -C} (= O) -, - OCH 2 -, - OCF 2 -, - CH 2 O -, - CF 2 O- or a single bond.
P ¹¹ is preferably a group represented by the formula (P-1) in the same manner as P described above and from the viewpoint of stability.

Specific examples of the compound (1) include the following formulas (I-1) to (I-3) and formulas (II-1) to (II-3). However, in this specification, r and r 'each independently represent an integer of 1 to 12, and Z represents a hydrogen atom or methyl.

As a method for producing the compound (1) of the present invention, the carbonyl compound represented by the formula (1-B) will be described as an example. First, for example, phenol, orthocresol, 2-methoxyphenol is added to the carbonyl compound. A bisphenol derivative represented by the formula (1-B-1), the formula (1-B-2) or the like is obtained by reacting phenols such as

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 obtained 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 formulas (1-A-1) to (1-A-45).

The obtained monophenol intermediate is reacted with a compound giving a structure of -B ^1- (A ³ -B ⁴ ) _n -E ¹ -B ³ -P to give the compound (1) and the formula (2) of the present invention. ) -Containing substituents can be prepared.
If B ¹ is —OC (═O) —, the corresponding carboxylic acid, carboxylic acid chloride as a compound giving the structure of B ^1- (A ³ -B ⁴ ) _n -E ¹ -B ³ -P, What is necessary is just to esterify with a monophenol intermediate using a carboxylic acid anhydride or a mesitylated compound of carboxylic acid.
When B ¹ is —O—, it may be etherified using a corresponding halide as a compound giving a structure of B _1- (A ³ -B ⁴ ) _n -E ¹ -B ³ -P.

Compounds giving the structure of H-B _1- (A ³ -B ⁴ ) _n -E ¹ -B ³ -P are represented by the formulas (5-A-1) to (5-A-124). Examples thereof include carboxylic acids and chlorides of these carboxylic acids. In addition, in this specification, k represents the integer of 1-12.

The compounds represented by the formulas (5-A-1) to (5-A-124) include compounds containing structural units of A ³ , B ⁴ , E ¹ , B ³ and P, for example, a condensation reaction, Esterification reaction, Williamson reaction, Ullmann reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heart wig reaction, Wittig reaction, Friedel-Craft reaction, Heck reaction or It can be produced by bonding by an aldol reaction or the like. 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- The method described in 6727 (1994), the method described in Advanced, Functional, Materials, Vol. 15, 1961-1972 are exemplified.

The compositions of the present invention, ^P 11 ^-E 11 as a substituent shown by the formula _{^{(2) - (B 11 -A}} 11) m -B 12 - may only contain. This compound may contain only 1 type and may contain 2 or more types.
In addition, as for the substituent at the terminal of the compound containing such a substituent, that is, the terminal substituent bonded to B ¹² , the substituent constituting the formula (2) is symmetrical as in -E ¹¹ -P ^11. Or an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a hydrogen atom, a halogen atom, a hydroxyl group, a carboxylic acid, a carboxylic acid ester, a nitrile group, It may be a nitro group, a trifluoromethyl group, a dimethylamino group, or the like.

Specifically, the compound having a substituent represented by the formula (2) (but different from the compound represented by the formula (1)) includes the compound represented by the formula (2A) and the formula (2B). It is preferable that it is a compound containing the compound represented by these.
^{P 11 -E 11 - (B 11} -A 11) m -B 12 -E 12 -P 12 (2A)
^{P 11 -E 11 - (B 11} -A 11) m -B 12 -F 11 (2B)
[Wherein P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² and m represent the same meaning as described above.
E ¹² is the same meaning as ^{E 11,} P ¹² represents the same meaning as ^{P 11.}
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 nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a carboxylic acid, a carboxylic acid ester, or a halogen. Represents an atom. ]

The compound containing the substituent of the formula (2) of the present invention includes (5-A-1) to (5-A-10), (5-A-51) to (5-A-56) and (6- a-1) ~ (6- a-10) as shown in a ^{P 11} -E ¹¹ - ^{(a compound B 11} -A ¹¹⁾ gives the structure of _m -B ¹² -H, the following (2-A- It can be obtained by reacting a compound as shown in 1) to (2-A-20). In the present specification, R represents a linear or branched alkyl group having 1 to 6 carbon atoms, and X represents a halogen atom.

B ¹² is, -C (= O) if ^{O-, P 11 -E 11 - (} B 11 -A 11) as compounds which provide a structure of ^{_{m -B 12 -H (5-A}} -1) ~ ( Carboxylic acid such as 5-A-10) and (5-A-51) to (5-A-56), its carboxylic acid chloride, its carboxylic acid anhydride, or its carboxylic acid mesitylated compound, etc. May be esterified with the corresponding hydroquinone derivatives (2-A-1) to (2-A-12) or (2-A-19).
B ¹² is, -OC (= O) - ^{if, P 11 -E 11 - (B} 11 -A 11) as compounds which provide a structure of ^{_{m -B 12 -H (6-A}} -1) ~ (6 What is necessary is just to esterify with a corresponding dicarboxylic acid derivative (2-A-13)-(2-A-18) or (2-A-20) using a phenol derivative etc. like -A-10).

The compounds containing the substituent of formula (2) are (5-A-1) to (5-A-10), (5-A-51) to (5-A-56), (6-A -1) ~ (6-a- 10) as shown in a ^{P 11 -E 11 - (B 11} -A 11) m -B 12 and compounds which provide the structure of -H, following (3-a-1 ) To (3-A-7) can also be synthesized by reacting the compounds.

