WO2023199630A1

WO2023199630A1 - Polymerizable compound and mixed composition

Info

Publication number: WO2023199630A1
Application number: PCT/JP2023/007522
Authority: WO
Inventors: 真之介吉岡; 憲之飛田; 啓貴中田
Original assignee: 住友化学株式会社
Priority date: 2022-04-11
Filing date: 2023-03-01
Publication date: 2023-10-19
Also published as: JP2023155605A

Abstract

Provided is a polymerizable compound that is capable of lowering the crystallization temperature of a polymerizable liquid crystal compound by being mixed with the polymerizable liquid crystal compound.

Description

Polymerizable compounds, mixed compositions

The present invention relates to a polymerizable compound, a mixed composition containing the polymerizable compound, a retardation film containing a cured product of the mixed composition, an elliptically polarizing plate, an optical display, and a flexible image display device.

Conventionally, one of the characteristics of a retardation film is that it is required to be capable of polarization conversion in the entire wavelength range. It is known that uniform polarization conversion is theoretically possible in the wavelength range shown.
Various polymerizable liquid crystal compounds that can constitute a retardation film exhibiting such reverse wavelength dispersion have been developed (for example, Patent Document 1).

JP 2017-101235 Publication

After forming a coating film by applying a composition obtained by dissolving a polymerizable liquid crystal compound in a solvent as disclosed in Patent Document 1 to a supporting base material, etc., the polymerizable liquid crystal compound contained in the coating film is dissolved in a liquid crystal. A coated type optical film can be obtained by converting to a phase state, drying the coating film to volatilize the solvent, and polymerizing by UV exposure. However, conventional polymerizable liquid crystal compounds often have poor solubility in various solvents due to their molecular structure, and such polymerizable liquid crystal compounds with low solubility are difficult to polymerize after volatilizing the solvent. It may crystallize during this time. Such a phenomenon may cause not only a decrease in film formability but also a decrease in the optical properties of the resulting optical film.

An object of the present invention is to provide a polymerizable compound that can lower the crystallization temperature of a polymerizable liquid crystal compound by mixing it with a polymerizable liquid crystal compound.

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides the following preferred embodiments.
[1] A polymerizable compound represented by the following formula (1).

[In formula (1),
L is selected from the group consisting of a single bond, an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbonyl group, and the hydrogen atom contained in the aliphatic hydrocarbon group is a halogen atom, -R ¹⁰ , -OR ¹⁰ may be substituted with a cyano group or a nitro group, and when L is an aliphatic hydrocarbon group having 2 to 13 carbon atoms, -CH ₂ - contained in the aliphatic hydrocarbon group is - May be substituted with O-, -S-, -CO-O-, -O-CO- or -NH- (however, if multiple -O- and/or -S- exist, these may be substituted with each other) (not adjacent), R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
m represents 0 or 1,
D ¹ and D ² are each independently -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, - Represents OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹² -CO-, or a single bond, and R ¹¹ and R ¹² are each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,
E ¹ , E ² , B ¹ and B ² each independently represent -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO -, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -O-C(=S)-O-, -CO-NR ¹¹ -, - NR ¹² represents -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, and R ¹¹ and R ¹² each independently, Represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms (however, when m is 0, E ¹ and E ² are -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O- CH ₂ -, -CH ₂ -O-, -S-CH ₂ - and -CH ₂ -S-),
G ¹ and G ² each represent a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group,
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; The hydrogen atoms contained in the group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , a cyano group, or a nitro group, and R ¹³ is an alkyl group having 1 to 4 carbon atoms. represents, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, and R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH ₂ - contained in the alkanediyl group is -O- or - May be replaced with CO-,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² is a polymerizable group). ]
[2] The polymerizable compound according to [1] above, which is non-liquid crystalline.
[3] The polymerizable compound according to [1] or [2] above, wherein L in formula (1) is an unsubstituted acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms or a carbonyl group.
[4] A mixed composition of the polymerizable compound according to any one of [1] to [3] above and a polymerizable liquid crystal compound different from the polymerizable compound.
[5] The mixed composition according to [4] above, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by formula (2).

[In formula (2),
Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent,
D ²¹ , D ²² , E ²¹ , E ²² , B ²¹ and B ²² each independently represent -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O -, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO -NR ¹¹ -, -NR ¹² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,
G ²¹ and G ²² each represent a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group,
A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; The hydrogen atoms contained in the group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , a cyano group, or a nitro group, and R ¹³ is an alkyl group having 1 to 4 carbon atoms. represents, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
F ²¹ and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, and R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH ₂ - contained in the alkanediyl group is -O- or - May be replaced with CO-,
P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ²¹ and P ²² is a polymerizable group). ]
[6] The mixed composition has formula (i):
Re1 (450) / Re1 (550) ≧ Re0 (450) / Re0 (550) (i) [In formula (i), Re0 (λ) is the in-plane area at the wavelength λ nm of the cured film formed from the polymerizable liquid crystal compound. Re1 (λ) represents the in-plane retardation value at the wavelength λ nm of the cured film formed from the mixed composition]
The mixed composition according to [4] or [5] above, which satisfies the following.
[7] P ¹ , F ¹ , B ¹ , A ¹ and E ¹ in formula (1) are the same as P ²¹ , F ²¹ , B ²¹ , A ²¹ and E ²¹ in formula (2), respectively. , and P ² , F ² , B ² , A ² and E ² in formula (1) are the same as P ²² , F ²² , B ²² , A ²² and E ²² in formula (2), respectively. , the mixed composition according to [5] or [6] above.
[8] The mixed composition according to any one of [5] to [7] above, wherein Ar in formula (2) is a group represented by any one of formulas (Ar-1) to (Ar-5). thing.

[In formulas (Ar-1) to (Ar-5),
* represents a joint;
Q ¹ represents -S-, -O- or -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
^Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, and R ¹⁵ is a hydrogen atom or a carbon number of 1 to 6 which may have a substituent. represents an alkyl group;
Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group,
Y ² represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. -CH ₂ - may be substituted with -O-, -CO-, -O-CO- or -CO-O-;
Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon atom 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , and Z ¹ and Z ² are bonded to each other to form an aromatic ring or aromatic heterocycle. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ax and Ay are a bond. may form a ring;
Y ³ and Y ⁴ each independently represent the following formula (Y ³ -1):

[In formula (Y ³ -1),
R ^Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ is a fluorine atom, a chlorine atom, Bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethyl A silyl group, a thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently represent -O-, -S-, -CO-, -COO-, - OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO- , -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, a linear or Represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or it may be a group represented by -B ³¹ -F ³¹ -P ³¹ , B ³¹ , F ³¹ and P ³¹ are respectively defined in the same manner as B ²¹ , F ²¹ and P ²¹ in the formula (2), and are the same as B ²¹ , F ²¹ and P ²¹ in the formula (2), respectively. May be present or different;
U ¹ represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group is , may be substituted by one or more of the above substituents ^X3 ;
T ¹ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² - or O-NU ² -, and U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group. (Any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ³¹ -A ³¹ ) _q -B ³² -F ³² - ^P32 , and each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents ^X3 , and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently substituted with -O -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, - NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or - It may be replaced by C≡C-, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the cycloalkyl group or cycloalkenyl group are each independently -O-, -CO-, -COO-, -OCO- or O-CO-O- may be substituted, and E ³¹ , A ³¹ , B ³² , F ³² and P ³² are each E in formula (2). ²¹ , A ²¹ , B ²¹ , F ²¹ and P ²¹ and may be the same or different from E ²¹ , A ²¹ , B ²¹ , F ²¹ and P ²¹ , respectively, and q is 0. It represents an integer of ~4, and if there are multiple E ³¹ and/or A ³¹ , they may be the same or different, and U ¹ and U ² may combine to form a ring. good〕
represents a group selected from ]
[9] Any one of the above [5] to [8], wherein A ²¹ and A ²² in formula (2) are each independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group Mixture composition as described.
[10] The mixed composition according to any one of [5] to [9] above, wherein P ²¹ and P ²² in formula (2) are each an acryloyloxy group.
[11] The area percentage value measured by liquid chromatography of the polymerizable compound represented by formula (1) is the same as that of the polymerizable compound represented by formula (1) and formula (2) contained in the mixed composition. The mixed composition according to any one of [5] to [10] above, which is 1% or more and less than 50% based on the total area value of the polymerizable liquid crystal compound.
[12] The mixed composition according to any one of [4] to [11] above, further comprising a photopolymerization initiator.
[13] The mixed composition according to any one of [4] to [12] above, further comprising an organic solvent.
[14] A retardation film comprising a cured liquid crystal film that is a cured product of the mixed composition according to any one of [4] to [13] above.
[15] The liquid crystal cured film has formula (ii):
0.75≦Re(450)/Re(550)<1.00 (ii)
[In formula (ii), Re (λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured film]
The retardation film according to [14] above, which satisfies the following.
[16] An elliptically polarizing plate comprising the retardation film according to [14] or [15] above.
[17] An optical display comprising the elliptically polarizing plate according to [16].
[18] A flexible image display device including the elliptically polarizing plate according to [16].

According to the present invention, it is possible to provide a polymerizable compound that can lower the crystallization temperature of a polymerizable liquid crystal compound by mixing it with a polymerizable liquid crystal compound.

Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various changes can be made without departing from the spirit of the present invention.

<Polymerizable compound>
The polymerizable compound of the present invention has the formula (1):

(hereinafter also referred to as "polymerizable compound (1)").

In formula (1), L represents a bond or group selected from the group consisting of a single bond, an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbonyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom, -R ¹⁰ , -OR ¹⁰ , a cyano group, or a nitro group, and L is an aliphatic hydrocarbon group having 2 to 13 carbon atoms. In this case, -CH ₂ - contained in the aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-O-, -O-CO- or -NH-. However, when a plurality of -O- and/or -S- are present, they are not adjacent to each other. R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. Hereinafter, a non-cyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms which may be substituted by the above group or into which the above group may be inserted is referred to as a ``non-cyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms which may have a substituent.'' Also called ``cycloaliphatic hydrocarbon group''.

When L in formula (1) is a bond or group selected from the group consisting of a single bond, an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms that may have a substituent, and a carbonyl group; , the solubility of the polymerizable compound (1) in various organic solvents is easily improved. The polymerizable compound (1) having such a structure is a polymerizable liquid crystal compound, especially other polymerizable liquid crystal compounds having a structure similar to that of the polymerizable compound (1) in the molecular structure, such as those described below. When mixed with a polymerizable liquid crystal compound represented by formula (2), etc., it has an excellent effect of lowering the crystallization temperature in the resulting mixed composition. If the crystallization temperature of the mixed composition with a polymerizable liquid crystal compound is high, the processing temperature should be adjusted to prevent crystallization after forming a coating film of the mixed composition and before removing the solvent and polymerizing the liquid crystal. It is necessary to maintain the temperature at a higher temperature than the curing temperature, which may cause problems such as heating affecting the resulting cured liquid crystal film and placing a load on other materials of the optical film, manufacturing equipment, etc. The polymerizable compound (1) of the present invention has an excellent effect of lowering the crystallization temperature of the mixed composition, so the processing temperature can be lowered, and the influence of heating on the optical properties of the liquid crystal cured film can be reduced. This is advantageous in terms of manufacturing efficiency. Such effects tend to be significantly higher than when L in formula (1) is a structure having a cyclic structure such as an alicyclic hydrocarbon group. The reason for this is, but is not limited to, the presence of the alicyclic hydrocarbon group or aromatic hydrocarbon group represented by G ¹ , G ² , A ¹ and A ² in formula (1). Because the group L does not have a rigid cyclic structure, the molecule becomes more flexible and its solubility in organic solvents is easily improved, resulting in a significant reduction in the crystallization temperature when mixed with a polymerizable liquid crystal compound. It is assumed that this can lead to

The aliphatic hydrocarbon group having 1 to 13 carbon atoms represented by L in formula (1) is an acyclic divalent aliphatic hydrocarbon group. The acyclic aliphatic hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. Preferably, a linear saturated hydrocarbon group is more preferable. Specific examples of the acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms which may have a substituent include methanediyl group, ethanediyl group, n-propanediyl group, i-propanediyl group , n-butanediyl group, n-pentanediyl group, n-hexanediyl group, n-heptanediyl group, n-octanediyl group, n-nonanediyl group, n-decanediyl group and other alkanediyl groups having 1 to 13 carbon atoms. It will be done.

The acyclic aliphatic hydrocarbon group represented by L in formula (1) is preferably an alkanediyl group having 1 to 13 carbon atoms which may have a substituent, more preferably an unsubstituted aliphatic hydrocarbon group. is an alkanediyl group having 1 to 13 carbon atoms, more preferably an unsubstituted alkanediyl group having 2 to 10 carbon atoms, and particularly preferably an unsubstituted alkanediyl group having 2 to 8 carbon atoms.

L in formula (1) is preferably an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms or a carbonyl group which may have a substituent, and more preferably an unsubstituted acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms. 13 acyclic aliphatic hydrocarbon group or carbonyl group. When L in formula (1) is a group having the above structure, the solubility of the polymerizable compound (1) in various organic solvents can be more easily reduced, and the crystallization temperature can be lowered when mixed with a polymerizable liquid crystal compound. It is easier to obtain the above-mentioned effects.

In formula (1), m represents the number 0 or 1.

In formula (1), D ¹ and D ² each independently represent -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S ) -O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹² -CO-, or a single bond, and R ¹¹ and R ¹² each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. D ¹ and D ² each have the role of a linking group that connects the group L and the cyclic structure represented by G ¹ or G ² . D ¹ and D ² are each independently -O-, -CO-O-, -O-CO-, -C(=S)-O-, -O-C(=S)-, -CO- It is preferably NR ¹¹ - or -NR ¹² -CO-, and more preferably -O-, -CO-O- or -O-CO-. It is preferable that R ¹¹ and R ¹² are each independently a hydrogen atom, a methyl group, or an ethyl group.
D ¹ and D ² may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable compound (1).

