WO2022168607A1

WO2022168607A1 - Polymerizable liquid crystal mixture and polymerizable liquid crystal composition

Info

Publication number: WO2022168607A1
Application number: PCT/JP2022/001808
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: 2021-02-05
Filing date: 2022-01-19
Publication date: 2022-08-11
Also published as: TW202242075A; KR20230138450A; CN116745664A; JP2022120659A

Abstract

A polymerizable liquid crystal compound represented by formula (1) that is capable of lowering the phase transition temperature of a liquid crystal composition without impairing optical characteristics.

Description

Polymerizable liquid crystal mixture, polymerizable liquid crystal composition

The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, a retardation film, a polarizing plate and an optical display formed from the polymerizable liquid crystal composition.

As an optical film such as a retardation film used in a flat panel display (FPD), for example, a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent is applied to a supporting substrate, and then obtained by polymerization. I have an optical film. Conventionally, as a polymerizable liquid crystal compound, for example, a nematic liquid crystal compound having a rod-like structure in which about 2 to 4 six-membered rings are linked is known.
On the other hand, the retardation film is required to be capable of polarization conversion in the entire wavelength region as one of its characteristics. In the wavelength range where the value [Re(λ)/Re(550)] divided by (550) is close to 1, or the wavelength range exhibiting the reverse chromatic dispersion of [Re(450)/Re(550)]<1, It is known that uniform polarization conversion is theoretically possible. Polymerizable liquid crystal compounds that can constitute such a retardation film are disclosed in Patent Documents 1 to 3, for example.

JP 2016-121339 A JP 2019-156733 A Japanese Patent Application Laid-Open No. 2020-41026

When aligning the polymerizable liquid crystal compound, for example, after applying a coating liquid containing the polymerizable liquid crystal compound to the supporting substrate, it is necessary to heat it to a temperature higher than the phase transition temperature of the polymerizable liquid crystal compound to cause the phase transition. If the phase transition temperature of the polymerizable liquid crystal compound is high, the support substrate may be adversely affected, usable support substrates may be restricted, and the heating temperature may be high, resulting in poor production efficiency. Further, if an additive is added to the polymerizable liquid crystal compound for the purpose of lowering the phase transition temperature, the additive disturbs the molecular orientation of the liquid crystal compound, and the desired optical properties may not be obtained. Furthermore, the desired optical properties may not be obtained due to precipitation of the additive or the polymerizable liquid crystal compound as crystals.

An object of the present invention is to provide a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing optical properties.

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 aspects.
[1] A polymerizable liquid crystal compound represented by formula (1).

[In formula (1),
k11, k12 and l each independently represent an integer of 1 or more;
B ¹¹ and B ¹² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, or a single bond, and R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or represents an alkyl group having 1 to 4 carbon atoms;
E ¹¹ and E ¹² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, or a single bond; G ¹¹ and G ¹² each independently represent a C 3-16 represents a divalent alicyclic hydrocarbon group, hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group or a nitro group, —CH ₂ — contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—, R ³ represents an alkyl group having 1 to 4 carbon atoms, A hydrogen atom contained in the alkyl group may be substituted with a fluorine atom;
A ¹¹ and A ¹² 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; A hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group or a nitro group;
F ¹¹ and F ¹² 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 ³ or a halogen atom, and the alkane —CH ₂ — contained in the diyl group may be replaced with —O— or —CO—;
P ¹¹ and P ¹² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹¹ and P ¹² is a polymerizable group);
each M independently represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms which may have a substituent;
Ar ¹¹ and Ar ¹² each independently represent a divalent aromatic group which may have a substituent. ]
[2] M in formula (1) is an optionally substituted divalent aliphatic hydrocarbon group having 2n carbon atoms (n represents an integer of 2 to 4), ] The polymerizable liquid crystal compound according to .
[3] Ar ¹¹ and Ar ¹² in formula (1) are each independently a group represented by any one of the following formulas (Ar-1) to (Ar-5), above [1] or [ 2].

[In the formulas (Ar-1) to (Ar-5),
* represents a bond;
Q ¹ represents -S-, -O- or -NR ¹¹ -, R ¹¹ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms,
Q ² represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms;
W ¹ and W ² each independently represent —O—, —S—, —CO—, —NR ¹¹ —, and R ¹¹ is a hydrogen atom or an optionally substituted C 1-6 represents an alkyl group;
Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group;
Y ² represents a CN group or an optionally substituted alkyl group having 1 to 12 carbon atoms, 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 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon number ⁶ to ²⁰ aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, —NR ¹¹ R ¹² or —SR ¹¹ ; may be formed, and R ¹¹ and R ¹² 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 having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; Ay represents a hydrogen atom; 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 heterocyclic ring; may be joined to form a ring;
Y ³ and Y ⁴ each independently represent the following formula (Y ³ -1):

[In the 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 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 - are 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- which may be replaced by a straight chain having 1 to 20 carbon atoms or represents a branched alkyl group, any hydrogen atom in which may be substituted with a fluorine atom, or may be a group represented by -B ³¹ -F ³¹ -P ³¹ , and B ³¹ , F ³¹ and P ³¹ are defined in the same manner as B ¹¹ , F ¹¹ and P ¹¹ in formula (1) above, and are the same as B ¹¹ , F ¹¹ and P ¹¹ in formula (1) respectively. may be different;
U ¹ represents 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, and the aromatic hydrocarbon group is , optionally substituted by one or more of said substituents X ³ ;
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, 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 heteroatom) or an organic group having 2 to 30 carbon atoms, or (E ³¹ -A ³¹ ) _q -B ³² -F ³² - P ³² , the alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group may each be unsubstituted or substituted by one or more substituents X ³ , the alkyl group may be substituted by said cycloalkyl group or cycloalkenyl group, and one —CH ₂ — or two or more non-adjacent —CH ₂ — in said 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 - may be replaced by C≡C-, and one —CH ₂ — or two or more non-adjacent —CH ₂ — in the cycloalkyl group or cycloalkenyl group are each independently —O—, —CO—, —COO—, —OCO— or O—CO—O—, and E ³¹ , A ³¹ , B ³² , F ³² and P ³² are each E in formula (1) ¹¹ , A ¹¹ , B ¹¹ , F ¹¹ and P ¹¹ , which may be the same as or different from E ¹¹ , A ¹¹ , B ¹¹ , F ¹¹ and P ¹¹ , respectively, q is 0 represents an integer of to 4, and when there are a plurality of 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 ]
[4] A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of [1] to [3] and a polymerizable liquid crystal compound represented by formula (2).

[In formula (2),
k21 and k22 each independently represent an integer of 1 or more;
B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, or a single bond, and R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or It represents an alkyl group having 1 to 4 carbon atoms.
E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, or a single bond; G ²¹ and G ²² each independently represent a C 3-16 represents a divalent alicyclic hydrocarbon group, hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group or a nitro group, —CH ₂ — contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—, R ³ represents an alkyl group having 1 to 4 carbon atoms, A hydrogen atom contained in the alkyl group may be substituted with a fluorine atom;
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; A hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group or a nitro group;
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 ³ or a halogen atom, and the alkane —CH ₂ — contained in the diyl group may be replaced with —O— or —CO—;
P21 and ^P22 each independently represent a hydrogen atom or a polymerizable group ⁽ provided that at least one of ^P21 and ^P22 is a polymerizable group);
Ar ²¹ each independently represents a divalent aromatic group which may have a substituent. ]
[5] The ratio of the peak area of the polymerizable liquid crystal compound (1) to the total peak area of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) measured by liquid chromatography is 0.1% or more. The polymerizable liquid crystal composition according to the above [4], which is 50% or less.
[6] The groups represented by A ¹¹ , A ¹² , B ¹¹ , B ¹² , E ¹¹ , E ¹² , F ¹¹ , F ¹² , G ¹¹ , G ¹² , P ¹¹ and P ¹² in formula (1) are , respectively, groups represented by A ²¹ , A ²² , B ²¹ , B ²² , E ²¹ , E ²² , F ²¹ , F ²² , G ²¹ , G ²² , P ²¹ and P ²² in formula (2); [4] or [5] above, wherein the groups represented by Ar ¹¹ and Ar ¹² in formula (1) are the same as the groups represented by Ar ²¹ in formula (2). The polymerizable liquid crystal composition according to 1.
[7] The polymerizable liquid crystal composition according to any one of [4] to [6], further comprising a photopolymerization initiator and an organic solvent.
[8] A retardation film formed from the polymerizable liquid crystal composition according to any one of [4] to [7].
[9] A polarizing plate comprising the retardation film of [8] above.
[10] An optical display comprising the polarizing plate of [9] above.

According to the present invention, it is possible to provide a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing the optical properties.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the gist of the present invention.

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

is represented by Hereinafter, the polymerizable liquid crystal compound of the present invention represented by formula (1) is also referred to as "polymerizable liquid crystal compound (1)".

In formula (1), k11 and k12 each independently represent an integer of 1 or more, and may be an integer of 1 to 5, for example. The sum of k11 and k12 is preferably 2-6, more preferably 2-4. From the viewpoint of excellent liquid crystallinity, k11 and k12 are each independently preferably 1 or 2. From the viewpoint of ease of production of the polymerizable liquid crystal compound (1), k11 and k12 are the same number. Preferably, k11 and k12 are both 1 in one preferred embodiment of the invention.