B ¹² is, -C (= O) if ^{O-, P 11 -E 11 - (} B 11 -A 11) compounds which provide a structure of ^{_{m -B 12 (5-A-}} 1) ~ (5-A -10), a carboxylic acid such as (5-A-51) to (5-A-56), a carboxylic acid chloride thereof, a carboxylic acid anhydride or a mesitylated compound of the carboxylic acid. What is necessary is just to esterify with a corresponding phenol derivative (3A-A-1)-(3A-A-12).
B ¹² is, -OC (= O) - ^{if, P 11 -E 11 - (B} 11 -A 11) compounds which provide a structure of ^{_{m -B 12 (6-A-}} 1) ~ (6-A- What is necessary is just to esterify with a corresponding carboxylic acid derivative (3A-A-13)-(3A-A-24) etc. using a phenol derivative etc. like 10).

Furthermore, as another synthesis method of the compound containing the substituent of the formula (2), (5-A-19) to (5-A-26), (5-A-11) to (5-A-14) ), (5-A-43), (5-A-44), (5-A-47), (5-A-48), (5-A-57) to (5-A-64), and ^{(B 11} -A ¹¹⁾ compounds which provide a structure of ^{_{m -B 12 -H (m = 2}} ) - (5-a-117) ~ (5-a-120) as shown in a ^{P 11} -E ¹¹ The method of making it react with a compound as shown by the following (3-A-1)-(3-A-7) is mentioned.

B ¹² is, -C (= O) if ^{O, P 11 -E 11 - (} B 11 -A 11) m -B 12 (m = 2) compounds which provide the structure of (5-A-19) ~ (5-A-26), (5-A-11) to (5-A-14), (5-A-43), (5-A-44), (5-A-47), (5 -A-48), (5-A-57) to (5-A-64), carboxylic acids such as (5-A-117) to (5-A-120), carboxylic acid chlorides thereof, What is necessary is just to esterify with a corresponding phenol derivative (3-A-1)-(3-A-7) etc. using a carboxylic anhydride or the mesitylated compound of the carboxylic acid.

  As a compound containing the substituent of Formula (2), (5-A-15) to (5-A-18), (5-A-27) to (5-A-42), (5-A-45) ), (5-A-46), (5-A-49), (5-A-50), (5-A-65) to (5-A-72), (5-A-121) to Examples thereof include compounds represented by (5-A-124).

As another synthesis method of the compound containing the substituent of formula (2), (5-A-1) to (5-A-10), (5-A-51) to (5-A-56) , (6-a-1) ~ (6-a-10) as shown in a ^{P 11} -E ¹¹ - and compounds which provide the structure of _{^{(B 11 -A 11) m -B}} 12 -H, (3- Examples thereof include a method of reacting a compound as shown in A-1) to (3-A-7) or a compound as shown in the following (3-B-1) to (3-B-8).

B ¹² is, -C (= O) if ^{O-, P 11 -E 11 - (} B 11 -A 11) compounds which provide a structure of ^{_{m -B 12 (5-A-}} 1) ~ (5-A -10), a carboxylic acid such as (5-A-51) to (5-A-56), a carboxylic acid chloride thereof, a carboxylic acid anhydride or a mesitylated compound of the carboxylic acid. What is necessary is just to esterify with a corresponding phenol derivative (3-A-1)-(3-A-7) etc.
B ¹² is, -OC (= O) - ^{if, P 11 -E 11 - (B} 11 -A 11) compounds which provide a structure of ^{_{m -B 12 (6-A-}} 1) ~ (6-A- What is necessary is just to esterify with a corresponding carboxylic acid derivative (3-B-1)-(3-B-8) etc. using a phenol derivative etc. like 10).

  Moreover, as a compound containing the substituent of Formula (2), said (5-A-19)-(5-A-26), (5-A-11)-(5-A-14), (5- A-43), (5-A-44), (5-A-47), (5-A-48), (5-A-57) to (5-A-64), (5-A- 117) to (5-A-120), and the following compounds (6-A-11) to (6-A-30) are exemplified.

As yet another method of synthesis of compounds containing a substituent of the formula (2) is, (6-A-11) ~ (6-A-30) as shown in a ^{P 11 -E 11 - (B 11} -A ¹¹⁾ a compound providing structure _m -B ¹² -H, and a method to compound reaction as shown in (3-B-1) ~ (3-B-8). B ¹² is, -OC (= O) - ^{if, P 11 -E 11 - (B} 11 -A 11) compounds which provide a structure of ^{_{m -B 12 (6-A-}} 11) ~ (6-A- What is necessary is just to esterify with a corresponding carboxylic acid derivative (3-B-1)-(3-B-8) etc. using a phenol derivative etc. like 30).

  Furthermore, as a compound which has a substituent of Formula (2), the following formula (III-1)-(III-19), (IV-1)-(IV-14), (V-1)-(V The compound represented by -5) is exemplified.

  Specific examples of the compound containing the substituent of formula (2) include, for example, compounds represented by the following formulas (IV-1) to (IV-14), (V-1) to (V-5), etc. Is mentioned.

These compounds are easy to manufacture or are commercially available.

  In the composition of this invention, it is preferable that compound (1) is contained normally 1-50 weight part with respect to a total of 100 weight part of this composition, and 1-30 weight part containing. Further preferred. When the compound (1) is 50 parts by weight or less, the resulting film has excellent thermal stability, and when it is 30 parts by weight or less, the resulting film has further excellent thermal stability.

  In addition, the composition of the present invention is for application to a substrate or for curing after film formation, as necessary, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, an organic solvent. One or more additives such as a crosslinking agent can be added.

(Polymerization initiator)
In general, it is preferable to add a polymerization initiator for polymerization, particularly a photopolymerization initiator, to the composition of the present invention.
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.
The amount of the polymerization initiator 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 composition of the present invention. . If it is in the said range, a composition can be polymerized, without disturbing the orientation of a composition.

(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 composition of the present invention can be controlled, and the stability of the resulting optical film and the storage stability of the 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 composition of the present invention. . If it is in the said range, the composition of this invention can be polymerized, without disturbing the orientation of a composition.