In formula (1), E ¹ , E ² , B ¹ and B ² are each independently -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O -, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO -NR ¹¹ -, -NR ¹² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. However, when m is 0, E ¹ and E ² are -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ - and not -CH ₂ -S-. E ¹ and E ² each have the role of a linking group that connects the group L or the cyclic structure represented by G ¹ or G ² and the cyclic structure represented by A ¹ or A ² . Furthermore, B ¹ and B ² each serve as a linking group between the cyclic structure represented by A ¹ or A ² and the polymerizable group. E ¹ , E ² , B ¹ and B ² each independently represent -O-, -CO-O-, -O-CO-, -C(=S)-O-, -O-C(=S )-, -CO-NR ¹¹ - or -NR ¹² -CO-, and -O-, -CO-O- or -O-CO- are more preferable. It is preferable that R ¹¹ and R ¹² are each independently a hydrogen atom, a methyl group, or an ethyl group.
E ¹ and E ² and B ¹ and B ² may be the same or different from each other, but if they are the same, the ease of industrial production of the polymerizable compound (1), productivity, etc. It is advantageous in this respect.

In formula (1), G ¹ and G ² each represent a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group. The aromatic hydrocarbon groups represented by G ¹ and G ² include divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , a cyano group, or a nitro group, and R ¹³ is an alkyl group having 1 to 4 carbon atoms. and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. Specifically, the divalent aromatic hydrocarbon groups represented by A ¹ and A ² in formula (1) include those exemplified. Among these, G ¹ and G ² are each preferably a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and more preferably a 1,4-cyclohexanediyl group.
G ¹ and G ² may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable compound (1).

In formula (1), A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , a cyano group, or a nitro group, where R ¹³ is the number of carbon atoms It represents an alkyl group of 1 to 4, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms represented by A ¹ and A ² include alicyclic hydrocarbon groups represented by formulas (a-1) to (a-4); A 5-membered or 6-membered alicyclic hydrocarbon group is preferred.

Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A ¹ and A ² include 6 to 20 carbon atoms represented by formulas (a-5) to (a-12). aromatic hydrocarbon groups.

Hydrogen atoms contained in the groups represented by formulas (a-1) to (a-12) above include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group, and tert-butyl group; methoxy group , an alkoxy group having 1 to 4 carbon atoms such as an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; a nitro group; substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc. may have been done.

A ¹ and A ² are preferably a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and more preferably a 1,4-phenylene group. In particular, when m is 1, it is preferable that G ¹ and G ² are each a 1,4-cyclohexanediyl group, and A ¹ and A ² are each a 1,4-phenylene group.
A ¹ and A ² may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable compound (1).

In formula (1), F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with fluorine. May be substituted with an atom. Furthermore, -CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-. F ¹ and F ² are each independently preferably an alkanediyl group having 3 to 10 carbon atoms, -(CF ₂ ) ₄ -, -(CF ₂ ) ₆ -, -(CF ₂ ) ₈ -, and A 4 or 6 alkanediyl group [-(CH ₂ ) ₄ - or -(CH ₂ ) ₆ -] is more preferred.
E ¹ and E ² may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable compound (1).

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. At least one of P ¹ and P ² is a polymerizable group, and the fact that both P ¹ and P ² are polymerizable groups improves the film hardness of a liquid crystal cured film obtained using the polymerizable compound. Preferable from this point of view.

The polymerizable group may be any reactive group that can polymerize the polymerizable compound (1). Specifically, vinyl group, vinyloxy group, styryl group, p-(2-phenylethenyl) phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group. Examples include a N-alkylamino group having 1 to 4 carbon atoms, an amino group, an oxiranyl group, an oxetanyl group, a formyl group, an isocyanato group, an isothiocyanato group, and the like. Further, the polymerizable group may include an ether bond or an ester bond that connects the above-exemplified group and F ¹ or F ² . As P ¹ and P ² , radically polymerizable groups or cationically polymerizable groups suitable for photopolymerization are preferred, and acryloyloxy or methacryloyloxy groups are particularly preferred because they are easy to handle and manufacture. Preferably, an acryloyloxy group is more preferable.

It is preferable that the polymerizable compound (1) is non-liquid crystalline. When the polymerizable compound (1) is a non-liquid crystal compound, when mixed with the polymerizable liquid crystal compound, it is less likely to affect the liquid crystallinity of the polymerizable liquid crystal compound, making it easier to obtain an optical film with excellent optical properties.

In formula (1), *-(D ¹ -G ¹ )m-E ¹ -A ¹ -B ¹ ^{-F 1} -P ¹ and *-(D ² -G ² )m-E ² -A Specific examples of ² -B ² -F ² -P ² include structures represented by formulas (R-1) to (R-106). In the formula, * represents a bond to the group L, and n represents an integer of 1 to 12. Note that the cyclohexane ring may be in the trans or cis form, but is preferably in the trans form. The polymerizable compound (1) may have a symmetrical structure or an asymmetrical structure around the group L.

The polymerizable compound (1) is manufactured by Methoden der Organic Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, Known organic synthesis reactions described in the New Experimental Chemistry Course (e.g. condensation reaction, esterification reaction, Williamson reaction) , Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, Aldol reaction etc.) can be manufactured by appropriately combining them depending on the structure.

For example, L in formula (1) is an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms, m is 0, E ¹ and E ² are both -CO-O-, and A ¹ A polymerizable compound (1) in which A ² , B ¹ and B ² , F ¹ and F ² , and P ¹ and P ² are the same, respectively, is a compound represented by formula (1-1) (hereinafter referred to as " It can be produced by subjecting a compound represented by formula (1-2) (hereinafter also referred to as "compound (1-2)") to an esterification reaction. In addition, P, F, B, and A in formula (1-1) are respectively P ¹ and P ² , F ¹ and F ² , B ¹ and B ² , and A ¹ and A ² in formula (1). Same as specified. Further, L in formula (1-2) is the same as defined as L in formula (1). P, F, B, A and L are determined depending on the desired polymerizable compound (1).

The esterification reaction between compound (1-1) and compound (1-2) is preferably carried out in the presence of a condensing agent. By performing the esterification reaction in the presence of a condensing agent, the esterification reaction can be performed efficiently and quickly.

As a condensing agent, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimidemeth-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl- Carbodiimide compounds such as 3-(3-dimethylaminopropyl)carbodiimide hydrochloride (commercially available as water-soluble carbodiimide: WSC), bis(2,6-diisopropylphenyl)carbodiimide, and bis(trimethylsilyl)carbodiimide, 2-methyl-6- Nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole , 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl- O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxysuccinimide, O-(6-chlorobenzotriazole-1- yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexa Fluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1 Examples include -methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, and trichloroacetic acid pentachlorophenyl ester.

The condensing agent is preferably a carbodiimide compound, 2,2'-carbonylbis-1H-imidazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris( dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N, N,N',N'-tetramethyluronium hexafluorophosphate, 2-chloro-1,3-dimethylimidazolinium chloride, and 2-chloro-1-methylpyridinium iodide, and from the economic point of view More preferred are carbodiimide compounds.

Among carbodiimide compounds, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3 -dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide) and bis(2,6-diisopropylphenyl)carbodiimide are preferred.

The amount of the condensing agent used is usually 0.8 to 1.2 mol per 1 mol of compound (1-1).

In the esterification reaction, additives such as N-hydroxysuccinimide, benzotriazole, paranitrophenol, and 3,5-dibutyl-4-hydroxytoluene may be added. The amount of these additives used is preferably 0.01 to 0.1 mol per 1 mol of compound (1-1).

Additionally, the esterification reaction may be performed in the presence of a catalyst. Examples of the catalyst include N,N-dimethylaminopyridine, N,N-dimethylaniline, dimethylammonium pentafluorobenzenesulfonate, and the like. Among them, N,N-dimethylaminopyridine and N,N-dimethylaniline are preferred, and N,N-dimethylaminopyridine is more preferred. When a catalyst is used, the amount used is preferably 0.01 to 0.1 mol per 1 mol of compound (1-1).

The esterification reaction is usually carried out in a solvent. Solvents include ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; aromatic solvents such as toluene, xylene, benzene or chlorobenzene. group hydrocarbon solvents; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; ester solvents such as ethyl lactate; halogenated hydrocarbon solvents such as chloroform and dichloromethane; dimethyl sulfoxide, N-methyl-2- Examples include aprotic polar solvents such as pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and hexamethylphosphoric triamide. These solvents may be used alone or in combination.

The solvent is preferably an aromatic hydrocarbon solvent such as toluene, xylene, benzene or chlorobenzene; an ethereal solvent such as tetrahydrofuran or dimethoxyethane; or a halogenated hydrocarbon solvent such as chloroform or dichloromethane, more preferably chloroform or dichloromethane. A halogenated hydrocarbon solvent such as dichloromethane.

The amount of compound (1-2) used in the reaction is preferably 0.25 to 0.6 mol, more preferably 0.3 to 0.5 mol, per 1 mol of compound (1-1). More preferably, it is 0.4 to 0.5 mol. When the amount of compound (1-2) used is at least the above lower limit, the yield of polymerizable compound (1) is good. In addition, when the amount of compound (1-2) used is below the above upper limit, post-treatment work for removing unreacted compound (1-1) can be easily performed, and production can be carried out with high productivity. obtain.

The amount of the solvent to be used is not particularly limited, but is preferably 0.5 to 50 parts by mass based on 1 part by mass of compound (1-1) and compound (1-2). The amount is more preferably 1 to 30 parts by weight, and even more preferably 1 to 20 parts by weight.

The conditions for the esterification reaction may be determined as appropriate. From the viewpoint of reaction yield and productivity, the temperature of the esterification reaction is preferably -20 to 100°C, more preferably -10 to 50°C, and even more preferably -5 to 30°C. Further, the time for the esterification reaction is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and even more preferably 1 to 24 hours. By performing the esterification reaction in the above temperature range and time range, the reaction yield is likely to be improved.

Compound (1-1) and compound (1-2) used in the above reaction can be produced by appropriately combining various known organic synthesis reactions described above depending on their structures.

Further, for example, L in formula (1) is a carbonyl group, m is 0, E ¹ and E ² are both -O-, A ¹ and A ² , B ¹ and B ² , F ¹ The polymerizable compound (1) in which F ² and P ¹ and P ² are the same can be produced by reacting the compound (1-1) with, for example, triphosgene in the presence of a base and a solvent. .

Examples of the base used in the reaction include amines such as trimethylamine, triethylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, and N,N-diethylaniline, pyridine such as pyridine, and N,N-dimethylaminopyridine. etc. Among these, N,N-diisopropylethylamine, triethylamine, and pyridine are preferred from the viewpoint of easily promoting the reaction.

The amount of base used in the reaction is preferably 1.0 to 1.5 mol per 1 mol of compound (1-1).

The amount of triphosgene used in the reaction is preferably 0.1 to 0.5 mol, more preferably 0.1 to 0.4 mol, and even more preferably 0.1 mol to 1 mol of compound (1-1). The amount is 1 to 0.3 mol. When the amount of triphosgene used is at least the above lower limit, the yield of the polymerizable compound (1) is good. Further, when the amount of triphosgene used is below the above upper limit, post-treatment work for removing unreacted compound (1-1) can be easily performed, and production can be carried out with good productivity.

Examples of the solvent in the above reaction include those that can be used in the esterification reaction of compound (1-1) and compound (1-2). The amount of the solvent used is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 1 part by weight of compound (1-1) and triphosgene. parts, more preferably 1 to 10 parts by mass.

The conditions for the reaction between compound (1-1) and triphosgene may be determined as appropriate. From the viewpoint of reaction yield and productivity, the reaction temperature is, for example, -20 to 60°C, preferably -20 to 40°C. Further, from the viewpoint of reaction yield and productivity, the reaction time may be, for example, 1 minute to 72 hours, preferably 1 to 48 hours, and more preferably 1 to 24 hours.

After each reaction by the above method is completed, treatments and operations that can be adopted in organic synthetic chemistry, such as post-treatments such as filtration, neutralization, extraction, and water washing, and isolation treatments such as distillation and crystallization, may be carried out as necessary. The desired compound can be isolated by applying

The structure of the obtained compound can be identified by measurements such as NMR spectrum, IR spectrum, mass spectrum, elemental analysis, etc.

<Mixed composition>
When the polymerizable compound (1) is added to a composition containing a polymerizable liquid crystal compound, it has an excellent effect of lowering the crystallization temperature in the resulting mixed composition. Therefore, the present invention is directed to a mixed composition of a polymerizable compound (1) and a polymerizable liquid crystal compound different from the polymerizable compound (1).

The above effects of the polymerizable compound (1) tend to become particularly noticeable when mixed with a polymerizable liquid crystal compound having a structure similar to that of the polymerizable compound (1) in its molecular structure. In the mixed composition of the present invention, the polymerizable compound (1) can be used in combination with various polymerizable liquid crystal compounds. It is preferable to combine it with a liquid crystal compound. As such a polymerizable liquid crystal compound, for example, formula (2):

(hereinafter also referred to as "polymerizable liquid crystal compound (2)"), and the mixed composition of the present invention includes polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2). It is preferable to include.

In formula (2), D ²¹ , D ²² , E ²¹ , E ²² , B ²¹ and B ²² each independently represent -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S -, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S) -O-, -CO-NR ¹¹ -, -NR ¹² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; , R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. D ²¹ and D ²² each have the role of a linking group that connects the group Ar and the cyclic structure represented by G ¹ or G ² . E ²¹ and E ²² each serve as a linking group that connects the cyclic structure represented by G ²¹ or G ²² and the cyclic structure represented by A ²¹ or A ²² . Furthermore, B ²¹ and B ²² each serve as a linking group between the cyclic structure represented by A ²¹ or A ²² and the polymerizable group.