In formula (1), l represents an integer of 1 or more, and may be an integer of 1 to 8, for example. l is preferably 1 to 6 from the viewpoint of excellent liquid crystallinity.

In formula (1), B ¹¹ and B ¹² each independently represent -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO -, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -,- NR ² —CO—, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S— or a single bond, wherein R ¹ and R ² each independently It represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. B ¹¹ and B ¹² each independently represent -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹ -, -NR ² -CO-, -CH ₂ -O -, -O-CH ₂ -, -CH ₂ -S-, -S-CH ₂ - or a single bond is preferred, and -O-CO- or -CO-O- is more preferred. When a plurality of B ¹¹ and B ¹² are present, they may be the same or different from each other, but from the viewpoint of ease of production of the polymerizable liquid crystal compound (1), the plurality of B ¹¹ are the same is preferably a group, and the plurality of B ¹² are preferably the same group. Moreover, it is more preferable that all of B ¹¹ and B ¹² are the same.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, tert-butyl group and the like, preferably carbon It is an alkyl group of number 1 or 2, more preferably a methyl group.

In formula (1), E ¹¹ and E ¹² each independently represent -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO -, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -,- represents NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; E ¹¹ and E ¹² are each independently preferably -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹ -, -NR ² -CO-, -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -S-, -S-CH ₂ - or a single bond, more preferably -O-CO- or -CO-O-. From the viewpoint of ease of production of the polymerizable liquid crystal compound (1), E ¹¹ and E ¹² may be the same or different, but are preferably the same group.

G ¹¹ and G ¹² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. A hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group or a nitro group, and the —CH _2- may be substituted with -O-, -S- or -NH-. R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. Examples of the divalent alicyclic hydrocarbon groups having 3 to 16 carbon atoms represented by G ¹¹ and G ¹² include heteroatoms represented by formulas (g-1) to (g-10). A good divalent alicyclic hydrocarbon group can be mentioned, and a 5- or 6-membered ring alicyclic hydrocarbon group is preferred.

The groups represented by the above formulas (g-1) to (g-10) are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group and tert-butyl group; alkoxy group having 1 to 4 carbon atoms; fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; cyano group; nitro group; optionally substituted with a halogen atom such as fluorine atom, chlorine atom and bromine atom .

G ¹¹ and G ¹² are each more preferably a 5- or 6-membered alicyclic hydrocarbon group represented by any one of formulas (g-1) to (g-4), and the formula (g A 6-membered alicyclic hydrocarbon group represented by -1) is more preferred, a cyclohexane-1,4-diyl group is particularly preferred, and a trans-cyclohexane-1,4-diyl group is particularly preferred.
G ¹¹ and G ¹² may be the same or different, but if they are the same, it is advantageous in terms of industrial ease of production and productivity of the polymerizable liquid crystal compound (1).

In formula (1), A ¹¹ and A ¹² 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 alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group or a nitro group.

As 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 ¹¹ and A ¹² , the above formulas (g-1) to An alicyclic hydrocarbon group consisting of a 5- or 6-membered ring represented by the formula (g-10), or a C6-20 represented by the formulas (a-1) to (a-8) degree of aromatic hydrocarbon groups.

As A ¹¹ and A ¹² , some of the hydrogen atoms of the groups exemplified above are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group or tert-butyl group; methoxy group or ethoxy group; alkoxy groups having 1 to 4 carbon atoms such as groups; fluoroalkyl groups having 1 to 4 carbon atoms such as trifluoromethyl groups; cyano groups; nitro groups; may

A ¹¹ and A ¹² are preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group. When k11 and k12 are 1, A ¹¹ and A ¹² are each preferably a 1,4-phenylene group, and when ^{k11 and k12 are 2 or more, A 11} ^and A ¹² bound to E ¹² is preferably the same as each other, and A ^{11 bound to E 11} ^and A ¹² bound to E ¹² are preferably 1,4-phenylene groups. When multiple A ¹¹ and A ¹² are present, they may be the same or different.

In formula (1), F ¹¹ and F ¹² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is substituted with —OR ³ or a halogen atom. -CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-. F ¹¹ and F ¹² are each independently preferably an alkanediyl group having 3 to 10 carbon atoms, —(CF ₂ ) ₄ —, —(CF ₂ ) ₆ —, —(CF ₂ ) ₈ —, and the number of carbon atoms 4 or 6 alkanediyl groups [-(CH ₂ ) ₄ - or -(CH ₂ ) ₆ -] are more preferred. E ¹¹ and E ¹² may be the same or different from each other, but when they are the same, it is advantageous in terms of industrial easiness of production and productivity of the polymerizable liquid crystal compound (1).

^P11 and ^P12 each independently represent a hydrogen atom or a polymerizable group. At least one of P ¹¹ and P ¹² is a polymerizable group, and both P ¹¹ and P ¹² are polymerizable groups. is preferable from the viewpoint of

The polymerizable group may be any reactive group capable of polymerizing the polymerizable liquid crystal 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, N-alkylamino group having 1 to 4 carbon atoms, amino group, oxiranyl group, oxetanyl group, formyl group, isocyanato group, isothiocyanato group, and the like. In addition, the polymerizable group may contain an ether bond or an ester bond that connects the group exemplified above and ^F11 or ^F12 , and it is preferable that they bond via an ether bond. As P ¹¹ and P ¹² , for example, a radically polymerizable group or a cationically polymerizable group suitable for photopolymerization is preferable. groups are preferred, and acryloyloxy groups are more preferred.

In formula (1), each M independently represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms which may have a substituent. When M in the formula (1) is a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms, another polymerizable liquid crystal having a structure similar to the polymerizable liquid crystal compound (1) in the molecular structure. Compounds such as the polymerizable liquid crystal compound represented by the formula (2) described later can be easily improved in solubility in a solvent, and the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound is excellent. Since it is excellent in the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound, a cured liquid crystal film can be obtained from the polymerizable liquid crystal compound at a lower processing temperature, so the effect of heating on the optical properties of the cured liquid crystal film can be reduced. It is also advantageous in terms of manufacturing efficiency. Such effects tend to be significantly enhanced, particularly when M in formula (1) is a structure having a cyclic structure such as an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The reason for this is, but is not limited to, the fact that the group M located between the divalent aromatic groups (Ar ¹¹ and/or Ar ¹² ) does not have a rigid cyclic structure, resulting in the It is speculated that the increased flexibility facilitates the improvement of the solubility, resulting in a significant decrease in the phase transition temperature.

The divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be linear or branched, and may be saturated or unsaturated. A saturated hydrocarbon group is preferable, and a linear saturated hydrocarbon group is more preferable. Specific examples of the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms include n-propanediyl group, i-propanediyl group, n-butanediyl group, n-pentanediyl group and n-hexanediyl group. , n-heptanediyl group, n-octanediyl group, n-nonanediyl group, n-decanediyl group and other alkanediyl groups having 3 to 13 carbon atoms. When there are multiple Ms, they may be the same or different.

A hydrogen atom contained in the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be replaced with a substituent. When M in formula (1) is a divalent aliphatic hydrocarbon group of 3 to 13 having a substituent, it is preferred that there is no cyclic structure in M including the substituent. In other words, the polymerizable liquid crystal compound (1) of the present invention is represented by the group Ar ¹¹ in the structure represented by -(Ar ¹¹ -O-CO-M-CO-O)- in formula (1). It does not contain a cyclic structure other than an alicyclic hydrocarbon group or an aromatic hydrocarbon group. Examples of substituents that the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may have include a halogen atom and an alkoxyl group having 1 to 4 carbon atoms.
The number of carbon atoms contained in the substituent is not included in the number of carbon atoms possessed by the aliphatic hydrocarbon group represented by M in formula (1).

Furthermore, M in the formula (1) is a divalent aliphatic hydrocarbon group having 2n carbon atoms (n represents an integer of 2 to 4) which may have a substituent, the polymerizable liquid crystal While sufficiently securing the effect of lowering the phase transition temperature of the compound and the effect of improving the solubility, the obtained liquid crystal cured film can exhibit more excellent reverse wavelength dispersion. The divalent aliphatic hydrocarbon group having 2n carbon atoms is preferably an alkanediyl group having 2n carbon atoms, and specific examples include n-butanediyl group, n-hexanediyl group and n-octanediyl group.

M in formula (1) is preferably an optionally substituted divalent alkanediyl group having 3 to 11 carbon atoms, more preferably an optionally substituted carbon number of 4 to 10 A divalent alkanediyl group of, more preferably a divalent alkanediyl group having 4, 6 or 8 carbon atoms which may have a substituent, particularly preferably an n-butanediyl group, an n-hexanediyl group and n - is an octanediyl group.