[Photosensitizer]
Examples of the photosensitizer include xanthones such as xanthone or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, and rubrene.
By using a photosensitizer, the polymerization of the composition can be made highly sensitive.
The usage-amount of a photosensitizer is 0.1 weight part-30 weight part normally with respect to a total of 100 weight part of the composition of this invention, Preferably it is 0.5 weight part-10 weight part. . If it is in the said range, a composition can be polymerized, without disturbing the orientation of a composition.

(Leveling agent)
As the beling agent, for example, an additive for radiation-curing paint (by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), paint 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 composition can be adjusted.
The amount of the leveling agent 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 composition of the present invention. If it is in the said range, a composition can be polymerized, without disturbing the orientation of a composition.

[Organic solvent]
As the organic solvent, any organic solvent may be used as long as it can dissolve the composition of the present invention, and optionally additives. Specifically, alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve or butyl cellosolve; ester systems such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone or propylene glycol methyl ether acetate Solvent; Ketone solvent such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; Aliphatic hydrocarbon solvent such as pentane, hexane or heptane; Aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene , Acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxy Tan, ethyl lactate, chloroform or phenol. These organic solvents may be used alone or in combination. Of these, alcohols, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, and the like are preferable because they are excellent in compatibility with the composition of the present invention, such as chloroform. Even if the halogenated hydrocarbon is not used, it can be dissolved and applied.

[Crosslinking agent]
The crosslinking agent is not particularly limited, and examples thereof include those known in the art, such as polyacrylates, polymethacrylates, urethane acrylates, polyisocyanates, epoxy compounds, oxetane compounds and the like. More specifically, triacrylates (manufactured by Shin-Nakamura Chemical Co., Ltd .: CBX-1N, CBX-0, A-TMPT-3EO, A-TMPT-6EO, A-TMPT-9EO, A-TMM-3, A-TMM-3L, A-TMM-3LMN, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-20E, TM-4EL, manufactured by SARTOMER: SR499, SR502, SR9035, SR368), tetraacrylates (manufactured by Shin-Nakamura Chemical Co., Ltd .: ATM-4E, ATM-35E), pentaacrylates (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-9530, manufactured by SARTOMER: SR399E), hexaacrylates (Shin Nakamura Chemical Co., Ltd .: A-DPH-6E, A-DPH-12E, A-DPH-6P, Kyoeisha Chemical Co., Ltd. Formula company made: UA-306H, UA-306I, manufactured by Nippon Kayaku Co., Ltd.: DPCA-60, DPCA-120), and the like.
By using a crosslinking agent, the crosslinking density of the film obtained by polymerizing the composition can be adjusted. Therefore, if the crosslink density is improved, the durability and reliability of the film can be improved.
The amount of the crosslinking agent 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 composition of the present invention. Within the above range, the composition can be polymerized without disturbing the orientation of the composition.

  The film of the present invention is a film containing a structural unit derived from a compound containing a substituent of the compound (1) and the formula (2) in the composition of the present invention mainly as an optical film, and by this composition, It can be formed unpolymerized or polymerized. Here, the optical film refers to a film that can transmit light and has an optical function, and the optical function refers to refraction, birefringence, and the like.

A method for polymerizing and producing the film of the present invention will be described below.
First, a solution of the composition of the present invention, optionally mixed with one or more of the above-described polymerization initiators, polymerization inhibitors, photosensitizers, leveling agents, organic solvents, crosslinking agents and the like. To prepare. However, it is necessary to use a solution that does not impair liquid crystallinity after a solution of the composition is formed into a film and dried. In particular, the organic solvent is preferably contained because the film formation becomes easy, and the polymerization initiator has a function of curing the obtained optical film.

It is preferable to adjust the solution of such a composition to a viscosity of usually 10 Pa · s or less, preferably about 0.1 to 7 Pa · s so as to be easily applied.
Moreover, it is suitable that the density | concentration of solid content in a composition solution shall be 5-50 weight% normally. By setting the solid content concentration within this range, the film thickness of the optical film is less likely to be uneven, making it easy to adjust the film thickness to an appropriate thickness, and providing the optical anisotropy necessary for optical compensation of the liquid crystal panel. Can be given.

  Then, the target film can be formed on a support base material by apply | coating the solution of a composition to a support base material, and drying and polymerizing.

Any material may be used as the supporting base material as long as it can form an alignment film on the surface thereof. For example, glass, a plastic sheet, a plastic film, a translucent film, etc. can be mentioned. As the translucent film, for example, polyolefin film such as polyethylene, polypropylene, norbornene polymer, polyvinyl alcohol film, polyethylene terephthalate film, polymethacrylate film, polyacrylate film, cellulose ester film, polyethylene naphthalate film, Examples include polycarbonate films, polysulfone films, polyethersulfone films, polyetherketone films, polyphenylene sulfide films, and polyphenylene oxide films.
Since the film obtained from the composition may require strength such as bonding, transportation, storage, etc., the film is not torn and easy to handle by using the support substrate.

In addition, the solution of the composition of the present invention may be applied directly on the supporting substrate, but in order to obtain a more uniform orientation, it may be applied on the alignment film formed on the supporting substrate. preferable.
The alignment film has solvent resistance that does not dissolve due to application of the solution containing the composition of the present invention, has heat resistance due to solvent removal, liquid crystal alignment heat treatment, peeling due to friction by rubbing, etc. And the like, and can be formed by a composition containing a polymer and optionally a solvent.
Examples of the polymer that forms the alignment film 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, Examples thereof include polymers such as acrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. These polymers may be used alone, or two or more of them may be mixed and 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.

The solvent is not particularly limited, and 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-butyrolactone Ester solvents such as propylene glycol methyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, heptane; toluene, Aromatic hydrocarbon solvents such as xylene and chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxy Ethane, ethyl lactate, can be used for various chloroform. These organic solvents may be used alone or in combination.
Further, 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.