D ²¹ , D ²² , E ²¹ , E ²² , B ²¹ and B ²² each independently represent -O-, -CO-O-, -O-CO-, -C(=S)-O-, - It is preferably OC(=S)-, -CO-NR ¹¹ - or -NR ¹² -CO-, and more preferably -O-, -CO-O- or -O-CO-. It is preferable that R ¹¹ and R ¹² are each independently a hydrogen atom, a methyl group, or an ethyl group.
D ²¹ and D ²² , E ²¹ and E ²² , and B ²¹ and B ²² may be the same or different from each other, but if they are the same, industrial production of the polymerizable liquid crystal compound (2) It is advantageous in terms of ease of use and productivity.

In formula (2), G ²¹ and G ²² each represent a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon groups represented by G ²¹ and G ²² include those similar to those exemplified as the aromatic hydrocarbon groups represented by G ¹ and G ² constituting the polymerizable compound (1). It will be done. Among these, G ²¹ and G ²² are each preferably a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and from the viewpoint of optical properties of the obtained liquid crystal cured film, it is a 1,4-cyclohexanediyl group. is more preferable.
^G21 and ^G22 may be the same or different from each other, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2). .

In formula (2), A ²¹ and A ²² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , a cyano group, or a nitro group, where R ¹³ is the number of carbon atoms It represents an alkyl group of 1 to 4, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. The divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A ²¹ and A ²² are those constituting the polymerizable compound (1). Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A ¹ and A ² include those similar to those exemplified. It will be done. Among these, 1,4-cyclohexanediyl group or 1,4-phenylene group is preferable as A ²¹ and A ²² , and 1,4-phenylene group is more preferable from the viewpoint of optical properties of the resulting cured liquid crystal film. In particular, it is preferred that G ²¹ and G ²² are each a 1,4-cyclohexanediyl group, and A ²¹ and A ²² are each a 1,4-phenylene group.
^A21 and ^A22 may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2). .

In formula (2), F ²¹ and F ²² each independently represent an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁴ or a halogen atom, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with fluorine. May be substituted with an atom. Furthermore, -CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-. The alkanediyl group having 1 to 12 carbon atoms represented by F ²¹ and F ²² is exemplified as the alkanediyl group having 1 to 12 carbon atoms represented by F ¹ and F ² constituting the polymerizable compound (1). Examples include those similar to those mentioned above. Among these, F ²¹ and F ²² are each independently preferably an alkanediyl group having 3 to 10 carbon atoms, -(CF ₂ ) ₄ -, -(CF ₂ ) ₆ -, -(CF ₂ ) ₈ -, More preferred is an alkanediyl group having 4 or 6 carbon atoms [-(CH ₂ ) ₄ -- or --(CH ₂ ) ₆ --].
E ²¹ and E ²² may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2).

P ²¹ and P ²² each independently represent a hydrogen atom or a polymerizable group. At least one of P ²¹ and P ²² is a polymerizable group, and the fact that both P ²¹ and P ²² are polymerizable groups improves the film hardness of a liquid crystal cured film obtained using the polymerizable liquid crystal compound. preferred from the viewpoint of Examples of the polymerizable groups represented by P ²¹ and P ²² include those similar to those exemplified as the polymerizable groups represented by P ¹ and P ² constituting the polymerizable compound (1).
Among these, a radically polymerizable group or a cationically polymerizable group is preferable, and an acryloyloxy group or a methacryloyloxy group is preferable, and an acryloyloxy group is more preferable because they are particularly easy to handle and manufacture.

In formula (2), Ar may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent (hereinafter, these will be collectively referred to as "a substituent"). (Also referred to as "an optional divalent aromatic group"). In the present invention, the divalent aromatic hydrocarbon group which may have a substituent means a divalent linking group containing at least one aromatic hydrocarbon ring, and which may have a substituent. A good divalent aromatic heterocyclic group means a divalent linking group containing at least one aromatic heterocycle. The aromatic hydrocarbon ring and aromatic heterocycle referred to herein are those in which the number of π electrons in the ring structure is [4n+2] (n represents an integer) according to Huckel's rule (in the case of an aromatic heterocycle, (Satisfies Huckel's rule, including non-covalently bonded electron pairs on heteroatoms such as -N= and -S-). Ar may contain one aromatic hydrocarbon ring or aromatic heterocycle, or may contain two or more. When containing one aromatic hydrocarbon ring or aromatic heterocycle, Ar may be a divalent aromatic hydrocarbon group which may have a substituent, or may have a substituent. It may also be a divalent aromatic heterocyclic group. If it contains two or more aromatic hydrocarbon rings or aromatic heterocycles, it may contain only aromatic hydrocarbon rings or only aromatic heterocycles, or it may contain only aromatic hydrocarbon rings and aromatic heterocycles. may contain one or more of each. Two or more aromatic hydrocarbon rings and/or aromatic heterocycles may be bonded to each other via a single bond or a divalent bonding group such as -CO-O- or -O-.

Examples of the aromatic hydrocarbon ring that can be included in Ar include a benzene ring, a naphthalene ring, an anthracene ring, and the like, with benzene rings and naphthalene rings being preferred. Examples of aromatic heterocycles include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring, Examples include a thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthroline ring. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

Among these, Ar preferably has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and preferably has a thiazole ring, benzothiazole ring, or benzofuran ring. More preferably, it has a benzothiazole ring. Note that when Ar has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, the aromatic heterocycle is D ²¹ or A substituent of the divalent linking group that may be directly bonded to D ²² and constitute the main chain of the polymerizable liquid crystal compound (2), and that is directly bonded to D ²¹ or D ²² However, it is preferable that the entire Ar group containing the aromatic heterocycle is sterically arranged in a direction substantially orthogonal to the molecular orientation direction.

In formula (2), the total number N _π of π electrons contained in the divalent aromatic group optionally having a substituent represented by Ar is preferably 8 or more, more preferably 12 or more. , particularly preferably 16 or more, particularly preferably 20 or more. Further, it is preferably 36 or less, more preferably 32 or less, even more preferably 30 or less, particularly preferably 26 or less, particularly preferably 24 or less.

Examples of the divalent aromatic group which may have a substituent represented by Ar in formula (2) include groups represented by the following formulas (Ar-1) to (Ar-5). It will be done. In the polymerizable liquid crystal compound represented by formula (2), these groups give a bulky molecular structure in the direction crossing the long axis direction, and the absorption wavelength in the short axis direction becomes a long wavelength, resulting in an oriented liquid crystal. They have a common feature in that the phase difference generated by the molecules has reverse wavelength dispersion.

* in formulas (Ar-1) to (Ar-5) represents a bond with D ²¹ or D ²² in formula (2).

In formula (Ar-1), Q ¹ represents -S-, -O- or -NR ¹⁵ -, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. . In formulas (Ar-3) and (Ar-4), Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

In formula (Ar-2), W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, and R ¹⁵ has a hydrogen atom or a substituent. represents an alkyl group having 1 to 6 carbon atoms.

In formula (Ar-1), Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group. In formula (Ar-2), Y ² represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent. Here, the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and -CH ₂ - contained in the alkyl group is -O-, -CO-, -O-CO- or - May be substituted with CO-O-.

In formulas (Ar-1) to (Ar-5), Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 3 to 20 carbon atoms; 20 alicyclic hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² may be combined with each other to form an aromatic ring or an aromatic heterocycle. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon number having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. It represents 2 to 30 organic groups, and Ax and Ay may be combined to form a ring.

In formula (Ar-1), Y ¹ is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and has 6 to 6 carbon atoms and may have a substituent. A 12 aromatic hydrocarbon group or an aromatic heterocyclic group having 3 to 12 carbon atoms is more preferred. The aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent is preferably an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. As used herein, "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and a fused aromatic hydrocarbon group formed by condensing two or more aromatic rings. Examples include aromatic hydrocarbon groups formed by bonding a hydrocarbon group and two or more aromatic rings. "Polycyclic aromatic heterocyclic group" means an aromatic heterocyclic group having at least one heteroaromatic ring and at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring. , an aromatic heterocyclic group formed by the condensation of one or more aromatic heterocycles and one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and at least one heteroaromatic ring and aromatic Examples include an aromatic heterocyclic group formed by bonding a ring and at least one ring selected from the group consisting of a heteroaromatic ring.

Examples of substituents that the aromatic hydrocarbon group or aromatic heterocyclic group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, and an alkylsulfinyl group having 1 to 6 carbon atoms. group, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, N-alkylamino group, N,N-dialkylamino group having 2 to 8 carbon atoms, sulfamoyl group, N-alkylsulfamoyl group having 1 to 6 carbon atoms and N,N-dialkylsulfa having 2 to 12 carbon atoms A moyl group is mentioned.

Examples of Y ¹ include groups represented by the following formulas (Y ¹ -1) to (Y ¹ -7).

In formulas (Y ¹ -1) to (Y ¹ -7), the * part represents a connecting part.

In formulas (Y ¹ -1) to (Y ¹ -7), Z ⁴ each independently represents a halogen atom or an organic group having 1 to 20 carbon atoms, such as a fluorine atom, a chlorine atom, a bromine atom , methyl group, ethyl group, isopropyl group, sec-butyl group, cyano group, nitro group, sulfone group, nitroxydo group, carboxyl group, trifluoromethyl group, methoxy group, thiomethyl group, N,N-dimethylamino group, N - Methylamino group is preferred, halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, cyano group, nitro group, trifluoromethyl group is more preferred, methyl group, ethyl group, isopropyl group, sec-butyl group A pentyl group and a hexyl group are particularly preferred.

In formulas (Y ¹ -1) to (Y ¹ -7), V ¹ and V ² are each independently -CO-, -S-, -NR ¹⁷ -, -O-, -Se- or - It represents SO ₂ -, and is preferably -S-, -NR ¹⁷ - or -O-. R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In formulas (Y ¹ -1) to (Y ¹ -7), W ³ to W ⁷ each independently represent -C= or -N=.

In formulas (Y ¹ -1) to (Y ¹ -7), at least one of V ¹ , V ² and W ³ to W ⁷ preferably represents a group containing S, N or O.

In formulas (Y ¹ -1) to (Y ¹ -7), a each independently represents an integer of 0 to 3, preferably 0 or 1. b each independently represents an integer of 0 to 2, preferably 0.

Any group represented by formula (Y ¹ -1) to formula (Y ¹ -7) is any group represented by formula (Y ¹ -8) to formula (Y ¹ -13) below. A group represented by formula (Y 1 -8) is preferable, and a group represented by formula (Y ¹ -8) is more preferable. Note that the * part represents a connecting part.

In formulas (Y ¹ -8) to (Y ¹ -13), Z ⁴ , a, b, V ¹ , V ² and W ³ are the same as those in (Y ¹ -1) to (Y ¹ -7) It has the same meaning as Z ⁴ , a, b, V ¹ , V ² and W ³ .

Specific examples of Y ¹ include groups represented by formulas (ar-1) to (ar-840) described in JP-A-2019-003177. Among these, groups represented by the following formulas are preferred.

In one embodiment of the present invention, the group represented by formula (Ar-1) specifically includes groups represented by the following formulas (Ar ¹ -1) to (Ar ¹ -126). The * part in the formula represents a connecting part with D ²¹ or D ²² in formula (2).

In one embodiment of the present invention, the group represented by formula (Ar-2) specifically includes groups represented by the following formulas (Ar ² -1) to (Ar ² -13). The * part in the formula represents a connecting part with D ²¹ or D ²² in formula (2).

In one embodiment of the present invention, the group represented by formula (Ar-3) specifically includes groups represented by the following formulas (Ar ³ -1) to (Ar ³ -23). The * part in the formula represents a connecting part with D ²¹ or D ²² in formula (2).

In addition to the groups specifically exemplified above, the groups represented by formulas (Ar-1) to (Ar-4) include, for example, JP-A No. 2011-207765, JP-A No. 2008-107767, WO2014/ The groups described in JP 010325 and the like may also be used.

In formula (Ar-5), Y ³ and Y ⁴ each independently represent the following formula (Y ³ -1):

selected from the groups represented by

In formula (Y ³ -1), R ^Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may be substituted with one or more substituents ^X3 .

Substituent X ³ is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group , diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently -O-, - S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH= CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- represents a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or -B ³¹ -F ³¹ -P ³¹ B ³¹ , F ³¹ and P ³¹ are each defined similarly to B ²¹ , F 21 and P 21 in formula (2) above, and each of B 31 , F ³¹ and P ³¹ in formula (2) is may be the same as or different from B ²¹ , F ²¹ and P ²¹ .

The substituent X ³ is preferably a fluorine atom, a chlorine atom, -CF ₃ , -OCF ₃ or a cyano group. R ^Y1 is preferably an alkyl group having 1 to 6 carbon atoms that is unsubstituted or substituted with a hydrogen atom or one or more fluorine atoms, and more preferably a hydrogen atom.

In formula (Y ³ -1), U ¹ represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and U ¹ has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , is an organic group having 2 to 30 carbon atoms. The aromatic hydrocarbon group may be substituted with one or more of the above substituents ^X3 .

U ¹ is preferably an organic group having an aromatic heterocycle in which one or more carbon atoms are substituted with a hetero atom, from the viewpoint of good wavelength dispersion. U ¹ is more preferably an organic group having an aromatic heterocycle that is a condensed ring of a 5-membered ring and a 6-membered ring, since it has good wavelength dispersion and exhibits high birefringence.

Specifically, U ¹ preferably has a group represented by the following formula. In addition, in the following formula, these groups have a bond with T ¹ at an arbitrary position.