In formula (1), Ar ¹¹ and Ar ¹² each independently represent a divalent aromatic group which may have a substituent. The divalent aromatic group which may have a substituent may be a divalent aromatic heterocyclic group and a divalent aromatic heterocyclic group. In the present invention, the divalent aromatic hydrocarbon group optionally having a substituent means a divalent linking group containing at least one aromatic hydrocarbon ring, even if it has a substituent A good divalent aromatic heterocyclic group means a divalent linking group containing at least one aromatic heterocyclic ring. The aromatic hydrocarbon ring and aromatic heterocyclic ring referred to herein are those having [4n+2] (n represents an integer) number of π electrons in the ring structure according to Hückel's rule (in the case of an aromatic heterocyclic ring, -N= and -S- which satisfy Hückel's rule including non-covalently bonded electron pairs on heteroatoms such as -S-. Ar ¹¹ and Ar ¹² may contain one aromatic hydrocarbon ring or aromatic heterocyclic ring, or may contain two or more. When containing one aromatic hydrocarbon ring or aromatic heterocyclic ring, Ar ¹¹ and Ar ¹² may each independently be a divalent aromatic hydrocarbon group which may have a substituent, It may be a divalent aromatic heterocyclic group optionally having a substituent. When it contains two or more aromatic hydrocarbon rings or aromatic heterocycles, it may contain only an aromatic hydrocarbon ring or only a plurality of aromatic heterocycles, and the aromatic hydrocarbon ring and the aromatic heterocycle may include 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, a divalent linking group such as -CO-O-, -O-.

Ar ¹¹ and Ar ¹² may be the same or different from each other, but when they are the same, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (1). In addition, when a plurality of Ar ¹¹ are present, the plurality of Ar ¹¹ may be the same or different, but are preferably the same group, and the plurality of Ar ¹¹ and Ar ¹² are all the same. more preferred.

Examples of the aromatic hydrocarbon ring that can be included in Ar ¹¹ and Ar ¹² include benzene ring, naphthalene ring, anthracene ring and the like, with benzene ring and naphthalene ring being preferred.
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, A thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, a phenanthroline ring, and the like are included. When Ar ¹¹ and Ar ¹² contain nitrogen atoms, the nitrogen atoms preferably have π electrons.

Among them, Ar ¹¹ and Ar ¹² preferably have an aromatic heterocyclic ring containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, a thiazole ring, a benzothiazole ring or a benzofuran ring and more preferably a benzothiazole ring. When Ar ¹¹ and Ar ¹² have an aromatic heterocyclic ring containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, the aromatic heterocyclic ring is constitutes a divalent linking group constituting the main chain of the compound represented by formula (1) by directly bonding to —CO—O— or —O—CO— adjacent to G ¹¹ , M or G ¹² of may be contained as a substituent of a divalent linking group that directly bonds to -CO-O- or -O-CO- adjacent to G ¹¹ , M or G ¹² , respectively; It is preferable that the entire Ar ¹¹ or Ar ¹² group including the aromatic heterocycle is sterically arranged in a direction substantially orthogonal to the molecular orientation direction.

In formula (1), the total number of π electrons contained in the optionally substituted divalent aromatic groups represented by Ar ¹¹ and Ar ¹² N _π is preferably 8 or more and more Preferably 12 or more, particularly preferably 16 or more, particularly preferably 20 or more. Also, it is preferably 36 or less, more preferably 32 or less, still more preferably 30 or less, particularly preferably 26 or less, and most preferably 24 or less.

The optionally substituted divalent aromatic groups represented by Ar ¹¹ and Ar ¹² in formula (1) are represented by the following formulas (Ar-1) to (Ar-5). group.

In formulas (Ar-1) to (Ar-5), * represents a bond.

In formula (Ar-1), Q ¹ represents -S-, -O- or -NR ¹¹ -, and R ¹¹ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. . In formulas (Ar-3) and (Ar-4), ^Q2 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.

In formula (Ar-2), W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹¹ -, and R ¹¹ is 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 optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group. In formula (Ar-2), Y ² represents a CN group or an optionally substituted alkyl group having 1 to 12 carbon atoms. Here, a 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 - It 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 ¹¹ R ¹² or —SR ¹¹ , Z ¹ and Z ² may combine with each other to form an aromatic or heteroaromatic ring. R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formulas (Ar-3) and (Ar-4), Ax is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. Ay is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, It represents an organic group having 2 to 30 carbon atoms, and Ax and Ay may combine to form a ring.

In formula (Ar-1), Y ¹ is preferably an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group, having 6 to 6 carbon atoms which may be substituted. 12 aromatic hydrocarbon groups or C 3-12 aromatic heterocyclic groups are more preferred. The optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group is preferably an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. As used herein, the term "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and a condensed aromatic hydrocarbon group formed by condensing two or more aromatic rings. A hydrocarbon group and an aromatic hydrocarbon group formed by combining two or more aromatic rings are included. "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 aromatic rings and heteroaromatic rings. , an aromatic heterocyclic group formed by condensing one or more aromatic heterocyclic rings with 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 aromatic heterocyclic groups formed by bonding with at least one ring selected from the group consisting of rings and heteroaromatic rings.

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. C1-6 alkylsulfonyl group, carboxy group, C1-6 fluoroalkyl group, C1-6 alkoxy group, C1-6 alkylsulfanyl group, C1-4 N-alkylamino groups, N,N-dialkylamino groups having 2 to 8 carbon atoms, sulfamoyl groups, N-alkylsulfamoyl groups having 1 to 6 carbon atoms and N,N-dialkylsulfa groups having 2 to 12 carbon atoms A moyl group is mentioned.

Y ¹ includes, for example, groups represented by the following formulas (Y ¹ -1) to (Y ¹ -7).

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

In formulas (Y ¹ -1) to (Y ¹ -7), each Z ⁴ 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, nitroxide 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 and trifluoromethyl group are more preferred, methyl group, ethyl group, isopropyl group and sec-butyl , pentyl and hexyl groups are particularly preferred.

In formulas (Y ¹ -1) to (Y ¹ -7), V ¹ and V ² are each independently -CO-, -S-, -NR ¹³ -, -O-, -Se- or - represents SO ₂ -, preferably -S-, -NR ¹³ - or -O-. R ¹³ 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), each a independently represents an integer of 0 to 3, preferably 0 or 1. Each b independently represents an integer of 0 to 2, preferably 0.

Any group represented by formulas (Y ¹ -1) to (Y ¹ -7) is any group represented by formulas (Y ¹ -8) to (Y ¹ -13) below. is preferred, and a group represented by formula (Y ¹ -8) is more preferred. In addition, * part represents a connection part.

In formulas (Y ¹ -8) to (Y ¹ ^-13 ), Z ⁴ , ^a , b, V ¹ , V ² and W ³ are 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 them, groups represented by the following formulas are preferable.

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). In the formula, the * part represents a connecting part.

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

In one embodiment of the present invention, specific examples of the group represented by formula (Ar-3) include groups represented by the following formulas (Ar ³ -1) to (Ar ³ -23). In the formula, the * part represents a connecting part.

The groups represented by formulas (Ar-1) to (Ar-4) are, in addition to the groups specifically exemplified above, for example, JP-A-2011-207765, JP-A-2008-107767, WO2014/ It may be a group described in JP-A-010325 or the like.

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

is selected from 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 ^optionally substituted by one or more substituents X3.

Substituent X ³ is 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 — are 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 which may be optionally substituted with a fluorine atom in the alkyl group, or —B ³¹ —F ³¹ —P ³¹ B ³¹ , F ³¹ and P ³¹ are defined in the same manner as B ¹¹ , F ¹¹ and P ¹¹ in formula (1) above, respectively, and may be the same as or different from B ¹¹ , F ¹¹ and P ¹¹ of

Substituent X ³ is preferably fluorine atom, chlorine atom, —CF ₃ , —OCF ₃ or cyano group. R ^Y1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms substituted with one or more fluorine atoms, 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 aromatic hydrocarbon rings and aromatic heterocycles , is an organic group having 2 to 30 carbon atoms. The aromatic hydrocarbon group may be substituted with one or more of said substituents ^X3 .

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

Specifically, U1 preferably has ^a group represented by the following formula. ^In the following formulas, these groups have bonds with T1 at arbitrary positions.

In formula (Y ³ -1), T ¹ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO- represents 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 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 heteroatom), or (E ³¹ -A ³¹ ) represents _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 by one or more substituents X3 ^, and the alkyl group may be the cycloalkyl group or optionally substituted by a cycloalkenyl group. One -CH ₂ - or two or more non-adjacent -CH ₂ - 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 - in an alkenyl group each independently represent -O-, -CO-, -COO-, -OCO- or O-CO-O - may be replaced. E ³¹ , A ³¹ , B ³² , F ³² and P ³² are defined in the same manner as E ¹¹ , A ¹¹ , B ¹¹ , F ¹¹ and P ¹¹ in formula (1), respectively, and E ¹¹ , A ¹¹ , B ¹¹ , ^F ¹¹ and P ¹¹ may be the same or different; ^q represents an integer of 0 to 4; may be different.

T ¹ is preferably -O-, -S-, -N=CU ² - or -NU ² - in terms of good birefringence and easy synthesis, and improves wavelength dispersion and birefringence. —O—, —S—, or —NU ² — are more preferable because they are easy to make.

U ² may be substituted with one or more of the aforementioned substituents X ³ , and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —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 by -CO-, -COO-, -OCO- or -O-CO-O-, or A cycloalkenyl group having 3 to 12 carbon atoms, or the alkyl or alkenyl group optionally substituted by the cycloalkyl group, cycloalkenyl group, or aryl group is preferred.