As a method for forming an alignment film on a support substrate, for example, a commercially available alignment film material, the above-described polymer or a constituent monomer as an alignment film material, and optionally a solvent are applied on the support substrate. Then, the method of annealing is mentioned.
The thickness of the obtained alignment film is usually about 10 nm to 10000 nm, and preferably about 10 nm to 1000 nm. If it is the said range, in the unpolymerized film preparation process mentioned later, the film formed from the composition of this invention can be oriented at a desired angle on an oriented film.
Moreover, these alignment films can be rubbed or irradiated with polarized ultraviolet rays as required. Thereby, the film formed from the composition of this invention can be oriented 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.
As described above, by using the alignment film, it is possible to easily obtain a desired alignment such as a homogeneous alignment, a homeotropic alignment, a hybrid alignment, etc., so that it is not necessary to control the refractive index by stretching. Therefore, an optical film excellent in uniformity with small in-plane variation of birefringence can be obtained. As a result, it is possible to form a large optical film that can cope with an increase in the size of the FPD on the support substrate.

  Examples of the method for applying the solution of the composition of the present invention on a supporting substrate or an alignment film include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. It is done. Moreover, you may apply | coat using coaters, such as a dip coater, a bar coater, and a spin coater.

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 it is preferable to obtain an unpolymerized film by drying most of the solvent before polymerization. Thereafter, a polymerization method is preferable because it tends to be excellent in film formability.
Examples of the solvent drying method include natural drying, ventilation drying, and vacuum drying. A specific heating temperature is suitably about 10 to 120 ° C, and preferably about 25 to 80 ° C. The heating time is suitably about 10 seconds to 60 minutes, preferably about 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.

For polymerization, if the substituent P of the compound (1) and the substituent P ¹¹ of the compound containing the substituent of the formula (2) are radically polymerizable or cationically polymerizable groups, visible light, ultraviolet light, laser light, etc. It can be cured by irradiating light. If these polymerizable groups are thermopolymerizable, they can be polymerized by heating.
Photopolymerization is preferable from the viewpoint of film formability, and polymerization by ultraviolet light is more preferable from the viewpoint of handleability.

Next, a method for producing the film of the present invention without polymerization will be described.
As such a method, for example, a solution of the composition of the present invention is applied on the alignment film of the supporting substrate on which the alignment film is formed and dried, a liquid crystal cell is produced, and the liquid crystal cell is prepared. Examples thereof include a method of injecting the composition to form a liquid crystal layer. In particular, the method of obtaining an unpolymerized film on an alignment film formed on a support substrate can reduce production costs, enables production of a film with a roll film, and good production efficiency. preferable.
In the resulting unpolymerized film, the composition of the present invention exhibits a liquid crystal phase such as a nematic phase and 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 100 ° C., a supporting substrate that is not necessarily sufficient in terms of heat resistance can be used. Moreover, even if it cools to about 30-10 degreeC after orientation, it does not crystallize.

In addition, after forming a film by non-polymerization as described above, the film may be polymerized and cured. Thereby, the orientation of the film having a structural unit derived from the composition of the present invention can be fixed.
The method for polymerizing the unpolymerized film can be appropriately adjusted according to the type of the compound contained in the composition. Examples include photopolymerization and thermal polymerization. Of these, photopolymerization is preferred. Thereby, since an unpolymerized film can be polymerized at low temperature, the selection range of the heat resistance of a support base material spreads. 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. In the polymerization step of the unpolymerized film, the composition is cross-linked by photopolymerization, so that it is not easily affected by the change in birefringence due to heat in the subsequent steps.

The film of the present invention is excellent in transparency, and has a single layer or a laminated structure (for example, about 2 to 4 layers), such as an optical film together with the above-described support substrate and / or alignment film or various optical films. It can be used for various applications. In addition, when laminating | stacking two or more layers, the same film may be sufficient and you may use it combining a different thing.
Examples of such an optical film include an optical film having excellent wavelength dispersion characteristics, such as 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 a transmission film. An optical compensation film for viewing angle compensation of a liquid crystal display is exemplified.
For example, the film of the present invention can be bonded to a polarizing film and used as an elliptically polarizing plate. Further, the film of the present invention can be further bonded to this elliptical polarizing plate as a broadband λ / 4 plate and used as a broadband circular polarizing plate.
In particular, in order to use the film of the present invention as a broadband λ / 4 plate or λ / 2 plate, it is derived from the compound (1) and the compound containing the substituent of formula (2) contained in the composition of the present invention. The content of the structural unit to be adjusted is adjusted as appropriate, the film thickness is adjusted, and the retardation value is adjusted.
Specifically, in the case of a λ / 4 plate, Re (550) of the obtained film may be adjusted to 113 to 163 nm, preferably 135 to 140 nm, more preferably about 137.5 nm. In the case of a λ / 2 plate, Re (550) of the obtained film may be adjusted to 250 to 300 nm, preferably 273 to 277 nm, more preferably about 275 nm.

  In addition, in order to use the film of the present invention as an optical film for a VA (vertical alignment) mode, the content of the structural unit derived from the composition of the present invention is appropriately adjusted, and the film thickness of the film is adjusted. Good. Specifically, the film thickness may be adjusted so that Re (550) is, for example, about 40 to 100 nm, preferably about 60 to 80 nm.

  That is, in the composition of the present invention, by changing the content of the compound containing the substituent of the compound (1) and the formula (2), the wavelength dependency of the refractive index of the film obtained, the wavelength dispersion characteristic, the tilt angle. The phase difference value can be controlled by adjusting the film thickness of the resulting film by adjusting the amount when the composition is applied and the concentration of the organic solvent. .