In formula (Y ³ -1), T ¹ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO- NU ² -, -OCO-NU ² - or O-NU ² -, where U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. A cycloalkenyl group, an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ³¹ -A ³¹ ) _q -B ³² -F ³² -P ³² . Each of the alkyl group, cycloalkyl group, cycloalkenyl group, and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents ^X3 , and the alkyl group is the cycloalkyl group. Alternatively, it may be substituted with a cycloalkenyl group. One -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO- , -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH -OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and the cycloalkyl group or cyclo One -CH ₂ - or two or more non-adjacent -CH ₂ -s in an alkenyl group are each independently -O-, -CO-, -COO-, -OCO- or O-CO-O - may be replaced. E ³¹ , A ³¹ , B ³² , F ³² and P ³² are defined similarly to E ²¹ , A ²¹ , B ²¹ , F ²¹ and P ²¹ in formula (2), respectively, and E ²¹ , A ²¹ , B ²¹ , F ²¹ and P ²¹ may be the same or different, q represents an integer from 0 to 4, and when there are multiple E ³¹ and/or A ³¹ , each may be the same or different. may also be different.

T ¹ is preferably -O-, -S-, -N=CU ² - or -NU ² - from the viewpoint of good birefringence and easy synthesis, improving wavelength dispersion and birefringence. -O-, -S-, or -NU ² - is more preferable from the viewpoint of easy conversion.

U ² may be substituted by one or more of the above substituents X ³ , and one -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently represent -O-, an alkyl group or alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, which may be replaced with -CO-, -COO-, -OCO- or -O-CO-O-, or It is preferably a cycloalkenyl group having 3 to 12 carbon atoms, or the above-mentioned alkyl group or alkenyl group which may be substituted with the cycloalkyl group, cycloalkenyl group, or aryl group.

Among them, in U ² , from the viewpoint of birefringence and solvent solubility, the hydrogen atom may be substituted with a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s are each independently More preferably, it is a linear alkyl group having 1 to 20 carbon atoms which may be replaced with -O-, -CO-, -COO- or -OCO-.

U ¹ and U ² may be combined to form a ring. In that case, examples include a cyclic group represented by -NU ¹ U ² or a cyclic group represented by -N=CU ¹ U ² .

Y ³ and Y ⁴ are each selected from the following formulas (Y ^3' -1) to (Y ^3' -47) from the viewpoint of easy availability of raw materials, good solubility, and high birefringence. It is particularly preferred to represent a group.

From the viewpoint of improving the orientation of the polymerizable liquid crystal compound (2) and facilitating industrial production and improving productivity, the group represented by formula (Ar-5) is specifically: The following groups may be mentioned. * in (Ar ⁵ -1) to (Ar ⁵ -20) below represents a bond with D ²¹ or D ²² in formula (2).

Among formulas (Ar-1) to (Ar-5), formulas (Ar-1), (Ar-2), and (Ar-5) are preferred, and formulas (Ar-1) and (Ar-5) are more preferred. Preferably, formula (Ar-1) is more preferable.

*-D ²¹ -G ²¹ -E ²¹ -A ²¹ -B ²¹ -F ²¹ -P ²¹ and *-D ²² -G 22 -E ²² -A ²² -B ²² ^-F in formula (2) Specific examples of ²² -P ²² include *-(D ¹ -G ¹ )m-E ¹ -A ¹ -B ¹ -F ¹ -P ¹ and *-(D ² -G ² )m-E ² -A ² -B ² -F ² -P Structures represented by formulas (R-46) to (R-106) exemplified as the ^second part can be mentioned.

In the present invention, examples of the polymerizable liquid crystal compound represented by formula (2) include compounds described in JP-A No. 2019-003177, JP-A No. 2019-073496, and the like.

When the mixed composition contains the polymerizable compound (1) and the polymerizable liquid crystal compound (2) having a molecular structure similar to that of the polymerizable compound (1), the crystallization temperature of the liquid crystal composition tends to decrease. In one embodiment of the present invention, as a combination of the polymerizable compound (1) and the polymerizable liquid crystal compound (2) whose molecular structures are similar or similar to each other, P ¹ , F ¹ , B ¹ in formula (1) , A ¹ and E ¹ are respectively the same as P ²¹ , F ²¹ , B ²¹ , A ²¹ and E ²¹ in formula (2), and P ² , F ² , B ² , A in formula (1) ² and E ² are preferably the same as P ²² , F ²² , B ²² , A ²² and E ²² in formula (2), respectively, and -(D ¹ -G ¹ ) _m - in formula (1) A moiety represented by E ¹ -A ¹ -B ¹ -F ¹ -P ¹ and P ² -F ² -B ² -A ² -E ² -(G ² -D ² ) _m -, and formula (2) -D ²¹ -G ²¹ -E ² in
¹ -A ²¹ -B ²¹ -F ²¹ -P ²¹ and P ²² -F ²² -B ²² -A ²² -E ²² -G ²² -D ²² - have a common or identical molecular structure It is more preferable to include a combination of the polymerizable compound (1) and the polymerizable liquid crystal compound (2). In such a mixed composition, the crystallization temperature of the mixed composition can be easily lowered effectively, and there is no need to raise the processing temperature to a high temperature in order to prevent crystallization of the polymerizable compound during film formation. Therefore, an optical film can be obtained from the polymerizable liquid crystal compound (2) at a lower processing temperature, which is advantageous in terms of reducing the influence of heating on the optical properties of the optical film and improving production efficiency. Note that the mixed composition may contain only one type of each of the polymerizable compound (1) and the polymerizable liquid crystal compound (2), or may contain multiple types of the polymerizable compound (1). It is preferable that at least one of them has a structure similar to, similar to, or the same as at least one of the polymerizable liquid crystal compounds (2).

The content of the polymerizable compound (1) and the polymerizable liquid crystal compound (2) in the mixed composition of the present invention depends on the type of the polymerizable compound (1) and/or the polymerizable liquid crystal compound (2), etc. The amount of polymerizable compound (1) relative to the total peak area of polymerizable compound (1) and polymerizable liquid crystal compound (2) measured by liquid chromatography may be determined as appropriate within the range in which the effects of the present invention can be obtained. The peak area ratio (hereinafter also referred to as "area percentage value") is preferably 1% or more and less than 50%. It is more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 8% by mass or more, and may be, for example, 10% by mass or more. When the content of the polymerizable compound (1) is at least the above lower limit, the crystallization temperature in the mixed composition is likely to be sufficiently lowered, and alignment defects are less likely to occur when producing a cured liquid crystal film. Further, the content of the polymerizable compound (1) is more preferably 45% by mass or less, still more preferably 40% by mass or less. When the content of the polymerizable compound (1) is below the above upper limit value, it is possible to maintain a good alignment state of liquid crystal when producing a cured liquid crystal film, and thus an optical film with excellent optical properties can be obtained. . Even when the polymerizable compound (1) of the present invention is blended in a relatively large amount with respect to a polymerizable liquid crystal compound, it hardly affects the alignment of liquid crystals, suppresses the occurrence of alignment defects, and produces an optical film with excellent optical properties. can be obtained.
In addition, when multiple compounds corresponding to the polymerizable compound (1) and/or the polymerizable liquid crystal compound (2) are included, the area percentage value of the polymerizable compound (1) is the total polymerizable compound (1) and the total polymerizable compound (1). It is calculated based on the total peak area with polymerizable liquid crystal compound (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, it can be measured and calculated by the method described in the Examples below.

By containing the polymerizable compound (1) and the polymerizable liquid crystal compound (2) in combination, the mixed composition of the present invention can be used when the polymerizable liquid crystal compound (2) is used alone or when the polymerizable liquid crystal compound (2) in formula (1) is used alone. The crystallization temperature can be significantly lowered compared to the case where a polymerizable compound in which the group L has a cyclic structure is used.
For example, the crystallization temperature of the mixed composition of the polymerizable compound (1) and the polymerizable liquid crystal compound (2) constituting the mixed composition of the present invention is preferably 91°C or lower, more preferably 90°C or lower, The temperature is more preferably 88°C or lower, particularly preferably 86°C or lower. Furthermore, when the polymerizable compound (1) of the present invention is used in combination with the polymerizable liquid crystal compound (2), the crystallization temperature is preferably lowered compared to when the polymerizable liquid crystal compound (2) is used alone. can be lowered by 3°C or more, more preferably 5°C or more, even more preferably 7°C or more, particularly preferably 8°C or more.
In addition, in this invention, the crystallization temperature of a mixed composition can be measured by the method described in the Example mentioned later. The crystallization temperature of a mixed composition containing two or more types of polymerizable compounds is measured using a mixed composition having the same composition as the polymerizable compounds constituting the mixed composition.

The mixed composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (2). Examples of such polymerizable liquid crystal compounds include, for example, 3.2 Non-chiral rod-like compounds in Chapter 3, Molecular Structure and Liquid Crystal Properties, of Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000). Liquid crystal molecules, 3.3 Compounds described in chiral rod-like liquid crystal molecules, compounds described in JP 2010-31223, JP 2011-207765, Japanese Patent No. 5962760, etc. Examples include polymerizable liquid crystal compounds that can exhibit reverse wavelength dispersion when formed into a cured film, and polymerizable liquid crystal compounds that can exhibit forward wavelength dispersion when formed into a cured film.

In the mixed composition of the present invention, a liquid crystal compound other than the polymerizable liquid crystal compound (2) may be used in combination with the polymerizable compound (1) as long as the effects of the present invention are obtained, but as the polymerizable liquid crystal compound, It is preferable that at least one kind of polymerizable liquid crystal compound (2) is included. In this case, the content of polymerizable compounds other than polymerizable compound (1) and polymerizable liquid crystal compound (2) is 20 parts by mass based on a total of 100 parts by mass of polymerizable compound (1) and polymerizable liquid crystal compound (2). It is preferably at most parts by mass, more preferably at most 10 parts by mass, even more preferably at most 5 parts by mass. In particular, if the content of a liquid crystal compound whose molecular structure is significantly different from that of the polymerizable compound (1) or the polymerizable liquid crystal compound (2) is too large, phase separation may occur and the appearance may be impaired. The polymerizable compound constituting the composition is preferably substantially composed of a polymerizable liquid crystal compound having a structure similar to that of polymerizable compound (1). In addition, the above-mentioned "similar" means, for example, -(D ¹ -G ¹ )m-E ¹ -A ¹ -B ¹ -F ¹ -P ¹ , -(D ² -G ² ) The moiety represented by m-E ² -A ² -B ² -F ² -P ² or -D ²¹ -G ²¹ -E ²¹ -A ²¹ -B ²¹ -F ²¹ - in formula (2) P ²¹ , -D ²² -G ²² -E ²² -A ²² -B ²² -F ²² -P ²² refers to a case that has a structure common to the moiety represented by Ar, and the above-mentioned "substantially""consistingof" means that the content of the polymerizable compound (1) and the polymerizable liquid crystal compound (2) is 90% by mass or more based on the total mass of the polymerizable compounds contained in the mixed composition. . In one embodiment of the present invention, the mixed composition does not contain any polymerizable compounds other than the polymerizable compound (1) and the polymerizable liquid crystal compound (2).

The content of the polymerizable compound in the mixed composition of the present invention (the total amount of all polymerizable compounds) is, for example, 70 to 99.5 parts by mass based on 100 parts by mass of the solid content of the polymerizable composition, The amount is preferably 80 to 99 parts by weight, more preferably 85 to 98 parts by weight, and even more preferably 90 to 95 parts by weight. If the total mass of the polymerizable compound is within the above range, it is advantageous from the viewpoint of orientation of the resulting cured liquid crystal film. In addition, in this specification, when simply referring to a polymerizable compound, it refers to the polymerizable compound (1) and the polymerizable liquid crystal compound (polymerizable compound (2) and/or the polymerizable liquid crystal compound (2) if included). other polymerizable liquid crystal compounds). Moreover, the solid content of the mixed composition means the amount of all components excluding volatile components such as organic solvents from the mixed composition.

In addition to the polymerizable compound (1) and the polymerizable liquid crystal compound, the mixed composition of the present invention further contains additives such as an organic solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, and a leveling agent. You can stay there. These components may be used alone or in combination of two or more.

In the present invention, the mixed composition preferably contains a solvent because it is usually applied to a substrate etc. in a state dissolved in a solvent. The solvent is preferably a solvent that can dissolve polymerizable compounds such as the polymerizable compound (1) and the polymerizable liquid crystal compound (2), and is preferably a solvent that is inert to the polymerization reaction of the polymerizable compound. By containing the polymerizable compound (1) and the polymerizable liquid crystal compound (2) in combination, the mixed composition of the present invention achieves a higher polymerization rate than when the polymerizable liquid crystal compound (2) is dissolved alone in a solvent. The solvent solubility of the liquid crystal compound (2) can be significantly improved. Therefore, various solvents can be applied. Examples of the solvent include alcohols such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether. Solvents: Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone, etc. Ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cycloaliphatic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; such as tetrahydrofuran and dimethoxyethane. Ether solvents; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone, etc. It will be done. These solvents can be used alone or in combination of two or more. Among these, organic solvents are preferred, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are more preferred, and from the viewpoint of productivity, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone are preferred. At least one selected from the group consisting of , cyclohexanone and N-methylpyrrolidone is more preferred.

The content of the solvent in the mixed composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, based on 100 parts by mass of the mixed composition. Therefore, the solid content in 100 parts by mass of the mixed composition is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the mixed composition becomes low, so that the thickness of the film upon application becomes approximately uniform, and unevenness tends to occur less easily. The solid content can be determined as appropriate in consideration of the thickness of the cured liquid crystal film to be produced. Since the mixed composition of the present invention contains a combination of the polymerizable compound (1) and the polymerizable liquid crystal compound (2), it has excellent solubility in solvents, so it can be used in organic solvents used during coating and storage. It is also advantageous in that the amount of

The mixed composition of the present invention may contain a polymerization initiator. A polymerization initiator is a compound that can initiate a polymerization reaction such as a polymerizable compound. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferred from the viewpoint of not depending on the phase state of the thermotropic liquid crystal.