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

U ¹ and U ² may combine to form a ring. In that case, for example, a cyclic group represented by -NU ¹ U ² or a cyclic group represented by -N=CU ¹ U ² can be mentioned.

Y ³ and Y ⁴ are each selected from the following formulas (Y ^3′ -1) to (Y ^3′ -47) in view 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 (1), making it easy to manufacture industrially, and improving the productivity, the group represented by the formula (Ar-5) specifically includes: The following groups are mentioned. * in (Ar ⁵ -1) to (Ar ⁵ -20) below represents a bond with -CO-O- or -O-CO- adjacent to G ¹¹ , M or G ¹² .

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 is Formula (Ar-1), and more preferred is Formula (Ar-1).

*-O-CO-G ¹¹ -E ¹¹ -(A ¹¹ -B ¹¹ ) _k11 -F ¹¹ -P ¹¹ and *-O-CO-G ¹² -E ¹² -(A ¹² -B ¹² ) _k12 -F ¹² -P ¹² include structures represented by formulas (R-1) to (R-100).
In the formula, * represents a bond to Ar ¹¹ or Ar ¹² , and n represents an integer of 2-12. The cyclohexane ring may be trans-form or cis-form, but preferably trans-form.

The polymerizable liquid crystal composition of the present invention comprises the polymerizable liquid crystal compound (1) of the present invention and formula (2):

[In formula (2),
k21 and k22 each independently represent an integer of 1 or more;
B ²¹ and B ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, or a single bond, and R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or It represents an alkyl group having 1 to 4 carbon atoms.
E ²¹ and E ²² are each independently -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹ -, -NR ² -CO-, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, or a single bond; G ²¹ and G ²² each independently represent a C 3-16 represents a divalent alicyclic hydrocarbon group, hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, -R ³ , -OR ³ , a cyano group or a nitro group, —CH ₂ — contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—, R ³ represents an alkyl group having 1 to 4 carbon atoms, A hydrogen atom contained in the alkyl group may be substituted with a fluorine atom;
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; A hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group or a nitro group;
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 ³ or a halogen atom, and the alkane —CH ₂ — contained in the diyl group may be replaced with —O— or —CO—;
P21 and ^P22 each independently represent a hydrogen atom or a polymerizable group ⁽ provided that at least one of ^P21 and ^P22 is a polymerizable group);
Ar ²¹ each independently represents a divalent aromatic group which may have a substituent. ]
(hereinafter also referred to as "polymerizable liquid crystal compound (2)"). To effectively lower the phase transition temperature of the polymerizable liquid crystal compound (2) while suppressing the occurrence of alignment defects by using the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in combination. can be done. Although the reason for this is not clear, when the polymerizable liquid crystal compound (1) of the present invention and the polymerizable liquid crystal compound (2) have structural units similar to each other, M in formula (1) is a fatty acid. The polymerizable liquid crystal compound (1), which is a group hydrocarbon group and has high molecular flexibility, enhances mutual compatibility, and in such a state, the two kinds of polymerizable liquid crystal compounds contained It is thought that the phase transition temperature can be greatly lowered while maintaining a high degree of orientational order. If phase transition is possible at a low temperature, a cured liquid crystal film can be produced from a polymerizable liquid crystal compound at a lower processing temperature, and such a cured liquid crystal film can be less affected by heating.
In particular, from the viewpoint of suppressing the occurrence of alignment defects and easily lowering the phase transition temperature of the polymerizable liquid crystal compound [as a mixture of polymerizable liquid crystal compounds (1) and (2)] without impairing the optical properties, the present -O-CO-G ¹¹ -E ¹¹ -(A ¹¹ -B ¹¹ ) _k11 -F ¹¹ -P ¹¹ and -O-CO-G ¹² -E ¹² -( A ¹² -B ¹² ) _k12 -F ¹² -P ¹² , —O—CO-G ²¹ -E ²¹ -(A ²¹ -B ²¹ ) _k21 -F ²¹ -P ²¹ of the polymerizable liquid crystal compound (2), and , —O—CO—G ²² —E ²² —(A ²² —B ²² ) _k22 —F ²² —P ²² preferably have similar structural units.

k21 and k22 in formula (2) each independently represent an integer of 1 or more, and may be an integer of 1 to 5, for example. The sum of k21 and k22 is preferably 2-6, more preferably 2-4. From the viewpoint of excellent liquid crystallinity, k21 and k22 are each independently preferably 1 or 2. From the viewpoint of ease of production of the polymerizable liquid crystal compound (2), k21 and k22 are the same number. Preferably, k21 and k22 are both 1 in one preferred embodiment of the invention. Moreover, from the viewpoint of excellent liquid crystallinity, k11 and k12 in formula (1) and k21 and k22 in formula (2) are preferably the same number, more preferably 1.

The groups represented by ^B21 , ^B22 , ^E21 , ^E22 , ^G21 , ^G22 , A21, ^A22 , ^F21 , ^F22 , ^P21 and ^P22 in formula ⁽ 2) include: Examples of groups represented by B ¹¹ , B ¹² , E ¹¹ , E ¹² , G ¹¹ , G ¹² , A ¹¹ , A ¹² , F ¹¹ , F ¹² , P ¹¹ and P ¹² in formula (1), respectively The same applies to each preferred embodiment. Further, the group represented by Ar ²¹ in formula (2) includes the same groups as those exemplified as the groups represented by Ar ¹¹ and Ar ¹² in formula (1), and preferred embodiments thereof. The same applies to

The groups represented by A ¹¹ , A ¹² , B ¹¹ , B ¹² , E ¹¹ , E ¹² , F ¹¹ , F ¹² , G ¹¹ , G ¹² , P ¹¹ and P ¹² in formula (1) are each is the same as the groups represented by A ²¹ , A ²² , B ²¹ , B ²² , E ²¹ , E ²² , F ²¹ , F ²² , G ²¹ , G ²² , P ²¹ and P ²² in formula (2); , the groups represented by Ar ¹¹ and Ar ¹² in formula (1) are each preferably the same as the group represented by Ar ²¹ in formula (2). When the group in the formula (1) and the group in the formula (2) have such a relationship, the compatibility between the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) is likely to be enhanced, and alignment defects may occur. while suppressing the phase transition temperature.

The contents of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition of the present invention are Depending on, it may be appropriately determined within the range in which the effect of the present invention can be obtained, but the polymerization for the total peak area of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) measured by liquid chromatography It is preferable that the ratio of the peak area of the liquid crystal compound (1) (hereinafter also referred to as "area percentage value") is 0.1% or more and 50% or less. It is more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 3% by mass or more. When the content of the polymerizable liquid crystal compound (1) is at least the above lower limit, the solubility of the polymerizable liquid crystal compound in solvents tends to improve, and the phase transition temperature tends to decrease sufficiently. Further, when the content of the polymerizable liquid crystal compound (1) is equal to or less than the above upper limit, the alignment state of the liquid crystal is maintained well when a cured liquid crystal film is produced from the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound. Therefore, an optical film having excellent optical properties can be obtained. When a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1) and/or the polymerizable liquid crystal compound (2) are included, the area percentage value of the polymerizable liquid crystal compound (1) is the total polymerizable liquid crystal compound. It is calculated with respect to the total peak area of (1) and all the polymerizable liquid crystal compounds (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and more specifically, it can be measured and calculated by the method described in Examples below.

The polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in combination, so that the polymerizable liquid crystal compound (2) is used alone. The transition temperature can be greatly lowered. For example, the phase transition temperature of the liquid crystal mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition of the present invention is preferably 153° C. or less, more preferably 150° C. 145° C. or lower, more preferably 145° C. or lower.
Further, the polymerizable liquid crystal compound (1) of the present invention, when used in combination with the polymerizable liquid crystal compound (2), compared to the case of using the polymerizable liquid crystal compound (2) alone, the phase transition temperature The temperature can be lowered by preferably 8°C or more, more preferably 10°C or more, still more preferably 12°C or more, and particularly preferably 15°C or more.
In the present invention, the phase transition temperature of the polymerizable liquid crystal compound can be measured by the method described in Examples below. When two or more polymerizable liquid crystal compounds are included, the phase transition temperature is measured using a polymerizable liquid crystal compound (mixture) having the same composition as the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition.

Furthermore, the polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in combination, so that the polymerizable liquid crystal compound (2) is used alone. Therefore, the effect of increasing the solubility of the polymerizable liquid crystal compound in the solvent is excellent.

The method for producing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) that constitute the polymerizable liquid crystal composition of the present invention is not particularly limited, and they are Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, and Comprehensive Organic Synthesis, respectively. , known organic synthesis reactions described in 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 appropriately combined according to the structure.