  Specifically, by increasing the content of the compound (1), Re (450) / Re (550) and the like can be changed, that is, chromatic dispersion can be reduced. Further, by increasing the content of compound (3A) or compound (3B), the composition can be oriented in the film direction and the tilt angle can be reduced.

Further, since the retardation value (retardation value, Re (λ)) of the film is determined as shown in Expression (6), the film thickness d is adjusted in order to obtain a desired Re (λ).
Re (λ) = d × Δn (λ) (6)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a refractive index anisotropy at a wavelength λnm.)
Therefore, the film thickness may be increased to increase the phase difference value, and the film thickness may be decreased to decrease the phase difference value.

The film thickness of the film of the present invention is preferably 0.1 to 10 μm, and 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.
Thus, the film of this invention can be made into a thin film compared with the film which has an equivalent retardation value with a stretched film. In addition, the wavelength dependence of the phase difference value can be reduced.

As a specific embodiment of the film of the present invention, a polarizing plate constituted by laminating the film of the present invention and a polarizing film will be described.
The polarizing plate is obtained by directly bonding the film 1 of the present invention and the polarizing film, that is, the polarizing film 2 (FIG. 1A), the film 1 and the polarizing film 2 through the adhesive 3. Bonded film (FIG. 1 (b)), film 1, film 1 ′ and polarizing film 2 bonded together in this order (FIG. 1 (c)), film 1 and optical film 1 ′ bonded In addition, the polarizing film 2 is directly bonded to the optical film 1 ′ (FIG. 1D), the optical film 1, the optical film 1 ′, and the polarizing film 2 in this order. And those bonded through adhesives 3 and 3 ′ (FIG. 1 (e)).

  As another polarizing plate, as the optical film 1 and the optical film 1 ′, a film made of the liquid crystal layer 11 or the liquid crystal layer 11 ′ and the alignment film 12 or the alignment film 12 ′ may be used. Specifically, the optical film 1 and the polarizing film 2 are directly bonded (FIG. 2A), and the optical film 1 and the polarizing film 2 are bonded via the adhesive 3 (FIG. 2 ( b)), optical film 1, optical film 1 ′ and polarizing film layer 2 directly bonded together in this order (FIG. 2 (c)), optical film 1 and optical film 1 ′ via adhesive 3 Bonding, the polarizing film 2 directly bonded to the optical film 1 ′ (FIG. 2D), the optical film 1, the optical film 1 ′, and the polarizing film 2 through the adhesive layers 3 and 3 ′. What was bonded (FIG.2 (e)) is mentioned.

Furthermore, as the optical film 1 and the optical film 1 ′, the alignment film 12 or the alignment film 12 ′ is not included, and a film made of the liquid crystal layer 11 or the liquid crystal layer 11 ′ may be used. Specifically, the optical film 1 and the polarizing film layer 2 are bonded together via the adhesive 3 (FIG. 2 (f)), and the optical film 1 and the optical film 1 ′ are bonded via the adhesive layer 3. The polarizing film layer 2 is bonded to the outside through the adhesive layer 3 ′ (FIG. 2 (g)).
In addition, as the optical film 1, a film including a support substrate 13, an alignment film 12 formed on the surface of the support substrate 13, and a liquid crystal layer 11 formed on the surface of the alignment film 12 is used. Also good. Specifically, the support substrate 13 in such a film is one in which the polarizing film layer 2 is bonded via an adhesive layer 3 ′ (FIG. 2 (h)).

FIG. 2 (i) shows a support substrate 13 or a support substrate 13 ′ as an optical film 1 and an optical film 1 ′, and an alignment film 12 formed on the surface of the support substrate 13 or the support substrate 13 ′. The structure is the same as that of FIG. 2G except that a film including the alignment film 12 ′ and the alignment film 12 or the liquid crystal layer 11 or the liquid crystal film 11 ′ formed on the surface of the alignment film 12 ′ is used. is there.
In FIG. 2 (j), a film composed of the liquid crystal layer 11 ′ is used as the optical film 1 ′, and a film composed of the liquid crystal layer 11, the alignment film 12, and the supporting base material 13 is used as the optical film 1. 2), except that 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. This is the structure.

Examples of the polarizing film include a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film, and a film obtained by drawing a polyvinyl alcohol film to adsorb iodine or a dichroic dye.
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.

As another embodiment of the film of the present invention, an optical member provided with the film of the present invention will be described.
As shown in FIG. 3, the optical member can include the film of the present invention and a color filter.
The color filter 8 and the film 1 of the present invention laminated in this order on the support base material 13 (FIG. 3A), and the film 1 of the present invention and the color filter 8 on the support base material 13 in this order. A laminate (FIG. 3B) is mentioned.
In addition, an alignment film 12 is laminated between the color filter 8 and the liquid crystal layer 11 and between the support base 13 and the liquid crystal layer 11 (see FIGS. 3C and 3D). It is done. Thereby, the liquid crystal layer 11 can obtain a good alignment.

  Since the optical film of the present invention can be formed by coating on an alignment film and polymerizing by ultraviolet irradiation, it can be formed on a color filter more easily than before, for example, a broadband λ / 4 or λ / 2 phase difference. Layers and optical films can be formed. In particular, in order to color the liquid crystal panel, a color filter is indispensable. However, if an optical member including such a color filter is used, the phase difference of the liquid crystal panel itself can be reduced.

In addition, the film of the present invention allows a flat panel display device (FPD) such as a reflective liquid crystal display and an organic electroluminescence (EL) display to function in any position, in any mode, and in any manner. It may be provided as.
For example, a liquid crystal display device (LCD) including a liquid crystal panel in which the above-described polarizing plate and a liquid crystal panel are bonded together, and an organic electroluminescence display device including an organic electroluminescence panel in which the above-described polarizing plate and a light-emitting layer are bonded together (EL), and LCD and EL provided with a color filter.