As the photopolymerization initiator, any known photopolymerization initiator can be used as long as it is a compound that can initiate the polymerization reaction of the polymerizable compound. Specifically, photopolymerization initiators that can generate active radicals or acids by the action of light can be mentioned, and among them, photopolymerization initiators that can generate radicals by the action of light are preferred. The photopolymerization initiators can be used alone or in combination of two or more.

As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as a photopolymerization initiator that generates active radicals, self-cleavable benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-Aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc. can be used, and hydrogen abstraction type benzophenone compounds, alkylphenone compounds, benzoin ether compounds, benzyl ketal compounds, dibenzo Suberone-based compounds, anthraquinone-based compounds, xanthone-based compounds, thioxanthone-based compounds, halogenoacetophenone-based compounds, dialkoxyacetophenone-based compounds, halogenobisimidazole-based compounds, halogenotriazine-based compounds, triazine-based compounds, etc. can be used. As the photopolymerization initiator that generates acid, iodonium salts, sulfonium salts, and the like can be used. From the viewpoint of excellent reaction efficiency at low temperatures, self-cleavable photopolymerization initiators are preferred, and acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, and oxime ester compounds are particularly preferred.

The content of the photopolymerization initiator is usually 0.1 parts by mass or more and 20 parts by mass or less, preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total amount of polymerizable compounds. Preferably it is 1 part by mass or more and 10 parts by mass or less. Within the above range, the reaction of the polymerizable groups will proceed sufficiently and the orientation of the polymerizable liquid crystal compound will not be easily disturbed.

From the viewpoint of stably advancing the polymerization reaction, the mixed composition may contain a polymerization inhibitor.
The degree of progress of the polymerization reaction of the polymerizable compound can be controlled by the polymerization inhibitor.

Examples of the polymerization inhibitor include radicals such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (such as butylcatechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical. Scavengers; thiophenols; β-naphthylamines, β-naphthols, and the like.

The amount is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of polymerizable compounds. When the content of the polymerization inhibitor is within the above range, polymerization can be carried out without disturbing the orientation of the polymerizable liquid crystal compound.

The mixed composition may contain a sensitizer. As the sensitizer, a photosensitizer is preferred. Examples of the sensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene such as anthracene and anthracene containing an alkoxy group (for example, dibutoxyanthracene, etc.); Compounds include phenothiazine and rubrene.

When the mixed composition contains a sensitizer, the polymerization reaction of the polymerizable compound contained in the mixed composition can be further promoted. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 parts by mass, based on 100 parts by mass of the total amount of polymerizable compounds. ~3 parts by mass.

The mixed composition may contain a leveling agent. A leveling agent is an additive that has the function of adjusting the fluidity of the composition and making the film obtained by applying the composition more flat, and examples include organically modified silicone oil, polyacrylate, and perfluorinated silicone oil. Examples include alkyl leveling agents. Among these, polyacrylate leveling agents and perfluoroalkyl leveling agents are preferred.

The content of the leveling agent in the mixed composition is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total amount of polymerizable compounds. When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal compound, and the resulting optically anisotropic layer tends to be smoother. When the content of the leveling agent in the polymerizable liquid crystal compound exceeds the above range, the resulting optically anisotropic layer tends to be uneven. In addition, the composition for forming an optically anisotropic layer may contain two or more types of leveling agents.

The mixed composition of the present invention includes a polymerizable compound (1) and a polymerizable liquid crystal compound (preferably a polymerizable liquid crystal compound (2)), each prepared separately, and optionally a solvent, a photoinitiator, It can be prepared by adding additives such as a polymerization inhibitor, photosensitizer, or leveling agent, and stirring and mixing at a predetermined temperature.

In the present invention, the mixed composition has the formula (i):
Re1 (450) / Re1 (550) ≧ Re0 (450) / Re0 (550) (i) [In formula (i), Re0 (λ) is the in-plane area at the wavelength λ nm of the cured film formed from the polymerizable liquid crystal compound. Re1 (λ) represents the in-plane retardation value at the wavelength λ nm of the cured film formed from the mixed composition]
It is preferable to satisfy the following. When the mixed composition satisfies the relationship of formula (i), an arbitrary retardation value can be adjusted by mixing the polymerizable compound (1) with the polymerizable liquid crystal compound (2).

The value of Re1(450)/Re1(550) in the above formula (i) is a value obtained by measuring the front retardation value at each wavelength using the mixed composition to be measured as a measurement sample. On the other hand, the value of Re0(450)/Re0(550) is determined by measuring a composition that differs from the mixed composition to be measured only in that it does not contain a compound corresponding to the polymerizable compound (1). is a value obtained by measuring the front phase difference value at each wavelength. The measurement conditions for Re1 (450)/Re1 (550) are the same as the measurement conditions for Re0 (450)/Re0 (550). A specific measurement method will be described in the Examples described below.

<Retardation film>
The polymerizable compound (1) of the present invention has high solubility in various solvents and has an excellent effect of lowering the crystallization temperature of the mixed composition when mixed with a polymerizable liquid crystal compound, so it can lower the crystallization temperature while suppressing crystallization. Films can be formed at processing temperatures. As a result, it is possible to suppress damage caused by heating at high temperatures and the occurrence of alignment defects caused by crystallized substances, and it is possible to form films without deteriorating the optical properties that can originally be expressed by the polymerizable liquid crystal compound used. This makes it possible to obtain a cured liquid crystal film with excellent optical properties. Therefore, the present invention also relates to a cured product of the mixed composition of the present invention, particularly a retardation film containing a cured liquid crystal film formed by curing the polymerizable liquid crystal compound in the composition in an oriented state. A retardation film composed of the cured liquid crystal film can sufficiently exhibit the optical properties that the polymerizable liquid crystal compound used can originally exhibit, and can be a retardation film having high optical performance.

The cured liquid crystal film constituting the retardation film of the present invention is a polymerizable compound (1) and a polymerizable liquid crystal compound, especially a polymerizable compound (1), because the polymerization reaction is easy and it is easy to obtain a uniform cured liquid crystal film. It is preferable that it is composed of a copolymer in an oriented state of a mixture of and a polymerizable liquid crystal compound (2).

In one aspect of the present invention, the retardation film of the present invention is preferably formed from the mixed composition of the present invention and includes a cured liquid crystal film that satisfies the following formula (ii), formulas (ii), (iii), and It is more preferable to include a liquid crystal cured film having the optical properties represented by (iv). Such a cured liquid crystal film is usually a cured product obtained by curing a polymerizable liquid crystal compound aligned horizontally with respect to the plane of the cured liquid crystal film (hereinafter also referred to as a "horizontally oriented cured liquid crystal film"). be.
0.75≦Re1(450)/Re1(550)<1.00 (ii)
1.00≦Re1(650)/Re1(550) (iii)
100nm≦Re1(550)≦180nm (iv)
[In the formula, Re1 (λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm, and Re = (nx (λ) - ny (λ)) x d (d is the thickness of the liquid crystal cured film. In the refractive index ellipsoid formed by the liquid crystal cured film, nx represents the principal refractive index at a wavelength λ nm in a direction parallel to the plane of the liquid crystal cured film, and ny represents the refractive index ellipsoid formed by the liquid crystal cured film. , represents the refractive index at a wavelength λnm in a direction parallel to the plane of the cured liquid crystal film and perpendicular to the direction of nx). ]

When the horizontally aligned liquid crystal cured film satisfies formulas (ii) and (iii), the horizontally aligned liquid crystal cured film has an in-plane retardation value at a short wavelength that is smaller than an in-plane retardation value at a long wavelength. It exhibits so-called reverse wavelength dispersion. Since the reverse wavelength dispersion is improved and the optical properties of the retardation film are further improved, Re1(450)/Re1(550) is preferably 0.78 or more, more preferably 0.80 or more, and , preferably 0.96 or less, more preferably 0.94 or less, still more preferably 0.92 or less. Further, Re(650)/Re(550) is preferably 1.01 or more, more preferably 1.02 or more.

The above in-plane retardation value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d, the desired in-plane retardation value (Re(λ): wavelength λ( In order to obtain the in-plane retardation value of the horizontally aligned liquid crystal cured film in nm), the three-dimensional refractive index and film thickness d may be adjusted.

In addition, when the horizontally aligned liquid crystal cured film satisfies formula (iii), the effect of improving the front reflection hue (coloring excellent in suppressing effects). A more preferable range of the in-plane retardation value is 120 nm≦Re(550)≦170 nm, and an even more preferable range is 130 nm≦Re(550)≦150 nm.

The retardation film of the present invention includes, for example,
forming a coating film of the mixed composition of the present invention, drying the coating film, and orienting the polymerizable liquid crystal compound in the mixed composition;
It can be produced by a method including a step of polymerizing the polymerizable compound (1) and the polymerizable liquid crystal compound by irradiating light while maintaining the alignment state to form a cured liquid crystal film.

A coating film of the mixed composition can be formed by applying the mixed composition onto a substrate or an alignment film described below.
Examples of the base material include a glass base material and a film base material, and a film base material is preferred, and a long roll-shaped film is more preferred since it can be manufactured continuously. Examples of resins constituting the film base material include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic esters; polyacrylic esters; triacetyl cellulose, diacetyl cellulose and cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. Among them, a film base material selected from triacetylcellulose, cyclic olefin resin, polymethacrylic acid ester, and polyethylene terephthalate is more preferable from the viewpoint of transparency when used in optical film applications.

Commercially available products may be used as the base material. Commercially available cellulose ester base materials include, for example, cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fuji Tac Film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY"; Examples include cellulose ester base materials. Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefin resins manufactured by JSR Corporation such as "Arton (registered trademark)"; Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Mitsui resins such as “APEL” (registered trademark) Examples include cyclic olefin resin manufactured by Kagaku Corporation. A commercially available cyclic olefin resin base material can also be used. Commercially available cyclic olefin resin base materials include cyclic olefin resin base materials manufactured by Sekisui Chemical Co., Ltd. such as "Escina (registered trademark)" and "SCA40 (registered trademark)"; "Zeonor Film (registered trademark)" Examples include cyclic olefin resin base materials manufactured by Optes Co., Ltd.; and cyclic olefin resin base materials manufactured by JSR Corporation such as "Arton Film (registered trademark)".

From the viewpoints of thinning the retardation film, ease of peeling the base material, handleability of the base material, etc., the thickness of the base material is usually 5 to 300 μm, preferably 10 to 200 μm, more preferably 10 to 50 μm. It is.

Examples of methods for applying the mixed composition to the base material include extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, slit coating method, microgravure method, die coating method, inkjet method, etc. . Other examples include a method of coating using a coater such as a dip coater, a bar coater, or a spin coater. Among these, when coating continuously in a roll-to-roll format, coating methods such as microgravure, inkjet, slit coating, and die coating are preferred; when coating on sheet substrates such as glass, uniformity A spin coating method with a high When coating in a roll-to-roll format, an alignment film-forming composition or the like is applied to a base material to form an alignment film, and then an optically anisotropic layer-forming composition is continuously applied on the obtained alignment film. It can also be painted.

Next, by removing the solvent by drying or the like, a dry coating film is formed. Examples of the drying method include natural drying, ventilation drying, heating drying, and reduced pressure drying. Among these, natural drying or heat drying is preferred. At this time, by heating the coating film obtained from the mixed composition, the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be oriented in a desired direction with respect to the plane of the coating film. The heating temperature of the coating film can be appropriately determined by considering the polymerizable compound (1) used, the polymerizable liquid crystal compound, and the material of the base material forming the coating film, etc. In order to cause a phase transition, the temperature usually needs to be higher than the liquid crystal phase transition temperature. In order to bring the polymerizable liquid crystal compound into a desired alignment state while removing the solvent contained in the mixed composition, for example, the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the mixed composition is adjusted. (phase transition temperature) or higher.

In one embodiment of the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal compound constituting the mixed composition of the present invention is preferably 25°C or more and 200°C or less. It is preferable that the phase transition temperature to the liquid crystal phase is within the above range from the viewpoints of easy industrial production and improved productivity. In the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal compound is usually 40°C or higher, more preferably 50°C or higher, and even more preferably The temperature is 60°C or higher, more preferably 180°C or lower, and even more preferably 160°C or lower from the viewpoint of productivity. In the mixed composition of the present invention, by including the polymerizable compound (1), the liquid crystal phase transition temperature is more likely to be lowered than when the mixed composition contains only the polymerizable liquid crystal compound. If the crystallization temperature of the mixed composition can be lowered and the phase transition temperature can also be lowered, it will be possible to form a film without exposing it to high temperature conditions, and the resulting optical film will have even higher optical properties. You can expect it to be granted.
Note that the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. When a plurality of polymerizable liquid crystal compounds are included, the above phase transition temperature is measured using a mixture of polymerizable liquid crystal compounds in which all polymerizable liquid crystal compounds constituting the mixed composition are mixed in the same ratio as the composition in the mixed composition. means temperature.

The mixed composition of the present invention contains the polymerizable compound (1) and is generally more effective in lowering the crystallization temperature than when it contains only a polymerizable liquid crystal compound. Therefore, in manufacturing a retardation film using the mixed composition of the present invention, excessive consumption of thermal energy can be suppressed, and production efficiency can be improved. Further, since the film can be formed by heating at a relatively low temperature, there is an advantage that the choice of supporting substrates to which the mixed composition is applied is expanded.

The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable compound used, the type of solvent, its boiling point, its amount, etc., but is usually 10 seconds to 10 minutes, preferably 0.5 to 5 minutes. It's a minute.

Removal of the solvent from the coating film may be performed simultaneously with heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, or may be performed separately, but it is preferably performed simultaneously from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature higher than the liquid crystal phase transition temperature, the coating film obtained from the mixed composition is coated under conditions that do not polymerize the polymerizable compound (1) and/or the polymerizable liquid crystal compound contained in the coating film. A preliminary drying step may be provided to appropriately remove the solvent in the film. Drying methods in this pre-drying step include natural drying, ventilation drying, heating drying, and vacuum drying, and the drying temperature (heating temperature) in this drying step depends on the type of polymerizable compound used and the amount of solvent used. It can be determined as appropriate depending on the type, boiling point, amount, etc.