For example, A ¹¹ and A ¹² , B ¹¹ and B ¹² , E ¹¹ and E ¹² , F ¹¹ and F ¹² , G ¹¹ and G ¹² , P ¹¹ and P ¹² , Ar ¹¹ and Ar ¹² and are the same polymerizable liquid crystal compound (1), the compound represented by formula (1-1) (hereinafter also referred to as "compound (1-1)") and the formula (1-2) represented by (hereinafter also referred to as “compound (1-2)”) and a compound represented by formula (1-3) (hereinafter also referred to as “compound (1-3)”). can be manufactured by P, F, B, A, E and G in formula (1-1) are respectively P ¹¹ and P ¹² , F ¹¹ and F ¹² , B ¹¹ and B ¹² , and A ¹¹ in formula (1). and A ¹² , E ¹¹ and E ¹² , G ¹¹ and G ¹² . M in formula (1-2) and Ar in formula (1-3) are the same as defined for M, Ar ¹¹ and Ar ¹² in formula (1), respectively. P, F, B, A, E, G and Ar are determined according to the desired polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2).

The reaction of compounds (1-1) to (1-3) is preferably carried out in the presence of a condensing agent.
Condensing agents include, for example, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3 -(3-dimethylaminopropyl)carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide carbodiimide such as 2-methyl-6-nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphorylazide, 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-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N, N',N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazo linium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro-1-methylpyridinium p-toluenesulfonate, trichloroacetic acid pentachlorophenyl ester, etc. .
Dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl) are used as condensing agents in terms of reactivity, cost, and many choices of solvents that can be used. ) carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, 2,2'-carbonylbis-1H-imidazole are preferred.

The polymerizable liquid crystal compound (2) can be produced, for example, by reacting the compound (1-1) with the compound (1-3).

In the present invention, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition may be prepared separately and then mixed to form a liquid crystal mixture. Further, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) can also be obtained as a liquid crystal mixture by reacting the compounds (1-1) to (1-3) in an appropriate ratio. Without isolating each polymerizable liquid crystal compound from the obtained liquid crystal mixture, if necessary, the liquid crystal mixture and the polymerizable liquid crystal compound (1) are mixed, or the liquid crystal mixture and the polymerizable liquid crystal compound (2 ), a desired polymerizable liquid crystal mixture can be prepared by controlling the contents of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the liquid crystal mixture. .
The former method makes it easy to adjust the contents of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) within a desired range, and to easily control the solvent solubility of the polymerizable liquid crystal compound. On the other hand, when the polymerizable liquid crystal mixture is prepared by the latter method, the synthesis is simple and the polymerizable liquid crystal composition can be produced more efficiently.

When the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) are prepared as a liquid crystal mixture, the amount of compound (1-2) used in the reaction is based on 100 parts by mass of compound (1-1). It is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass. The amount of the compound (1-3) used in the reaction is preferably 1 part by mass or more and 70 parts by mass or less, and 10 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the compound (1-1). is more preferable. By adjusting the amounts of the compound (1-1), the compound (1-2) and the compound (1-3) within the above range, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) at a desired ratio. It is easy to prepare a liquid crystal mixture containing and.

The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) as long as it does not affect the effects of the present invention. Examples of such polymerizable liquid crystal compounds include, for example, Liquid Crystal Handbook (Liquid Crystal Handbook Editing Committee, published by Maruzen Co., Ltd. on October 30, 2000), Chapter 3 Molecular Structure and Liquid Crystalline, 3.2 Nonchiral Rod Liquid crystal molecules, 3.3 Compounds described in chiral rod-like liquid crystal molecules, compounds described in JP-A-2010-31223, liquid crystals such as those described in JP-A-2011-207765 and Japanese Patent No. 5962760 A polymerizable liquid crystal compound capable of exhibiting reverse wavelength dispersion and a polymerizable liquid crystal compound capable of exhibiting forward wavelength dispersion when made into a cured film are exemplified.

When the polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the content of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less with respect to 100 parts by mass of compound (2) in total. In particular, if the content of the liquid crystal compound having a molecular structure significantly different from that of the polymerizable liquid crystal compound (1) or the polymerizable liquid crystal compound (2) is too large, phase separation may occur and the appearance may be impaired. The polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition is preferably substantially composed of a polymerizable liquid crystal compound having a structure similar to that of the polymerizable liquid crystal compound (1). The above-mentioned “similar” means, for example, —O—CO—G ¹¹ —E ¹¹ —(A ¹¹ —B ¹¹ ) _k11 —F ¹¹ —P ¹¹ , —O—CO of the polymerizable liquid crystal compound (1). -G ¹² -E ¹² -(A ¹² -B ¹² ) _k12 -F ¹² -P ¹² The case of having a structure common to the portion represented by Ar ¹¹ or Ar ¹² , and the above "substantially "consisting substantially" means that the content of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) is 90% with respect to the total mass of the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition of the present invention. % or more. In one aspect of the present invention, the polymerizable liquid crystal composition does not contain polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2).

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition of the present invention (the total amount of all polymerizable liquid crystal compounds) is, for example, 70 to 99.5 with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, still more preferably 90 to 95 parts by mass. If the total mass of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of orientation of the resulting cured liquid crystal film. In this specification, the polymerizable liquid crystal compound includes the polymerizable liquid crystal compound (1), the polymerizable liquid crystal compound (2), and other polymerizable liquid crystal compounds different from these when included. (Hereinafter, these are collectively referred to as a "polymerizable liquid crystal mixture"). The solid content of the polymerizable liquid crystal composition means all components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.

The polymerizable liquid crystal composition of the present invention contains, in addition to the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), an organic solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and the like. It may further contain additives. Each of these components may be used alone or in combination of two or more.

In the present invention, the polymerizable liquid crystal mixture preferably contains a solvent because it is usually applied to a base material or the like in a state of being dissolved in a solvent. The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound such as the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and is inert to the polymerization reaction of the polymerizable liquid crystal compound. is preferred. The polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in combination, so that the polymerizable liquid crystal compound (2) alone is dissolved in a solvent. As a result, the solvent solubility of the polymerizable liquid crystal compound (2) can be significantly improved. Therefore, various solvents can be applied. Examples of solvents include water, alcohols such as 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. Solvent; 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 ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; 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; be done. These solvents can be used alone or in combination of two or more. Among these, organic solvents are preferred, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are more preferred. From the viewpoint of productivity, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone , cyclohexanone and N-methylpyrrolidone is more preferred.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal 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 polymerizable liquid crystal composition is low, so that the thickness of the film becomes substantially uniform and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the cured liquid crystal film to be produced. Since the polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in combination, it has excellent solubility in solvents, and thus can be used during coating and storage. It is also advantageous in that the amount of organic solvent used can be reduced.

The polymerizable liquid crystal composition of the invention preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound capable of generating a reactive species by the contribution of light and initiating a polymerization reaction of a polymerizable liquid crystal or the like. Examples of reactive species include active species such as radicals, cations, and anions. Among them, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint that reaction control is easy. As a photoinitiator, only 1 type may be used and you may use it in combination of 2 or more type.

Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, benzylketal compounds, alkylphenone compounds, acylphosphine oxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts. be done. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Corporation ), Seikuol BZ, Seikuol Z, Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka Optomer SP- 152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arkles NCI-831, Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ -PP (manufactured by Nihon SiberHegner Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).
In the present invention, the polymerizable liquid crystal mixture composition preferably contains at least one photopolymerization initiator, and may contain two or more photopolymerization initiators.

Since the photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity, it is preferable that the maximum absorption wavelength is 300 nm to 400 nm, more preferably 300 nm to 380 nm. Polymerization initiators and oxime photopolymerization initiators are preferred.

α-Acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1 -one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one and the like, more preferably 2-methyl-2-morpholino-1-( 4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG and 907 (manufactured by BASF Japan Ltd.) and Seikuol BEE (manufactured by Seiko Kagaku Co., Ltd.).

The oxime-based photopolymerization initiator generates methyl radicals when exposed to light. Due to this methyl radical, polymerization of the polymerizable liquid crystal compound in the deep part of the cured liquid crystal film to be formed proceeds favorably. Moreover, from the viewpoint of more efficiently progressing the polymerization reaction in the depth of the cured liquid crystal film to be formed, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more. Triazine compounds and oxime ester-type carbazole compounds are preferable as photopolymerization initiators capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more, and oxime ester-type carbazole compounds are more preferable from the viewpoint of sensitivity. Oxime ester-type carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Commercially available oxime ester-type carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by BASF Japan Ltd.), Adeka Optomer N-1919, and Adeka Arkles NCI-831 (manufactured by BASF Japan Ltd.). , manufactured by ADEKA Corporation) and the like.

The amount of the photopolymerization initiator added is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 100 parts by mass of the polymerizable liquid crystal compound. is 1 to 15 parts by mass. Within the above range, the reaction of the polymerizable group proceeds sufficiently and the alignment of the polymerizable liquid crystal compound is less likely to be disturbed.

By using a sensitizer, the sensitivity of the photopolymerization initiator can be increased. Examples of photosensitizers include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. Examples of photosensitizers include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the total amount of the polymerizable liquid crystal compound. 1 to 3 parts by mass.