[LCD]
As the LCD, for example, as shown in FIG. 4, an LCD configured by bonding the polarizing plate 4 of the present invention and the liquid crystal panel 6 through an adhesive layer 5 can be mentioned.
According to this configuration, by applying a voltage to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules can be driven and the optical shutter effect can be exhibited.

[EL]
As the EL, for example, as shown in FIG. 5, there may be mentioned one constituted by laminating the polarizing plate 4 of the present invention and the light emitting layer 7 through the adhesive layer 5. In the organic electroluminescence panel, the polarizing plate 4 functions as a broadband circular polarizing plate. The light emitting layer 7 is composed of at least one layer made of a conductive organic compound.

Examples of the composition of the present invention will be described in detail below. In addition, confirmation of thermophysical properties, such as liquid crystallinity of each compound, was performed by heating up and observing solid with a polarizing microscope with a hot stage.
<Production Example of Compound (J-1) of Formula (1)>
Compound (J-1) has the following structure.

The acrylate derivative (PG-e) and the acrylate derivative (PG-c) used for (J-1) etc. were synthesized by the following method.

(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 a container containing 228 g (0.96 mol) of the white solid (PG-b) obtained in the previous item 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 a yellow liquid mainly composed of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d) obtained in the previous item, 147 g (0.50 mol) of white solid (PG-c) obtained in the previous item, 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-1A) used for (J-1) 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-1A))
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 obtained crystals were purified by silica gel column chromatography to obtain 6.5 g of yellow crystals (J-1A). The yield was 41% based on 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene.

(Synthesis example of J-1)
In a container, (J-1A) 5.6 g (12 mmol), (4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e) 5.9 g (14 mmol) 4-dimethylaminopyridine 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-1), 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 Compound (J-3-1) of Formula (2)>
The compound (J-3-1) has the following structure.

(Synthesis example of J-3-1)
In a container, 6.8 g (35 mmol) of 4-cyano-4′-hydroxybiphenyl, 12.3 g (42 mmol) of 4- (6-acryloxyhexyloxy) benzoic acid (PG-c), 4-dimethylaminopyridine,. 5 g (4 mmol) and 98 g of chloroform were mixed, and then 10.4 g (50 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 25 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. After adding 123 g, the solid matter was removed by filtration, the filtrate was separated, and the organic layer was taken out, 123 g of 2N hydrochloric acid was added to the obtained organic layer, and after separating and washing, the solvent was distilled off, The solid obtained was added to methanol, and the obtained solid was carefully washed with methanol. -1) 14.7 g was obtained. The yield was 91% with 4-cyano-4'-hydroxybiphenyl reference.
In addition, (J-3-1) showed a liquid crystal phase at a temperature of 113 ° C. to 210 ° C. when the temperature was raised.

<Production Example of Compound (J-3-2) of Formula (2)>
The compound (J-3-2) has the following structure.

(Synthesis example of J-3-2)
(J-3-2) was prepared in the same manner except that 4-cyano-4'-hydroxybiphenyl used in (Synthesis example of J-3-1) was changed to 4-bromo-4'-hydroxybiphenyl. Synthesized. The yield of the obtained white solid compound (J-3-2) was 76% based on 4-bromo-4′-hydroxybiphenyl.
In addition, (J-3-2) showed a liquid crystal phase at a temperature of 103 ° C. to 187 ° C. when the temperature was raised.

<Production Example of Compound (J-3-3) of Formula (2)>
The compound (J-3-3) has the following structure.

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

Monotetrahydropyranyl protected hydroquinone (PG-i) was synthesized by the method described in the patent literature (Japanese Patent Application Laid-Open No. 2004-262848).

(Synthesis example of (PG-f))
150 g (0.90 mol) of ethyl 4-hydroxybenzoate, 187 g (1.35 mol) of potassium carbonate and 450 g of 4-chlorobutyl acetate N, N-dimethylacetamide were added and stirred at 100 ° C. for 14 hours. . After cooling, 450 g of methyl isobutyl ketone was poured into the reaction solution and filtered. The obtained filtrate was poured into water, separated and washed with water, and the organic layer was taken out. Thereafter, the organic layer was washed several times with water, and then the solvent was distilled off to obtain 257 g of a colorless and transparent liquid mainly composed of (PG-f).

(Synthesis example of (PG-g))
To 257 g of the colorless and transparent liquid mainly composed of (PG-f) obtained in the previous item, 770 g of methanol and 513 g of water were added and stirred. Next, 110 g (2.75 mol) of sodium hydroxide was added dropwise, and the mixture was stirred at about 65 ° C. for 2 hours. After cooling, 35% hydrochloric acid was slowly added until the pH was 2 or less. The precipitated white solid was filtered while washing with water and dried under reduced pressure at 50 ° C. to obtain 181 g of (PG-g) white solid. The yield was 94% based on ethyl 4-hydroxybenzoate.

(Synthesis example of (PG-h))
The inside of a container containing 181 g (0.86 mol) of the white solid (PG-g) obtained in the previous section and 157 g (1.29 mol) of N, N-dimethylaniline was replaced with nitrogen, and then 1450 g of N, N-dimethylacetamide was obtained. And dissolved. The reaction solution was cooled to 0 ° C., 117 g (1.29 mol) of acrylic acid chloride was slowly added dropwise, and the mixture was further stirred for 2 hours. After completion of the reaction, when 1N hydrochloric acid was added to the reaction solution, crystals were precipitated. The crystals were taken out by filtration. The crystals were dissolved by adding ethyl acetate, washed twice with water, and then the solvent was distilled off under reduced pressure to obtain 175 g (0.66 mol) of a white solid of (PG-h). The yield was 77% based on (PG-g).