Next, in the obtained dry coating film, the polymerizable compound (1) and the polymerizable liquid crystal compound are polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, thereby polymerizing the polymerizable liquid crystal compound that exists in the desired orientation state. A cured liquid crystal film is formed which is a polymer as a mixture of the compound (1) and the polymerizable liquid crystal compound. Since the mixed composition of the present invention can be highly polymerized by irradiation with light such as high-intensity ultraviolet rays while suppressing damage to the polymerizable compound, a photopolymerization method is usually used as the polymerization method. . In photopolymerization, the light irradiated onto the dry coating film is appropriately selected depending on the type of polymerization initiator, the type of polymerizable compound, and the amount thereof contained in the dry coating film. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and active electron beams. Among these, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use photopolymerization equipment that is widely used in the field. It is preferable to select the types of polymerizable compounds and polymerization initiators to be contained in the mixed composition. Moreover, during polymerization, the polymerization temperature can also be controlled by irradiating the dry coating film with light while cooling it with an appropriate cooling means. By employing such a cooling means and polymerizing the polymerizable compound at a lower temperature, a cured liquid crystal film can be appropriately formed even if a base material with relatively low heat resistance is used. It is also possible to promote the polymerization reaction by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation of the base material due to heat). A patterned cured film can also be obtained by performing masking or development during photopolymerization.

Examples of the light source of the active energy ray include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, and a wavelength range. Examples include an LED light source that emits light in the range of 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The ultraviolet irradiation intensity is usually 10 mW/cm ² to 3,000 mW/cm ² . The ultraviolet irradiation intensity is preferably in a wavelength range effective for activating a cationic polymerization initiator or a radical polymerization initiator. The light irradiation time is usually 0.1 seconds to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and even more preferably 10 seconds to 1 minute. When irradiated once or multiple times with such ultraviolet irradiation intensity, the cumulative amount of light is usually 10 mJ/cm ² to 3,000 mJ/cm ² , preferably 50 mJ/cm ² to 2,000 mJ/cm ² , more preferably It is 100 mJ/cm ² to 1,000 mJ/cm ² . If the cumulative amount of light is below this range, the polymerizable liquid crystal compound may not be sufficiently cured, and good transferability may not be obtained. On the other hand, if the cumulative amount of light is above this range, the retardation film including the cured liquid crystal film may be colored.

The thickness of the cured liquid crystal film can be appropriately selected depending on the display device to which it is applied, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

A coating film of the mixed composition may be formed on the alignment film. The alignment film has an alignment regulating force that causes the polymerizable liquid crystal compound to align the liquid crystal in a desired direction. The alignment film facilitates liquid crystal alignment of the polymerizable liquid crystal compound. The state of liquid crystal alignment, such as horizontal alignment, vertical alignment, hybrid alignment, and tilted alignment, changes depending on the properties of the alignment film and the polymerizable liquid crystal compound, and the combination thereof can be arbitrarily selected. For example, if the alignment film is a material that exhibits horizontal alignment as an alignment regulating force, the polymerizable liquid crystal compound can form horizontal alignment or hybrid alignment; if the alignment film is a material that exhibits vertical alignment, the polymerizable liquid crystal compound can form a vertical or tilted orientation. Expressions such as horizontal and vertical refer to the direction of the long axis of the oriented polymerizable liquid crystal compound with respect to the plane of the optically anisotropic layer. For example, vertical alignment means that the long axis of the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the optically anisotropic layer. Vertical here means 90°±20° with respect to the plane of the optically anisotropic layer.

If the alignment film is made of an oriented polymer, the alignment regulating force can be adjusted arbitrarily by changing the surface condition and rubbing conditions, and if it is made of a photo-alignable polymer, it can be adjusted by changing the polarized light irradiation conditions. It is possible to arbitrarily adjust it by etc. Moreover, liquid crystal alignment can also be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

The alignment film formed between the base material and the liquid crystal cured film is insoluble in the solvent used when forming the liquid crystal cured film on the alignment film, and is insoluble in the solvent used to remove the solvent and align the liquid crystal. It is preferable that the material has heat resistance in heat treatment. Examples of the alignment film include an alignment film made of an oriented polymer, a photo-alignment film, a groove alignment film, a stretched film stretched in the orientation direction, etc. When applied to a long roll-shaped film, A photo-alignment film is preferred because the orientation direction can be easily controlled.

The thickness of the alignment film is usually in the range of 10 nm to 5000 nm, preferably in the range of 10 nm to 1000 nm, and more preferably in the range of 30 to 300 nm.

The oriented polymers used in the rubbed alignment film include polyamides and gelatins having amide bonds in the molecule, polyimides having imide bonds in the molecule, polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, Examples include polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic esters. Among them, polyvinyl alcohol is preferred. These oriented polymers may be used alone or in combination of two or more.

The rubbing method involves coating a substrate with an oriented polymer composition on a rotating rubbing roll wrapped with a rubbing cloth and annealing it to form an oriented polymer film on the surface of the substrate. An example is a method of contacting.

The photo-alignment film is made of a polymer, oligomer or monomer having a photo-reactive group. The photo-alignment film can obtain alignment regulating power by irradiating it with polarized light. A photo-alignment film is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

A photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light. Specifically, it is one that induces the orientation of molecules by irradiation with light, or that causes a photoreaction that is the origin of the liquid crystal alignment ability, such as an isomerization reaction, a dimerization reaction, a photocrosslinking reaction, or a photodecomposition reaction. be. Among the photoreactive groups, those that cause a dimerization reaction or a photocrosslinking reaction are preferred in terms of excellent orientation. The photoreactive group capable of causing the above reaction is preferably one having an unsaturated bond, especially a double bond, such as a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C More preferably, the group has at least one selected from the group consisting of a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C═C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. A chalcone group and a cinnamoyl group are preferred from the viewpoint of easy control of reactivity and expression of alignment regulating force during photoalignment. Examples of the photoreactive group having a C=N bond include groups having structures such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N=N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and those having an azoxybenzene as a basic structure. Examples of the photoreactive group having a C═O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

The polarized light may be irradiated either directly from the film surface or by irradiating the polarized light from the base material side and allowing the polarized light to pass through. Moreover, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range in which a polymer having a photoreactive group or a photoreactive group of a monomer can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of light sources used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF, with high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps being more preferable. These lamps are preferable because they emit a high intensity of ultraviolet light with a wavelength of 313 nm. Polarized light can be irradiated by passing the light from the light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

<Elliptical polarizing plate>
The present invention includes an elliptically polarizing plate including the retardation film of the present invention. The elliptically polarizing plate includes a polarizing film as well as a retardation film. A polarizing film is a film in which dichroic dyes are uniaxially oriented. In order to uniaxially align dichroic dyes, a film (hereinafter also referred to as a "polarizer") that is uniaxially stretched after impregnating iodine or an organic dichroic dye in a polymer such as polyvinyl alcohol, or a polymerizable Polymerization containing a dichroic dye formed by orienting a dichroic dye and a polymerizable liquid crystal compound from a composition containing a liquid crystal compound and a dichroic dye (hereinafter also referred to as "composition for forming a polarizing film") It can be produced from an optically anisotropic layer (hereinafter also referred to as a "polarizing film") made of a polymer of a polarizing liquid crystal compound. That is, the dichroic dye included in the stretched polymer or the polymerizable liquid crystal compound exhibits a polarizing function by anisotropically absorbing light.

Polarizers are usually manufactured using a process of uniaxially stretching a polyvinyl alcohol resin film, a process of dyeing the polyvinyl alcohol resin film with a dichroic dye such as iodine, and a process of adsorbing the dichroic dye. It can be produced through a step of treating a polyvinyl alcohol-based resin film on which is adsorbed with a boric acid aqueous solution, and a step of washing with water after the treatment with the boric acid aqueous solution.

The thickness of the polarizer is usually 30 μm or less, preferably 18 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. The thickness is usually 1 μm or more, and may be, for example, 5 μm or more.

Uniaxial stretching of the polyvinyl alcohol film can be performed before, simultaneously with, or after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before or during the boric acid treatment. Of course, uniaxial stretching can also be performed in multiple stages as shown here. Uniaxial stretching methods include stretching uniaxially in the film transport direction between rolls with different circumferential speeds, stretching uniaxially in the film transport direction using hot rolls, and stretching in the width direction using a tenter. can be adopted. Further, the uniaxial stretching may be carried out by dry stretching in the atmosphere, or by wet stretching in which the polyvinyl alcohol film is stretched in a swollen state using a solvent such as water.
The stretching ratio is usually about 3 to 8 times. Alternatively, after applying an aqueous solution containing polyvinyl alcohol onto a thermoplastic resin film, a drying treatment may be performed, and the film may be stretched together with the thermoplastic resin film by the above method.

Staining of a polyvinyl alcohol film with a dichroic dye can be carried out, for example, by immersing the polyvinyl alcohol film in an aqueous solution containing the dichroic dye. Specifically, iodine and dichroic organic dyes are used as the dichroic dye.

A protective film can be included on one or both sides of the polarizer. A thermoplastic resin film can be used as the protective film. The linear polarizer and the protective film can be laminated via an adhesive or the like. The film formed from a thermoplastic resin may be subjected to surface treatment (for example, corona treatment, etc.) in order to improve adhesion with the polarizer, and a thin layer such as a primer layer (also referred to as an undercoat layer) may be applied. may be formed.

The thermoplastic resin constituting the thermoplastic resin film is preferably a transparent film, and includes, for example, cellulose resin such as triacetyl cellulose; polyester resin such as polyethylene terephthalate and polyethylene naphthalate; polyether sulfone resin; polysulfone resin; Polycarbonate resins; polyamide resins such as nylon and aromatic polyamides; polyimide resins; polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers; cyclic polyolefin resins having cyclo and norbornene structures (also referred to as norbornene resins); Examples include meth)acrylic resin; polyarylate resin; polystyrene resin; polyvinyl alcohol resin. Among these, the thermoplastic resin film is preferably a cyclic polyolefin resin film, a cellulose ester resin film, a polyester resin film, or a (meth)acrylic resin film.

A hard coat layer may be formed on the thermoplastic resin film. The hard coat layer may be formed on one side or both sides of the thermoplastic resin film. By providing a hard coat layer, it is possible to obtain a thermoplastic resin film with improved hardness and scratch resistance. The hard coat layer is, for example, a cured layer of active energy ray curable resin, preferably ultraviolet ray curable resin. Examples of the ultraviolet curable resin include (meth)acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, and epoxy resin. The hard coat layer may contain additives to improve strength. The additive is not particularly limited, and may include inorganic fine particles, organic fine particles, or a mixture thereof.

A polarizing film, that is, an optically anisotropic layer made of a polymer of a polymerizable liquid crystal compound containing a dichroic dye, can control the hue arbitrarily, can be made significantly thinner, and does not undergo stretching relaxation due to heat. Therefore, since it has non-shrinkage properties, it can be suitably used for flexible display applications, for example.

The polarizing film is formed by applying a polarizing film-forming composition onto an alignment film formed on a base material as needed, and aligning the dichroic dye contained in the polarizing film-forming composition. be done. The polarizing film has a thickness of 0.1 μm or more and 5 μm or less, more preferably 0.3 μm or more and 4 μm or less, and still more preferably 0.5 μm or more and 3 μm or less. When the film thickness is within this range, it is easy to obtain the necessary light absorption, and alignment defects are less likely to occur due to a decrease in the alignment regulating force of the alignment film.

In order to obtain polarization characteristics in the XY plane, the dichroic dye and the polymerizable liquid crystal compound should be aligned horizontally with respect to the substrate surface, and polarization characteristics in the Z direction (thickness direction of the polarizing film) may be obtained. In order to obtain such properties, the dichroic dye and the polymerizable liquid crystal compound may be aligned perpendicularly to the substrate surface.

An optically anisotropic layer in which a dichroic dye and a polymerizable liquid crystal compound are aligned horizontally to the substrate surface has an absorbance A1 (λ) in the alignment direction and an absorbance A2 (λ) in the vertical direction within the alignment plane for light with a wavelength of λ nm. The ratio (dichroic ratio) is preferably 7 or more, more preferably 20 or more, and still more preferably 40 or more. The higher this value is, the better the absorption selectivity of the polarizing plate is. Although it depends on the type of dichroic dye, in the case of a liquid crystal cured film cured in a nematic liquid crystal phase, the dichroic ratio is about 5 to 10.

By mixing two or more types of dichroic dyes with different absorption wavelengths, polarizing films with various hues can be produced, and polarizing films that absorb in the entire visible light range can be produced. A polarizing film having such absorption characteristics can be used in a variety of applications.

The polymerizable liquid crystal compound in the composition for forming a polarizing film is a compound that has a polymerizable group and has liquid crystallinity (hereinafter also referred to as polymerizable liquid crystal compound (3)). A polymerizable group means a group that participates in a polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by active radicals, acids, etc. generated from a photopolymerization initiator, which will be described later. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group, and the like. Among these, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferred, and methacryloyloxy group or acryloyloxy group is more preferred. The liquid crystal may be either thermotropic liquid crystal or lyotropic liquid crystal, but thermotropic liquid crystal is preferable when mixed with a dichroic dye described below.