By adding a polymerization inhibitor, it is possible to control the polymerization reaction of the polymerizable liquid crystal compound. Examples of polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as alkyl ethers such as butylcatechol; pyrogallols, 2,2,6,6-tetramethyl-1- Radical scavengers such as piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound (1) without disturbing the alignment, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound. , preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

Furthermore, the polymerizable liquid crystal composition of the present invention may contain a leveling agent. The leveling agent is an additive that has the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the film obtained by coating it more flat. leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all from Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all from Momentive Performance Materials Japan G.K.) ), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M), Megafac (registered trademark) R-08 , R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482 , F-483 (all manufactured by DIC Corporation), F-top (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered Trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.) , trade names E1830, E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: BM Chemie), etc. mentioned. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound.
When the content of the leveling agent is within the above range, it is preferable because the polymerizable liquid crystal compound can be easily oriented and the resulting cured liquid crystal film tends to be smoother. The polymerizable liquid crystal composition may contain two or more leveling agents.

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

<Retardation film>
In the polymerizable liquid crystal composition of the present invention, the phase transition temperature of the polymerizable liquid crystal compound is low, and a cured liquid crystal film can be produced at a lower processing temperature. membranes can be obtained. In addition, since it has high solubility in solvents and excellent coating properties and film-forming properties, it is possible to suppress the occurrence of orientation defects caused by undissolved polymerizable liquid crystal compounds and precipitates and deposits in the composition. . Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to form a film without deteriorating the optical properties that the polymerizable liquid crystal compound can originally express, and the cured liquid crystal has excellent optical properties. membranes can be obtained. Therefore, the present invention provides a cured product of the polymerizable liquid crystal composition of the present invention, particularly a cured product of the polymerizable liquid crystal composition, wherein the polymerizable liquid crystal compound (1) in the polymerizable liquid crystal composition and the polymerization The present invention also relates to a retardation film comprising a cured liquid crystal film obtained by curing the liquid crystal compound (2) in an aligned 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 may be composed of a homopolymer of the polymerizable liquid crystal compound (1) in an aligned state and a homopolymer of the polymerizable liquid crystal compound (2). It may be composed of a copolymer in an oriented state of a mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). Since the polymerization reaction is easy and a uniform cured liquid crystal film can be easily obtained, the cured liquid crystal film constituting the retardation film of the present invention is an alignment of the mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). It is preferably composed of a copolymer in a state.

In one aspect of the present invention, the retardation film of the present invention is a cured product of the polymerizable liquid crystal composition of the present invention and has optical properties represented by the following formulas (i), (ii) and (iii). Includes liquid crystal cured film. The 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 "horizontally aligned cured liquid crystal film").
Re(450)/Re(550)≤1.00 (i)
1.00≦Re(650)/Re(550) (ii)
100 nm≦Re(550)≦180 nm (iii)
[In the formula, Re (λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured film, Re = (nx (λ) - ny (λ)) × 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 the direction parallel to the plane of the liquid crystal cured film, and ny is the refractive index ellipsoid formed by the liquid crystal cured film. , represents the refractive index at the wavelength λnm in the direction parallel to the plane of the liquid crystal cured film and perpendicular to the direction of nx). ]

When the horizontally aligned liquid crystal cured film satisfies the formulas (i) and (ii), 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 chromatic dispersion. Since the reverse wavelength dispersion is improved and the optical properties of the retardation film are further improved, Re(450)/Re(550) is preferably 0.70 or more, more preferably 0.78 or more, and , preferably 0.90 or less, more preferably 0.88 or less, still more preferably 0.86 or less, particularly preferably 0.85 or less, particularly preferably 0.84 or less. In addition, Re(650)/Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and still more preferably 1.02 or more.

The 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 the film thickness d should be adjusted.

Further, when the horizontally aligned liquid crystal cured film satisfies the formula (iii), the effect of improving the front reflection hue (coloration suppressing effect). A more preferable range of the in-plane retardation value is 120 nm≦Re(550)≦170 nm, and a further preferable range is 130 nm≦Re(550)≦150 nm.

In one aspect of the present invention, the retardation film of the present invention is a cured product of the polymerizable liquid crystal composition of the present invention, and has optical properties represented by the following formulas (iv), (v) and (vi). Includes liquid crystal cured film. The cured liquid crystal film is usually a cured product obtained by curing a polymerizable liquid crystal compound in a state of being aligned in a direction perpendicular to the plane of the cured liquid crystal film (hereinafter also referred to as a "cured vertically aligned liquid crystal film").
Rth(450)/Rth(550)≦1.00 (iv)
1.00≦Rth(650)/Rth(550) (v)
−100 nm≦Rth(550)≦−40 nm (vi)
[In the formula, Rth (λ) represents the retardation value in the thickness direction at the wavelength λ nm of the cured liquid crystal film, and is Rth = ((nx (λ) + ny (λ)) / 2-nz) × d (d is represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at the wavelength λnm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, and ny represents the liquid crystal cured film formed In the refractive index ellipsoid, it is parallel to the plane of the liquid crystal cured film and represents the refractive index at the wavelength λnm in the direction perpendicular to the direction of the nx, and nz is the refraction formed by the liquid crystal cured film In the index ellipsoid, it represents the refractive index at a wavelength λ nm in the direction perpendicular to the plane of the cured liquid crystal film).
]

When the vertically aligned liquid crystal cured film satisfies the formulas (iv) and (v), an elliptically polarizing plate provided with a retardation film containing the vertically aligned liquid crystal cured film can suppress a decrease in ellipticity on the short wavelength side. , the oblique reflection hue can be improved. The value of Rth(450)/Rth(550) in the vertically aligned liquid crystal cured film is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.90 or less, more preferably 0.90 or less. It is 88 or less, more preferably 0.86 or less, particularly preferably 0.85 or less, particularly preferably 0.84 or less. Also, Rth(650)/Rth(550) is preferably 1.0 or more, more preferably 1.01 or more, and still more preferably 1.02 or more.

Further, when the vertically aligned liquid crystal cured film satisfies the formula (vi), the oblique reflection hue is improved when an elliptically polarizing plate provided with a retardation film containing the vertically aligned liquid crystal cured film is applied to an organic EL display device. can be done. The film thickness direction retardation value Rth (550) of the vertically aligned liquid crystal cured film is more preferably −90 nm or more, more preferably −80 nm or more, and more preferably −50 nm or less.

The retardation film of the present invention is, for example,
forming a coating film of the polymerizable liquid crystal composition of the present invention, drying the coating film, and orienting the polymerizable liquid crystal compound in the polymerizable liquid crystal composition;
It can be produced by a method including a step of forming a cured liquid crystal film by polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining the alignment state.

The coating film of the polymerizable liquid crystal composition can be formed by coating the polymerizable liquid crystal composition on a base material, an alignment film described below, or the like.
Examples of the substrate include glass substrates and film substrates, and resin film substrates are preferable from the viewpoint of workability. Examples of resins constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Cellulose esters such as diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalates; polycarbonates; polysulfones; polyethersulfones; polyetherketones; Such a resin can be used as a base material by forming a film by known means such as a solvent casting method and a melt extrusion method. The surface of the base material may have a protective layer formed of acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and may be subjected to release treatment such as silicone treatment, corona treatment, Surface treatment such as plasma treatment may be applied.

A commercially available product may be used as the base material. Commercially available cellulose ester substrates include, for example, cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; and 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 olefins 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 such as "APEL" (registered trademark) Cyclic olefin-based resins manufactured by Kagaku Co., Ltd. can be mentioned. A commercially available cyclic olefin resin base material can also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd. such as “Escina (registered trademark)” and “SCA40 (registered trademark)”; Optes Co., Ltd. cyclic olefin resin base material such as "; JSR Co., Ltd. cyclic olefin resin base material such as "Arton Film (registered trademark)".

The thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm, from the viewpoint of thinning of the retardation film, ease of peeling of the substrate, handleability of the substrate, and the like.

Examples of methods for applying the polymerizable liquid crystal composition to a substrate or the like include coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography. and other known methods.

Then, a dry coating film is formed by removing the solvent by drying or the like. Drying methods include natural drying, ventilation drying, heat drying and reduced pressure drying. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent is removed by drying from the coating film, and the polymerizable liquid crystal compound is moved in a desired direction (e.g., horizontal or vertical direction) with respect to the coating film plane. direction). The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material for forming the coating film. , the temperature must be equal to or 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 polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smectic phase) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition It can be heated to a temperature above the transition temperature or nematic phase transition temperature.

The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), and usually each single polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2). can undergo a liquid crystal phase transition at a temperature lower than the temperature at which it transitions to the liquid crystal phase. In one aspect of the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture constituting the polymerizable liquid crystal composition of the present invention is preferably 25° C. or higher and 153° C. or lower. When the phase transition temperature to the liquid crystal phase is within the above range, a cured liquid crystal film can be produced at a lower processing temperature, and while suppressing deterioration in optical properties due to heating, the high optical properties that the polymerizable liquid crystal compound can originally exhibit. A liquid crystal cured film having properties can be obtained. Moreover, in the production of a retardation film using the polymerizable liquid crystal composition of the present invention, excessive consumption of thermal energy can be suppressed, and production efficiency can be improved. Furthermore, there is an advantage that the selection of supporting substrates for coating the polymerizable liquid crystal composition is widened because the liquid crystal phase transition can be performed by heating at a relatively low temperature. In the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture is usually 40° C. or higher, more preferably 50° C. or higher, more preferably 50° C. or higher, from the viewpoint that the obtained liquid crystal cured film is a compound capable of exhibiting reverse wavelength dispersion characteristics. is 60° C. or higher, more preferably 150° C. or lower, still more preferably 145° C. or lower, and particularly preferably 144° C. or lower from the viewpoint of achieving more remarkable effects of the present invention.
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. The phase transition temperature in the polymerizable liquid crystal mixture of the present invention containing at least two polymerizable liquid crystal compounds is obtained by polymerization in which all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal mixture are mixed in the same ratio as the composition in the polymerizable liquid crystal mixture. means the temperature measured using a mixture of liquid crystalline compounds.