(Synthesis example of (PG-j))
2. 25.3 g (130 mmol) of monotetrahydropyranyl-protected hydroquinone (PG-i) obtained by the synthesis method of Patent Literature (Japanese Patent Application Laid-Open No. 2004-262848), and (PG-g) white solid obtained in the previous section 4 g (124 mmol), 4-dimethylaminopyridine 1.5 (12 mmol), and 251 g of chloroform were added. Subsequently, 30.6 g (148 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 63 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. Then, after adding 314 g of 2N hydrochloric acid, the liquid obtained by filtering and removing a solid substance was liquid-separated and the organic layer was obtained. A little solvent was distilled off from the washed organic layer to obtain 100 g of a pale yellow liquid.
To the obtained liquid were added 229 g of tetrahydrofuran and 229 g of 2N hydrochloric acid, and the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature, separated, and the organic layer was taken out. When the taken-out organic layer was charged into normal heptane, a white solid was precipitated, and thus the solid was taken out. The obtained solid was carefully washed with ethanol and dried to obtain 45.7 g of (PG-j). The yield was 80% based on (PG-i).

(Synthesis example of J-3-3)
In a container, 10.7 g (30 mmol) of (PG-j), 4.4 g (24 mmol) of trans-4-butylcyclohexanecarboxylic acid, 0.3 g (2 mmol) of 4-dimethylaminopyridine, and 35 g of chloroform were mixed. , N′-dicyclohexylcarbodiimide (DCC) (5.9 g, 29 mmol) was dissolved in chloroform (9 g), added dropwise at room temperature, and stirred for 48 hours. Then, after adding 44 g of 2N hydrochloric acid, the solid matter was removed by filtration, the filtrate was separated, and the organic layer was taken out. When the solvent of the obtained organic layer was distilled off and added to methanol, a white solid was precipitated, and was separated by filtration to obtain a solid. The obtained solid was carefully washed with methanol. Then, it dried and 3.3g of compounds (J-3-3) which is a white solid was obtained. The yield was 21% based on (PG-j).
In addition, (J-3-3) showed a liquid crystal phase at a temperature of 76 ° C. to 237 ° C. when the temperature was raised.

<Production Example of Compound (J-3-4) of Formula (2)>
The compound (J-3-4) has the following structure.

(Synthesis example of J-3-4)
In a container, 1.5 g (12 mmol) of 4-hydroxyanisole, 5.0 g (12 mmol) of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e), 4-dimethylaminopyridine,. 1 g (1 mmol) and 40 g of chloroform were mixed, and then 3.0 g (14 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 10 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. Then, after adding 49 g of 2N hydrochloric acid, the solid substance was removed by filtration, the filtrate was separated, and the organic layer was taken out. After 49 g of 2N hydrochloric acid was added to the obtained organic layer for separation and washing, the solvent was distilled off and added to methanol to obtain a solid. The obtained solid was carefully washed with methanol. The compound (J-3-1) 4.5g which is a white solid was obtained. The yield was 72% based on 4-hydroxyanisole.
In addition, (J-3-4) showed a liquid crystal phase at a temperature of 78 ° C. to 244 ° C. at the time of temperature increase.

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 film having a thickness of 89 nm was formed.
Subsequently, the surface was subjected to rubbing treatment, and then a coating solution (mixed solution) having the composition shown in Table 1 was applied to the surface subjected to rubbing treatment by spin coating and dried at 135 ° C. for 1 minute.
Subsequently, after being left at 50 ° C. for 1 minute, the film was held at 50 ° C. and irradiated with ultraviolet rays of 1200 mJ / cm ² to produce an optical film having a thickness of 1.16 μm.

In Table 1, the weight% in the table other than the solvent means the weight% of the solid content with the coating solution being 100% by weight. Also,
LC242 (manufactured by BASF, m = m ′ = 4 compound in (III-6) above)). Note that LC242 exhibited a liquid crystal phase at a temperature of 65 ° C. to 125 ° C. when the temperature was increased.
Photopolymerization initiator: Irgacure 907 (manufactured by Ciba Specialty Chemicals),
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone was used.
<Measurement of liquid crystal>
The compounds were collected from the ratios shown in Table 3 from which the photopolymerization initiator, leveling agent and solvent were removed from Table 1. The compounds were well ground in a mortar and mixed uniformly. The solid was heated with a polarizing microscope equipped with a hot stage to obtain a liquid. The liquid was cooled, and liquid crystallinity at 70 ° C. was confirmed. It was confirmed that each composition took a liquid crystal state at 70 ° C.

<Measurement of optical properties>
The front retardation value and tilt angle of the produced optical film were measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments). In addition, since the glass substrate used for the base material has no birefringence, the front retardation value and the tilt angle of the produced optical film can be obtained by measuring the film with the base material with a measuring machine. The obtained optical measurement front phase difference value was measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and [Re (447.3) / Re (546.9)] was calculated. The film thickness derived from the liquid crystal layer of the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation). When the above measurement was performed, the front retardation value of the produced optical film was 119.1 nm, and the tilt angle was 8.7 deg. Further, since the film thickness of the liquid crystal layer was 1.16 μm, the refractive index anisotropy Δn at a wavelength of 546.9 nm showed 0.103 from the formula (6), and [Re (447.3) / Re (546.9)] = 1.060. The results are shown in Table 2.
From these results, it was found that a low wavelength dispersion optical film that was transparent and uniformly oriented at a low tilt was obtained.

(Example 2)
Using the coating liquid of Table 1, an optical film was prepared in the same manner as in Example 1, and an optical film having a thickness of 1.09 μm was prepared.
The optical characteristics of the obtained optical film were measured in the same manner as in Example 1. The results are shown in Table 3.
From these results, it was found that a low wavelength dispersion optical film that was transparent and uniformly oriented at a low tilt was obtained.