When the polymerizable liquid crystal compound (3) is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase or a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. When exhibiting a polarizing function as a cured film through a polymerization reaction, the liquid crystal state of the polymerizable liquid crystal compound (3) is preferably a smectic phase, and a higher smectic phase is preferred from the viewpoint of high performance. preferable. Among them, higher-order smectic liquid crystal compounds forming smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase or smectic L phase are used. More preferred are higher-order smectic liquid crystal compounds that form a smectic B phase, smectic F phase, or smectic I phase. When the liquid crystal phase formed by the polymerizable liquid crystal compound (3) is one of these higher-order smectic phases, a polarizing film with higher polarizing performance can be manufactured. In addition, a polarizing film having such high polarization performance can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. The Bragg peak is a peak derived from the periodic structure of molecular orientation, and a film having a periodic interval of 3 to 6 Å can be obtained. In the present invention, the polarizing film preferably contains a polymer of polymerizable liquid crystal in which the polymerizable liquid crystal compound (3) is oriented in a smectic phase, from the viewpoint of obtaining higher polarizing properties.

As the polymerizable liquid crystal compound (3), one type may be used alone, or two or more types may be used in combination. The composition for forming a polarizing film may contain other polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (3), but from the viewpoint of obtaining a polarizing film with a high degree of alignment order, the composition for forming a polarizing film may contain The ratio of the polymerizable liquid crystal compound (3) to the total mass of all polymerizable liquid crystal compounds contained is preferably 51% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. .

The content of the polymerizable liquid crystal compound (3) in the composition for forming a polarizing film is preferably 40 to 99.9% by mass, more preferably 60 to 99.9% by mass, based on the solid content of the composition for forming a polarizing film. It is % by mass, more preferably 70 to 99 % by mass. When the content of the polymerizable liquid crystal compound (3) is within the above range, the orientation of the polymerizable liquid crystal compound (3) tends to be high. Note that in this specification, the solid content refers to the total amount of components excluding the solvent from the composition for forming a polarizing film.

Dichroic dye refers to a dye that has a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The dichroic dye preferably has a property of absorbing visible light, and more preferably has a maximum absorption wavelength (λMAX) in the range of 380 to 680 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes, among which azo dyes are preferred. Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, with bisazo dyes and trisazo dyes being preferred. Dichroic dyes may be used alone or in combination, but in order to obtain absorption in the entire visible light range, it is preferable to combine two or more types of dichroic dyes, and it is preferable to combine three or more types of dichroic dyes. is more preferable.

Examples of azo dyes include compounds represented by formula (I) (hereinafter sometimes referred to as "compound (I)").
T1-A1(-N=N-A2)p-N=N-A3-T2(I)
[In formula (I), A1, A2 and A3 are each independently a 1,4-phenylene group which may have a substituent, and a naphthalene-1,4-diyl group which may have a substituent. group, a benzoic acid phenyl ester group that may have a substituent, a 4,4'-stilbenylene group that may have a substituent, or a divalent heterocyclic group that may have a substituent , T1 and T2 are electron-withdrawing groups or electron-emitting groups, and are located at substantially 180 degrees with respect to the azo bond plane. p represents an integer from 0 to 4. When p is 2 or more, each A2 may be the same or different from each other. The -N=N- bond may be replaced by a -C=C-, -COO-, -NHCO-, or -N=CH- bond within a range that exhibits absorption in the visible region. ]

The content of the dichroic dye (the total amount if multiple types are included) is usually 1 to 60 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound, from the viewpoint of obtaining good light absorption characteristics. The amount is preferably 1 to 40 parts by weight, more preferably 1 to 20 parts by weight. When the content of the dichroic dye is within this range, it is possible to secure the necessary light absorption and obtain sufficient polarization performance, and the polarizing film has excellent polarization performance because it does not easily inhibit the alignment of liquid crystal molecules. can be obtained.

A protective film or the like may be laminated on at least one surface of the polarizing film thus obtained, similar to the structure of the polarizer described above.

The elliptically polarizing plate of the present invention includes the retardation film of the present invention and the polarizing film. For example, the retardation film of the present invention and the polarizing film are combined with an adhesive layer or a pressure-sensitive adhesive layer. The elliptically polarizing plate of the present invention can be obtained by laminating the elliptically polarizing plate through the laminate.

In one embodiment of the present invention, when the retardation film of the present invention including a horizontally aligned liquid crystal cured film and a polarizing film are laminated, the slow axis (optical axis) of the horizontally aligned liquid crystal cured film constituting the retardation film It is preferable to laminate the polarizing film so that the angle formed between the polarizing film and the absorption axis of the polarizing film is 45±5°.

The elliptically polarizing plate of the present invention may have a configuration similar to that of a conventional general elliptically polarizing plate, or a polarizing film and a retardation film. Such structures include, for example, adhesive layers (sheets) used to bond elliptically polarizing plates to display elements such as organic EL, and adhesive layers used to protect the surfaces of polarizing films and retardation films from scratches and dirt. Protective films and the like can be mentioned.

The elliptically polarizing plate of the present invention can be used in various display devices, especially optical displays.
A display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Display devices include liquid crystal displays, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, touch panel display devices, electron emission display devices (e.g. field emission display (FED), surface field emission display device). (SED)), electronic paper (display devices using electronic ink or electrophoretic elements, plasma display devices, projection display devices (e.g., grating light valve (GLV) display devices, display devices with digital micromirror devices (DMD)) ) and piezoelectric ceramic displays.Liquid crystal display devices include transmissive liquid crystal display devices, transflective liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection type liquid crystal display devices. These display devices may be display devices that display two-dimensional images, or stereoscopic display devices that display three-dimensional images.In particular, the elliptically polarizing plate of the present invention uses organic electroluminescence ( It can be suitably used for EL) display devices and inorganic electroluminescence (EL) display devices.These display devices (optical displays) can display good images by being equipped with the elliptically polarizing plate of the present invention which has excellent optical properties. Characteristics can be expressed.

Furthermore, the elliptically polarizing plate of the present invention can be suitably incorporated into a flexible image display device. The flexible image display device includes, for example, a laminate for a flexible image display device and an organic EL display panel, the laminate for a flexible image display device is arranged on the viewing side of the organic EL display panel, and is configured to be foldable. has been done. In addition to the above-described elliptically polarizing plate of the present invention, the laminate for a flexible image display device may include a window, a touch panel touch sensor, and the like. Although the order of stacking them is arbitrary, it is preferable that they are stacked in the order of the window, the elliptically polarizing plate, and the touch panel touch sensor from the viewing side, or in the order of the window, the touch panel touch sensor, and the elliptically polarizing plate.

It is preferable if an elliptically polarizing plate is present on the viewing side of the touch panel touch sensor, since the pattern of the touch panel touch sensor becomes less visible and the visibility of the displayed image improves. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. Further, the laminate for a flexible image display device may include a light shielding pattern formed on at least one surface of any one of the window, the elliptically polarizing plate, and the touch panel touch sensor.

The window is placed on the viewing side of the flexible image display device and plays the role of protecting other components from external shocks or environmental changes such as temperature and humidity. Conventionally, glass has been used as such a protective layer, but the window in a flexible image display device is not rigid and hard like glass, but has flexible characteristics. The window is made of a flexible transparent base material, and may include a hard coat layer on at least one surface.

The window, touch panel touch sensor, etc. that constitute the laminate for a flexible image display device are not particularly limited, and conventionally known ones can be employed.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, "%" and "parts" in the examples mean % by mass and parts by mass, respectively, unless otherwise specified.

HPLC measurement used for analysis of each compound may be performed under any conditions as long as peaks derived from each polymerizable compound and polymerizable liquid crystal compound can be separated. An example of HPLC measurement conditions is shown below.
(Measurement condition)
Measuring device: HPLC LC-10AT (manufactured by Shimadzu Corporation)
Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle size 3 μm) Temperature: 40°C
Mobile phase A: 0.1% (v/v)-TFA/water Mobile phase B: 0.1% (v/v)-TFA/acetonitrile Gradient: 0 min 70%-B
30min 100%-B
60min 100%-B
60.01min 70%-B
75min 70%-B
Flow rate: 0.5mL/min
Injection volume: 5μL
Detection wavelength: 254nm

1. Preparation of Polymerizable Compounds Polymerizable compound (1) and polymerizable liquid crystal compound (2) were each prepared according to the following methods.

(1) Preparation of polymerizable compound (1) (i) Synthesis example 1
According to the following scheme, a compound represented by formula (1-1a) (hereinafter referred to as "compound (1-1a)") and a compound represented by formula (1-2a) (hereinafter referred to as "compound (1-2a)") )"), a polymerizable compound represented by formula (1-A) (hereinafter referred to as "polymerizable compound (1-A)") was synthesized.

A nitrogen atmosphere was placed in a 100 mL four-neck flask equipped with a Dimroth condenser and a thermometer, and 14.41 g of compound (1-1a) and compound (1-2a) were synthesized with reference to patent document (JP 2010-1284). ) (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.00 g, DMAP (N,N-dimethylaminopyridine, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 0.18 g, BHT (dibutylhydroxytoluene, Fuji Film Wako Pure Chemical Industries, Ltd.) 75 g of chloroform (manufactured by Kanto Kagaku Co., Ltd.) were added and mixed. Next, 9.06 g of IPC (diisopropylcarbodiimide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and the mixture was reacted overnight at 0°C. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was dropped into methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in an amount three times the mass of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30° C. to obtain 4.56 g of polymerizable compound (1-A). As a result of analyzing the obtained polymerizable compound (1-A) by HPLC measurement, the purity of the polymerizable compound (1-A) was 97.7% in area percentage. The yield of polymerizable compound (1-A) was 23.8% based on compound (1-2a).

(ii) Synthesis examples 2 to 4
Polymerizable compounds (1-B) to ( 1-D) were prepared respectively. Table 1 shows the results of HPLC analysis.

(iii) Synthesis example 5
A nitrogen atmosphere was placed in a 50 mL four-neck flask equipped with a Dimroth condenser and a thermometer, and 6.00 g of compound (1-1b) synthesized with reference to patent document (JP 2010-1284), hexanediol (Fuji Film 0.82 g (manufactured by Wako Pure Chemical Industries, Ltd.), 0.04 g DMAP (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 0.16 g (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 0.16 g of BHT (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and chloroform (manufactured by Kanto Chemical Co., Ltd.). After adding and mixing 25 g of IPC (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) using a dropping funnel, 1.90 g of IPC (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was further added and reacted overnight at 0°C. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was dropped into methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in an amount three times the mass of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 20 g of methanol, and then dried under reduced pressure at 30° C. to obtain 4.82 g of polymerizable compound (1-E). As a result of analyzing the obtained polymerizable compound (1-E) by HPLC measurement, the purity of the above compound (1-6) was 97.8% in area percentage. The yield of polymerizable compound (1-E) was 74.8% based on hexanediol.

(iv) Synthesis example 6
Polymerizable compound (1-E) was synthesized from compound (1-1a) and triphosgene according to the scheme below.

A 100 mL four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 10.00 g of compound (1-1a), 1.87 g of triphosgene (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and chloroform (manufactured by Kanto Kagaku Co., Ltd.) were added. After adding and mixing 100 g of diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) using a dropping funnel, 4.89 g of diisopropylethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was further added and reacted overnight. After the reaction was completed, 9.4 g of 0.5M hydrochloric acid was added, stirred, and then left to stand and separated to remove the aqueous layer, which was repeated twice. Thereafter, 9.4 g of water was added, stirred, and then allowed to stand still for liquid separation. Chloroform was distilled off from the collected organic layer using an evaporator to obtain a viscous liquid. The obtained liquid was cooled to 5° C. or lower to solidify and was scraped out of the container to obtain 8.6 g of polymerizable compound (1-F). As a result of analyzing the obtained polymerizable compound (1-F) by HPLC measurement, the purity of the polymerizable compound (1-F) was 97.8% in area percentage.
The yield of polymerizable compound (1-F) was 82.0% based on compound (1-1a).

Structure of compound (1-1) and compound (1-2) used/Compound (1-1a):

・Compound (1-1b):

・Compound (1-2a):

・Compound (1-2b):

・Compound (1-2c):

・Compound (1-2d):

(2) Preparation of polymerizable liquid crystal compound (2) (i) Synthesis example 7
According to the following scheme, a compound represented by formula (2-1a) (hereinafter referred to as "compound (2-1a)") and a compound represented by formula (2-2a) (hereinafter referred to as "compound (2-2a)") )"), a polymerizable liquid crystal compound represented by formula (2-A) (hereinafter referred to as "polymerizable liquid crystal compound (2-A)") was synthesized.

A nitrogen atmosphere was placed in a 100 mL four-necked flask equipped with a Dimroth condenser and a thermometer, and 11.02 g of compound (2-1a) synthesized with reference to the patent document (JP 2010-31223). 4.22 g of compound (2-2a) synthesized with reference to 2011-207765), 0.02 g of DMAP (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 0.20 g of BHT (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) , and 58 g of chloroform (manufactured by Kanto Kagaku Co., Ltd.) were added and mixed, and then 4.05 g of IPC (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and these were incubated at 0°C. The reaction was allowed to occur overnight. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was dropped into acetonitrile (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in an amount three times the mass of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 20 g of acetonitrile, and then dried under reduced pressure at 30° C. to obtain 11.75 g of polymerizable liquid crystal compound (2-A). The yield of polymerizable liquid crystal compound (2-A) was 81% based on compound (2-2a).

2. Solubility evaluation: Put 1.00 g of N-methylpyrrolidone (NMP) and a stirrer into a vial at 25°C, and add each of the above synthetic compounds while stirring with a magnetic stirrer (HS-30DN, AS ONE). The mixture was added until there was no undissolved material visually confirmed. When undissolved residue was confirmed, the solubility of each polymerizable compound in NMP was calculated as a weight percent concentration from (weight of each polymerizable compound)/(weight of each polymerizable compound + weight of NMP). The results were evaluated using the following criteria.
A: 20-30wt%
B: 10-20wt%
C: 5-10wt%
D: 0-5wt%
In addition to the above, similar solubility evaluations were performed using cyclopentanone or methyl ethyl ketone as the solvent. The results are shown in Table 2.