The heating time can be appropriately determined according to the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point and its amount, etc., but it is usually 15 seconds to 10 minutes, preferably 0.5 to 10 minutes. Five minutes.

The removal of the solvent from the coating film may be performed at the same time as the heating of the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or may be performed separately, but from the viewpoint of improving productivity, it is preferably performed at the same time. Before heating the polymerizable liquid crystal compound to a liquid crystal phase transition temperature or higher, the solvent in the coating film is moderately removed under conditions where the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize. A pre-drying step may be provided for removal. Examples of the drying method in the preliminary drying step include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method, and the drying temperature (heating temperature) in the drying step depends on the type of polymerizable liquid crystal compound used, the can be determined as appropriate according to the type of , its boiling point, its amount, and the like.

Next, in the obtained dry coating film, while maintaining the alignment state of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized by light irradiation, thereby forming a polymer of the polymerizable liquid crystal compound present in a desired alignment state. A certain liquid crystal cured film is formed. The polymerizable liquid crystal 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 liquid crystal compound. is used. In photopolymerization, the light with which the dry coating film is irradiated is appropriately selected according to the type of polymerization initiator contained in the dry coating film and the type and amount of the polymerizable liquid crystal compound. Specific examples thereof include at least one kind 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 them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a widely used photopolymerization apparatus in the field can be used. It is preferable to select the types of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. The polymerization temperature can also be controlled by light irradiation while cooling the dry coating film with an appropriate cooling means during polymerization. By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a cured liquid crystal film can be properly formed even if a substrate having relatively low heat resistance is used. It is also possible to accelerate the polymerization reaction by raising the polymerization temperature within a range in which problems caused by heat during light irradiation (such as deformation of the base material due to heat) do not occur. A patterned cured film can also be obtained by performing masking or development during the photopolymerization.

Examples of the light source of the active energy ray include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, and wavelength ranges. LED light sources, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc., which emit light in the range of 380 to 440 nm can be used.

The UV irradiation intensity is usually 10 to 3,000 mW/cm ² . The UV irradiation intensity is preferably in the wavelength range effective for activation of the photopolymerization initiator. The light irradiation time is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. be. When irradiated once or multiple times with such an irradiation intensity of ultraviolet rays, the cumulative amount of light is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm. ² .

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

A coating film of the polymerizable liquid crystal composition may be formed on the alignment film. The alignment film has an alignment regulating force that aligns the polymerizable liquid crystal compound in a desired direction. For example, there are a horizontal alignment film having an alignment control force for horizontally aligning the polymerizable liquid crystal compound and a vertical alignment film having an alignment control force for vertically aligning the polymerizable liquid crystal compound. The alignment regulation force can be arbitrarily adjusted by the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed from a photo-orientable polymer, it can be arbitrarily adjusted by polarized irradiation conditions, etc. It is possible to

The alignment film preferably has solvent resistance so that it does not dissolve when the polymerizable liquid crystal composition is applied, etc., and also has heat resistance in the heat treatment for removing the solvent and for aligning the polymerizable liquid crystal compound, which will be described later. Examples of the alignment film include an alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, etc., and the precision of the orientation angle and the A photo-alignment film is preferable from the viewpoint of quality.

Examples of the oriented polymer include polyamides and gelatins having amide bonds in the molecule, polyimides having imide bonds in the molecule and their hydrolysates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, poly Oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Among them, polyvinyl alcohol is preferred. Orientation polymer can be used individually or in combination of 2 or more types.

An oriented film containing an oriented polymer is usually produced by applying a composition in which an oriented polymer is dissolved in a solvent (hereinafter sometimes referred to as an "oriented polymer composition") to a substrate and removing the solvent, or It can be obtained by applying an oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method). Examples of the solvent include the same solvents as those previously exemplified as solvents that can be used in the polymerizable liquid crystal composition.

The concentration of the oriented polymer in the oriented polymer composition may be within a range in which the oriented polymer material can be completely dissolved in the solvent. 0.1 to 10% is more preferable.

A commercially available alignment film material may be used as it is as the alignment polymer composition. Commercially available alignment film materials include Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

Examples of the method for applying the orienting polymer composition to the substrate include the same methods as those exemplified as the method for applying the polymerizable liquid crystal composition to the substrate.

Examples of methods for removing the solvent contained in the oriented polymer composition include natural drying, ventilation drying, heat drying, and vacuum drying.

A rubbing treatment can be performed as necessary in order to impart an alignment regulating force to the alignment film (rubbing method). As a method for imparting an alignment regulating force by a rubbing method, a rubbing cloth is wound around a rotating rubbing roll, and an orienting polymer composition is applied to the substrate and then annealed to form an orientation polymer composition on the substrate surface. A method of contacting a film of an oriented polymer can be mentioned. A plurality of regions (patterns) with different alignment directions can be formed in the alignment film by masking during the rubbing process.

A photo-alignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "composition for forming a photo-alignment film") to a substrate, and after removing the solvent, polarized light (preferably polarized UV). The photo-alignment film is also advantageous in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

A photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light. Specific examples include groups involved in photoreactions that cause liquid crystal alignment ability, such as orientation induction of molecules caused by light irradiation, isomerization reactions, dimerization reactions, photocrosslinking reactions, photodecomposition reactions, and the like. Among them, a group involved in a dimerization reaction or a photocrosslinking reaction is preferable from the viewpoint of excellent orientation. As the photoreactive group, a group having an unsaturated bond, particularly a double bond is preferable, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond Groups having at least one selected from the group consisting of a heavy bond (N=N bond) and a carbon-oxygen double bond (C=O bond) are particularly preferred.

Photoreactive groups having a C═C bond include vinyl groups, polyene groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups and cinnamoyl groups.
Photoreactive groups having a C═N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. The photoreactive group having an N=N bond includes an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. A benzophenone group, a coumarin group, an anthraquinone group, a maleimide group and the like can be mentioned as the photoreactive group having a C═O bond. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

Among them, a photoreactive group that participates in a photodimerization reaction is preferable, the amount of polarized light irradiation required for photoalignment is relatively small, and a photoalignment film having excellent thermal stability and stability over time can be easily obtained. Cinnamoyl and chalcone groups are preferred. As the polymer having a photoreactive group, a polymer having a cinnamoyl group having a cinnamic acid structure at the end of the polymer side chain is particularly preferred.

A photo-alignment inducing layer can be formed on the substrate by applying the composition for forming a photo-alignment film onto the substrate. Examples of the solvent contained in the composition include the same solvents as those previously exemplified as solvents that can be used in the polymerizable liquid crystal composition, and are appropriately selected according to the solubility of the polymer or monomer having a photoreactive group. can do.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of polymer or monomer and the thickness of the desired photo-alignment film. It is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer, as long as the properties of the photo-alignment film are not significantly impaired.

Examples of the method of applying the composition for forming a photo-alignment film onto the substrate include the same methods as the method of applying the orientation polymer composition onto the substrate. Examples of methods for removing the solvent from the coated composition for forming a photo-alignment film include natural drying, ventilation drying, heat drying, and vacuum drying.

In order to irradiate with polarized light, the composition for forming a photo-alignment film coated on the substrate, from which the solvent has been removed, may be directly irradiated with polarized UV. A format in which light is transmitted and irradiated may be used. 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 the photoreactive group of the polymer or monomer having a photoreactive group can absorb the light energy. Specifically, UV (ultraviolet rays) with a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of the light source used for the polarized irradiation include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and an ultraviolet light laser such as KrF or ArF. preferable. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because of their high emission intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be emitted 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.

It should be noted that multiple regions (patterns) with different liquid crystal orientation directions can be formed by masking when performing rubbing or polarized light irradiation.

A groove alignment film is a film having an uneven pattern or a plurality of grooves on its surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at regular intervals, liquid crystal molecules are aligned along the grooves.

As a method for obtaining a grooved alignment film, after exposure through an exposure mask having patterned slits on the surface of a photosensitive polyimide film, development and rinsing are performed to form an uneven pattern, and a plate having grooves on the surface. A method of forming a layer of UV curable resin before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a UV curable resin film before curing formed on the substrate, A method of pressing a roll-shaped master plate having a plurality of grooves to form unevenness and then curing the same may be used.

Furthermore, as the material exhibiting the alignment control force for aligning the polymerizable liquid crystal compound in the direction perpendicular to the plane of the cured liquid crystal film, in addition to the above-described aligning polymer, fluorine-based polymers such as perfluoroalkyl, silane compounds, and the like. You may use the polysiloxane compound etc. which are obtained by the condensation reaction of.