(Example 3)
Using the coating liquid of Table 1, an optical film was prepared in the same manner as in Example 1, and an optical film having a thickness of 0.92 μm was prepared.
The optical characteristics of the obtained optical film were measured in the same manner as in Example 1. The results are shown in Table 3.
From these results, it was found that a low wavelength dispersion optical film that was transparent and uniformly oriented at a low tilt was obtained.

Example 4
Using the coating liquid of Table 1, an optical film was prepared in the same manner as in Example 1, and an optical film having a thickness of 1.03 μm was prepared.
The optical characteristics of the obtained optical film were measured in the same manner as in Example 1. The results are shown in Table 3.
From these results, it was found that a low wavelength dispersion optical film that was transparent and uniformly oriented at a low tilt was obtained.

(Comparative Example 1)
Using the coating liquid of Table 1, an optical film was prepared in the same manner as in Example 1, and an optical film having a thickness of 1.00 μm was prepared.
The optical characteristics of the obtained optical film were measured in the same manner as in Example 1. The results are shown in Table 3.
From these, an optical film that was transparent and uniformly oriented at a low tilt was obtained. However, since [Re (447.3) / Re (546.9)] was larger than those of Examples 1 to 4, It was found that the dispersion characteristics are large and the performance is inferior.

  According to the composition of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

It is sectional drawing which shows the polarizing plate of this invention. It is sectional drawing which shows another polarizing plate of this invention. It is sectional drawing which shows the optical member of this invention. It is sectional drawing which shows the liquid crystal panel of this invention. It is sectional drawing which shows the organic electroluminescent panel of this invention.

Explanation of symbols

1, 1 'film 2, 2' polarizing film 3, 3 ', 5 adhesive 4 polarizing plate 6 liquid crystal panel 7 light emitting layer 8 color filter 11, 11' liquid crystal layer 12, 12 'alignment film 13, 13' supporting substrate

Claims (14)

A composition comprising a compound represented by formula (1) and a compound having a substituent represented by formula (2) (however, different from the compound represented by formula (1)).

[Where:
EWG each independently represents a nitro group, a nitrile group or a trifluoromethyl group.
p and q represent the integer of 0-4 each independently. However, 1 ≦ p + q ≦ 8.
R ′ and R ″ each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
s and t each independently represent an integer of 0 to 4. When s and t are 2 to 4, R ′ and R ″ may be the same as or different from each other.
A ³ and A ¹¹ each independently represent a 5- to 20-membered bivalent cyclic hydrocarbon group or a 5- to 20-membered bivalent heterocyclic group. The cyclic hydrocarbon group and 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 substituted.
B ¹ , B ² and B ³ are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ¹ —, —NR ¹ —C (═O) —, —OCH ₂ —, —O—C (═O) —O— or a single bond is represented. Wherein, ^{R 1} represents an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.
B ^{4 is, -CR 1 R 2 -, -} 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 ^1. —, —NR ¹ —C (═O) —, —OCH ₂ —, —NR ¹ —, —CH ₂ O—, —CH═CH—C (═O) —O—, —O—C (═O ) —CH═CH— or a single bond. Here, R < ¹ > and R < ² > represent a C1-C4 alkyl group or a hydrogen atom each independently.
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. The alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
E ² represents a hydrogen atom, a linear or cyclic alkyl group having 1 to 12 carbon atoms, or an unsaturated hydrocarbon group having 2 to 12 carbon atoms. The alkyl group and the unsaturated hydrocarbon group include 1 to 1 carbon atoms. A 4 alkyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom may be substituted.
P is a hydrogen atom or a group represented by formulas (P-1) to (P-5).

Here, R < ¹ > -R < ⁵ > represents a C1-C4 alkyl group or a hydrogen atom each independently.
B ¹¹ and ^{B 12} 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—, —O—C ( = O) -CH = CH- or a single bond. Here, 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.
E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. The alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and may contain —O— or —C (═O) —. Good.
m represents an integer of 1 to 3. When m is 2 or 3, the structural units consisting of A ¹¹ and B ¹¹ may be the same as or different from each other.
P ¹¹ represents a group represented by formulas (P-1) to (P-5). ] A compound having a substituent represented by formula (2) (however, different from a compound represented by formula (1)), a compound represented by formula (2A) and a compound represented by formula (2B) The composition according to claim 1, which is a compound comprising
^{P 11 -E 11 - (B 11} -A 11) m -B 12 -E 12 -P 12 (2A)
^{P 11 -E 11 - (B 11} -A 11) m -B 12 -F 11 (2B)
[Wherein P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² and m represent the same meaning as described above.
E ¹² is the same meaning as ^{E 11,} P ¹² represents the same meaning as ^{P 11.}
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 nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, —COOH, or a halogen atom. ] A ³ has the formula (A-1) ~ The composition according to claim 1 or 2, or a group represented by (A-5).
The composition according to any one of claims 1 to 3, wherein P of the compounds represented by formula (1) and formula (2) is a group represented by formula (P-1).   A film formed from the composition according to any one of claims 1 to 4.   The film obtained by superposing | polymerizing the composition as described in any one of Claims 1-4.   The film according to claim 5 or 6, which functions as a λ / 4 plate having a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the film of 113 to 163 nm.   The film according to claim 5 or 6, which functions as a λ / 2 plate having a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the film of 250 to 300 nm. A polarizing plate comprising a film according to any one of claims 5-8. An optical member comprising the film according to any one of claims 5-8.   The flat panel display which mounts the polarizing plate of Claim 9, or the optical member of Claim 10.   The manufacturing method of the unpolymerized film which apply | coats the solution containing the composition as described in any one of Claims 1-4 to a support base material, and makes it dry.   The manufacturing method of the unpolymerized film which apply | coats the solution containing the composition as described in any one of Claims 1-4 on the orientation film | membrane formed on the support base material, and dries.   The manufacturing method of the film which hardens | cures the unpolymerized film obtained by the manufacturing method of Claim 12 or 13 by superposition | polymerization.