3. Measurement of thermal properties 1.00 g of each of the above polymerizable compounds was weighed into a vial tube, and further 2.00 g of chloroform was added and dissolved. The obtained solution was applied to a rubbed glass substrate with a PVA alignment film and dried. This substrate was placed on a cooling/heating device ("LNP94-2" manufactured by Japan Hitech), heated from room temperature to 150.degree. C., and then cooled to room temperature. The state of the temperature change was observed using a polarizing microscope (LEXT, manufactured by Olympus Corporation), and the temperature at which the phase transition occurred was measured. The results are shown in Table 2.

In the thermophysical properties in Table 2, "Cr" means crystalline phase, "I" means liquid phase, "Sm" means smectic liquid crystal phase, and "N" means nematic liquid crystal phase, and the temperature located between each symbol (°C ) indicates that the phase state has changed. For example, in Synthesis Example 1, the crystalline phase changed to the liquid phase at 65°C, and in Synthesis Example 6, the crystalline phase changed to the smectic liquid crystalline phase at 111°C, and the smectic liquid crystalline phase changed to the nematic liquid crystalline phase at 128°C. This shows that there was a phase transition from a nematic liquid crystal phase to a liquid phase at 132°C.

4. Preparation of mixed composition (1) Example 1
The polymerizable liquid crystal compound (2-A) obtained in Synthesis Example 7 and the polymerizable compound (1-A) obtained in Synthesis Example 1 were placed in a vial tube under the above HPLC measurement conditions. ) and the polymerizable liquid crystal compound (2-A) so that the peak area of the polymerizable compound (1-A) is 30% relative to the total peak area of 100% to obtain a mixture of polymerizable compounds (1). Ta. A photopolymerization initiator, a leveling agent, a polymerization inhibitor, and a solvent were added to 100 parts by mass of the mixture (1) according to the composition shown in Table 3, and the mixture was stirred at 80°C for 30 minutes using a carousel. 1) was obtained.
The blending amount of the solvent was set so that the mass % of the liquid crystal mixture was 13% with respect to the total amount of the mixed composition (solution).

Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan)
Leveling agent: polyacrylate compound (BYK-361N; manufactured by BYK Chemie Japan)
Polymerization inhibitor: BHT (manufactured by Wako Pure Chemical Industries, Ltd.)
Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Kagaku Co., Ltd.)

The thermal properties of the mixed composition (1) were confirmed using the same procedure as the method used to measure the thermal properties of the polymerizable compound, and the nematic phase transition temperature was 150°C.

(2) Example 2
A mixed composition (2) was prepared in the same manner as in Example 1, except that polymerizable compound (1-E) was used instead of polymerizable compound (1-A). The nematic phase transition temperature of mixed composition (2) was 137°C.

(3) Example 3
The polymerizable compound (1-A) and the polymerizable liquid crystal compound (2-A) were measured under the above HPLC measurement conditions, and the total peak area of the polymerizable compound (1-A) and the polymerizable liquid crystal compound (2-A) was 100 A mixed composition (3) was prepared in the same manner as in Example 1, except that the mixture was mixed so that the peak area of the polymerizable compound (1-A) was 3%.

(4) Example 4
The total peak area of the polymerizable liquid crystal compound (1-A) and the polymerizable liquid crystal compound (2-A) was measured using the HPLC measurement conditions described above. A mixed composition (4) was prepared in the same manner as in Example 1, except that the mixture was mixed so that the peak area of the polymerizable compound (1-A) was 50% relative to 100%.

(5) Comparative example 1
Pour the polymerizable liquid crystal compound (2-A) into a vial, add a polymerization initiator, leveling agent, polymerization inhibitor, and solvent according to the composition shown in Table 3, and stir at 80°C for 30 minutes using a carousel. A mixed composition (5) was obtained. The nematic phase transition temperature of mixed composition (5) was 154°C.

(6) Comparative example 2
A mixed composition (6) was obtained in the same manner as in Example 1, except that polymerizable compound (1-D) was used instead of polymerizable compound (1-A).

5. Creation of optical film (1) Preparation of composition for forming photo-alignment film The following components were mixed and the resulting mixture was stirred at 80° C. for 1 hour to obtain a composition for forming photo-alignment film.
Photoalignable material represented by the following formula (5 parts):

(Number average molecular weight: approx. 28,000)
Solvent (95 parts): cyclopentanone

(2) Production of optical film (retardation film) An optical film was produced as follows. Cycloolefin polymer film (COP) (ZF-14, manufactured by Zeon Corporation) was processed using a corona treatment device (AGF-B10, manufactured by Kasuga Denki Co., Ltd.) at an output of 0.3 kW and a processing speed of 3 m/min. Treated once. The composition for forming a photo-alignment film was applied with a bar coater to the corona-treated surface, dried at 80°C for 1 minute, and coated using a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.). , polarized UV exposure was performed with an integrated light amount of 100 mJ/cm ² . The thickness of the obtained alignment film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation) and was found to be 100 nm.

Mixed compositions (1) to (6) were applied onto the alignment film using a bar coater, dried at 120°C for 1 minute, and then heated using a high-pressure mercury lamp (Unicure VB-15201BY-A, Ushio Inc.) An optical film was produced by irradiating ultraviolet rays (under a nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: 1000 mJ/cm ² ) using a commercially available commercially available commercially available commercially available commercially available product.

Using the optical film produced above as a measurement sample, the front retardation values for light with wavelengths of 450 nm and 550 nm were measured using a measuring device ("KOBRA-WR" manufactured by Oji Scientific Instruments Co., Ltd.), and α value = Re1 ( 450)/Re1(550) was calculated. Note that the value of Re0(450)/Re0(550) was measured using a mixed composition (4) containing only the polymerizable liquid crystal compound (2-A) as a measurement sample.

6. Evaluation of crystallization temperature Mixed compositions (1) to (6) were applied onto the alignment film using a bar coater, and the substrate was placed on a cooling and heating device and dried at 120°C for 1 minute. Cooled to room temperature. The changes in temperature were observed using a polarizing microscope, and the temperature at which crystals formed was measured. The results are shown in Table 4.

As shown in Table 4, according to the mixed composition of the present invention, the crystallization temperature can be lowered.

7. Evaluation of orientation defects The optical film produced above was cut into 10 cm square pieces, and the number of orientation defects on the screen was visually confirmed using a polarizing microscope (LEXT, manufactured by Olympus Corporation) for evaluation. In the mixed compositions of Examples 1 to 3, there were no orientation defects at all, but in the mixed composition of Example 4, in which the area percentage value of the polymerizable compound (1) was 50%, orientation defects occurred, and the polymerizable compound ( It has been found that if the amount of 1) is too large, it may affect the optical properties of the resulting optical film.

Claims

A polymerizable compound represented by the following formula (1).

[In formula (1),
L is selected from the group consisting of a single bond, an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbonyl group, and the hydrogen atom contained in the aliphatic hydrocarbon group is a halogen atom, -R 10 , -OR 10 may be substituted with a cyano group or a nitro group, and when L is an aliphatic hydrocarbon group having 2 to 13 carbon atoms, -CH 2 - contained in the aliphatic hydrocarbon group is - May be substituted with O-, -S-, -CO-O-, -O-CO- or -NH- (however, if multiple -O- and/or -S- exist, these may be substituted with each other) (not adjacent), R 10 represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
m represents 0 or 1,
D 1 and D 2 are each independently -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, - Represents OC(=S)-, -OC(=S)-O-, -CO-NR 11 -, -NR 12 -CO-, or a single bond, and R 11 and R 12 are each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,
E 1 , E 2 , B 1 and B 2 each independently represent -CR 11 R 12 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO -, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -O-C(=S)-O-, -CO-NR 11 -, - NR 12 represents -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond, and R 11 and R 12 each independently, Represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms (however, when m is 0, E 1 and E 2 are -CR 11 R 12 -, -CH 2 -CH 2 -, -O- CH 2 -, -CH 2 -O-, -S-CH 2 - and -CH 2 -S-),
G 1 and G 2 each represent a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group,
A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; The hydrogen atoms contained in the group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R 13 , -OR 13 , a cyano group, or a nitro group, and R 13 is an alkyl group having 1 to 4 carbon atoms. represents, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
F 1 and F 2 each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR 14 or a halogen atom, and R 14 represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH 2 - contained in the alkanediyl group is -O- or - May be replaced with CO-,
P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 1 and P 2 is a polymerizable group). ]
The polymerizable compound according to claim 1, which is non-liquid crystalline.
The polymerizable compound according to claim 1, wherein L in formula (1) is an unsubstituted acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms or a carbonyl group.
A mixed composition of the polymerizable compound according to claim 1 and a polymerizable liquid crystal compound different from the polymerizable compound.
The mixed composition according to claim 4, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by formula (2).

[In formula (2),
Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent,
D 21 , D 22 , E 21 , E 22 , B 21 and B 22 each independently represent -CR 11 R 12 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O -, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO -NR 11 -, -NR 12 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond, R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,
G 21 and G 22 each represent a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group,
A 21 and A 22 each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; The hydrogen atoms contained in the group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R 13 , -OR 13 , a cyano group, or a nitro group, and R 13 is an alkyl group having 1 to 4 carbon atoms. represents, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
F 21 and F 22 each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with -OR 14 or a halogen atom, and R 14 represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH 2 - contained in the alkanediyl group is -O- or - May be replaced with CO-,
P 21 and P 22 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 21 and P 22 is a polymerizable group). ]
The mixed composition has formula (i):
Re1 (450) / Re1 (550) ≧ Re0 (450) / Re0 (550) (i) [In formula (i), Re0 (λ) is the in-plane area at the wavelength λ nm of the cured film formed from the polymerizable liquid crystal compound. Re1 (λ) represents the in-plane retardation value at the wavelength λ nm of the cured film formed from the mixed composition]
The mixed composition according to claim 4, which satisfies the following.
P 1 , F 1 , B 1 , A 1 and E 1 in formula (1) are respectively the same as P 21 , F 21 , B 21 , A 21 and E 21 in formula (2), and the formula ( Claim 5, wherein P 2 , F 2 , B 2 , A 2 and E 2 in 1) are the same as P 22 , F 22 , B 22 , A 22 and E 22 in formula (2), respectively. Mixture composition as described.
The mixed composition according to claim 5, wherein Ar in formula (2) is a group represented by any one of formulas (Ar-1) to (Ar-5).

[In formulas (Ar-1) to (Ar-5),
* represents a joint;
Q 1 represents -S-, -O- or -NR 15 -, R 15 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W 1 and W 2 each independently represent -O-, -S-, -CO-, -NR 15 -, and R 15 is a hydrogen atom or a carbon number of 1 to 6 which may have a substituent. represents an alkyl group;
Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group,
Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. -CH 2 - may be substituted with -O-, -CO-, -O-CO- or -CO-O-;
Z 1 , Z 2 and Z 3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon atom 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR 15 R 16 or -SR 15 , and Z 1 and Z 2 are bonded to each other to form an aromatic ring or aromatic heterocycle. R 15 and R 16 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ax and Ay are a bond. may form a ring;
Y 3 and Y 4 each independently represent the following formula (Y 3 -1):

[In formula (Y 3 -1),
R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X 3 , and the substituent X 3 is a fluorine atom, a chlorine atom, Bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethyl A silyl group, a thioisocyano group, or one -CH 2 - or two or more non-adjacent -CH 2 -s each independently represent -O-, -S-, -CO-, -COO-, - OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO- , -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, a linear or Represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or it may be a group represented by -B 31 -F 31 -P 31 , B 31 , F 31 and P 31 are respectively defined in the same manner as B 21 , F 21 and P 21 in the formula (2), and are the same as B 21 , F 21 and P 21 in the formula (2), respectively. May be present or different;
U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group is , may be substituted by one or more of the above substituents X3 ;
T 1 is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU 2 -, -CO-NU 2 -, -OCO-NU 2 - or O-NU 2 -, and U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group. (Any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E 31 -A 31 ) q -B 32 -F 32 - P32 , and each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents X3 , and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH 2 - or two or more non-adjacent -CH 2 -s in the alkyl group are each independently substituted with -O -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO 2 -, -O-CO-O-, -CO-NH-, - NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or - It may be replaced by C≡C-, and one -CH 2 - or two or more non-adjacent -CH 2 -s in the cycloalkyl group or cycloalkenyl group are each independently -O-, -CO-, -COO-, -OCO- or O-CO-O- may be substituted, and E 31 , A 31 , B 32 , F 32 and P 32 are each E in formula (2). 21 , A 21 , B 21 , F 21 and P 21 and may be the same or different from E 21 , A 21 , B 21 , F 21 and P 21 , respectively, and q is 0. It represents an integer of ~4, and if there are multiple E 31 and/or A 31 , they may be the same or different, and U 1 and U 2 may combine to form a ring. good〕
represents a group selected from ]
The mixed composition according to claim 5, wherein A 21 and A 22 in formula (2) are each independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group.
The mixed composition according to claim 5, wherein P21 and P22 in formula (2) are each an acryloyloxy group.
The area percentage value measured by liquid chromatography of the polymerizable compound represented by formula (1) is the polymerizable compound represented by formula (2) and the polymerizable compound represented by formula (1) contained in the mixed composition. The mixed composition according to claim 5, wherein the mixed composition is 1% or more and less than 50% based on the total area value of the liquid crystal compounds.
The mixed composition according to claim 4, further comprising a photopolymerization initiator.
The mixed composition according to claim 4, further comprising an organic solvent.
A retardation film comprising a cured liquid crystal film that is a cured product of the mixed composition according to claim 4.
The liquid crystal cured film has the formula (ii):
0.75≦Re(450)/Re(550)<1.00 (ii)
[In formula (ii), Re (λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured film]
The retardation film according to claim 14, which satisfies the following.
An elliptically polarizing plate comprising the retardation film according to claim 14.
An optical display comprising the elliptically polarizing plate according to claim 16.
A flexible image display device comprising the elliptically polarizing plate according to claim 16.