When a silane compound is used as the material for forming the alignment film, the constituent elements include Si element and C element from the viewpoint of easily reducing the surface tension and increasing the adhesion to the layer adjacent to the alignment film. Compounds are preferred, and silane compounds can be suitably used. A silane-containing ionic compound or the like can be used as the silane compound, and the use of such a silane compound can increase the vertical alignment regulating force. As the silane compound, one type may be used alone, two or more types may be used in combination, and other materials may be mixed and used. When the silane compound is a nonionic silane compound, a silane compound having an alkyl group at the molecular end is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable, from the viewpoint of easily increasing the vertical alignment control force. .

The thickness of the alignment film (orientation film containing an alignment polymer or photo-alignment film) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm, still more preferably. is in the range from 10 to 300 nm, particularly preferably from 50 to 250 nm.

The present invention includes a polarizing plate (elliptically polarizing plate) containing the retardation film of the present invention. The polarizing plate of the invention usually contains the retardation film of the invention and a polarizing film.
A polarizing film is a film having a polarizing function, and includes a stretched film to which a dye having anisotropic absorption is adsorbed, a film including a film coated with a dye having anisotropic absorption as a polarizer, and the like. Dyes having absorption anisotropy include, for example, dichroic dyes.

A film containing, as a polarizer, a stretched film to which a dye having anisotropic absorption is adsorbed is usually produced by uniaxially stretching a polyvinyl alcohol resin film and dyeing the polyvinyl alcohol resin film with a dichroic dye. At least a polarizer produced through a step of adsorbing a dichroic dye, a step of treating a polyvinyl alcohol resin film to which the dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution. It is produced by sandwiching a transparent protective film on one side with an adhesive interposed therebetween.

　Polyvinyl alcohol-based resin is obtained by saponifying polyvinyl acetate-based resin. Polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other monomers copolymerizable therewith. Other monomers copolymerizable with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The degree of saponification of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol resin is generally about 1,000 to 10,000, preferably 1,500 to 5,000.

A film obtained by forming such a polyvinyl alcohol resin is used as a raw film for a polarizing film. The method of forming the polyvinyl alcohol-based resin into a film is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, at the same time as, or after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. It is also possible to carry out uniaxial stretching in these multiple stages. In the uniaxial stretching, the film may be uniaxially stretched between rolls having different circumferential speeds, or may be uniaxially stretched using hot rolls. The uniaxial stretching may be dry stretching in which the film is stretched in the atmosphere, or wet stretching in which the polyvinyl alcohol resin film is stretched in a swollen state using a solvent. The draw ratio is usually about 3 to 8 times.

Dyeing a polyvinyl alcohol resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol resin film in an aqueous solution containing a dichroic dye.

Specifically, iodine and dichroic organic dyes are used as dichroic dyes. Dichroic organic dyes include C.I. I. Dichroic direct dyes composed of disazo compounds such as DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo are included. The polyvinyl alcohol-based resin film is preferably immersed in water before being dyed.

When iodine is used as the dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed.
The content of iodine in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40°C. The immersion time (dyeing time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed.
The content of the dichroic organic dye in this aqueous solution is usually about 1×10 ⁻⁴ to 10 parts by weight, preferably 1×10 ⁻³ to 1 part by weight, more preferably about 1×10 −3 to 1 part by weight, per 100 parts by weight of water. is 1×10 ⁻³ to 1×10 ⁻² parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. The immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in the boric acid aqueous solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, the boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in that case is usually 0.1 to 0.1 per 100 parts by mass of water. It is about 15 parts by mass, preferably 5 to 12 parts by mass. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, more preferably 60 to 80°C.

The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of water in the water washing process is usually about 5 to 40°C.
The immersion time is usually about 1 to 120 seconds.

After washing with water, a drying treatment is applied to obtain a polarizer. The drying treatment can be performed using, for example, a hot air dryer or a far-infrared heater. The drying temperature is usually about 30 to 100°C, preferably 50 to 80°C. The drying time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. The drying process reduces the moisture content of the polarizer to a practical level. Its moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the moisture content is within the above range, it is easy to obtain a polarizer having moderate flexibility and excellent thermal stability.

The thickness of the polarizer obtained by subjecting the polyvinyl alcohol resin film to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying is preferably 5 to 40 μm.

Examples of the film coated with a dye having anisotropic absorption include a film obtained by coating a composition containing a dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal. mentioned. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same resin films as the base material that can be used in the production of the cured liquid crystal film.

It is preferable that the film coated with a dye having anisotropic absorption is thin, but if it is too thin, the strength tends to decrease and workability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5 to 3 μm.

Specific examples of the film coated with a dye having absorption anisotropy include the film described in JP-A-2012-33249.

The polarizing film may be obtained by laminating a transparent protective film via an adhesive on at least one surface of the polarizer thus obtained. As the transparent protective film, a transparent film similar to the resin film exemplified above as the base material that can be used in the production of the cured liquid crystal film can be preferably used.

The polarizing plate of the present invention comprises the retardation film of the present invention and a polarizing film. The elliptically polarizing plate of the present invention can be obtained by laminating the layers together.

In one aspect of the present invention, when the retardation film of the present invention containing 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 and the absorption axis of the polarizing film is preferably 45±5°.

The polarizing plate of the present invention may have a structure like a conventional general elliptically polarizing plate, or a polarizing film and a retardation film. Such a configuration includes, for example, an adhesive layer (sheet) for bonding an elliptically polarizing plate to a display element such as an organic EL, and a polarizing film and a retardation film used for the purpose of protecting the surface from scratches and stains. protection film, etc.

The 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 source. Examples of display devices include liquid crystal displays, organic electroluminescence (EL) displays, inorganic electroluminescence (EL) displays, touch panel displays, electron emission displays (e.g. field emission displays (FED), surface field emission displays). (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (e.g. grating light valve (GLV) display device, display device having digital micromirror device (DMD) ) and piezoelectric ceramic displays, etc. 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, projection liquid crystal display devices, and the like. These display devices may be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images. EL) display device and inorganic electroluminescence (EL) display device can be suitably used.These display devices (optical displays) are provided with the polarizing plate of the present invention having excellent optical properties, thereby exhibiting excellent image display properties. can be expressed.

The present invention will be described in more detail below with reference to examples. "%" and "parts" in the examples mean % by mass and parts by mass, respectively, unless otherwise specified.

[HPLC measurement]
HPLC measurement may be performed under any conditions as long as the peaks derived from the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) 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: 0min 70% -B
30min 100%-B
60min 100%-B
60.01min 70%-B
75min 70%-B
Flow rate: 0.5mL/min
Injection volume: 5 μL
Detection wavelength: 254 nm

<Preparation of polymerizable liquid crystal compound>
Synthesis Example 1: Preparation of Polymerizable Liquid Crystal Compound (2) A polymerizable liquid crystal compound represented by the following formula (2-1-1) (hereinafter referred to as “polymerizable liquid crystal compound (2-1-1)”) is prepared as follows. was synthesized according to the scheme of

A 100 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and compound (E-1) 11.02 g synthesized with reference to Patent Document (JP 2010-31223), Patent Document (JP 2010-31223), 2011-207765) 4.22 g of the compound (D-2) synthesized with reference to, DMAP (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02 g, BHT (manufactured by Wako Pure Chemical Industries, Ltd.) 0.20 g, and After adding and mixing 58 g of chloroform (manufactured by Kanto Chemical Co., Ltd.), 4.05 g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and these were reacted overnight at 0°C. let me After completion of the reaction, insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) having a mass three times the mass of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was collected by filtration, washed with 20 g of acetonitrile three times, and dried at 30° C. under reduced pressure to obtain 11.75 g of polymerizable liquid crystal compound (2-1-1). The yield of polymerizable liquid crystal compound (2-1-1) was 81% based on compound (D-2).

Synthesis Example 2: Preparation of mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2)

A 100 mL-four-necked flask equipped with a Dimroth condenser and a thermometer was set to a nitrogen atmosphere, compound (E-1) 10.91 g, compound (D-2) 4.22 g, compound (F-3) (Jun Wako Yakukogyo Co., Ltd.) 0.06 g, DMAP (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02 g, BHT (manufactured by Wako Pure Chemical Industries, Ltd.) 0.20 g, and chloroform (manufactured by Kanto Chemical Co., Ltd.) ) was added and mixed, then 4.05 g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and these were allowed to react at 0° C. overnight. After completion of the reaction, insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) having a mass three times the mass of chloroform contained in the solution to precipitate a solid.
Subsequently, the precipitated solid was removed by filtration, washed with 20 g of acetonitrile three times, and then dried under reduced pressure at 30° C. to obtain a polymerizable liquid crystal compound (2-1-1) and a polymerizable liquid crystal compound (1-1 12.34 g of the mixture of -1) was obtained. The obtained mixture contained 5.0% of the polymerizable liquid crystal compound (1-1-1) with respect to the total mass of the mixture. The yield of the mixture was 85.0% based on compound (D-2). Note that n in the above formula (1-1-1) is n=2.

Synthesis Examples 3-13
In the same manner as in Synthesis Example 2, except that compounds (F-4) to (F-10), (F-1) or (F-2) shown in Table 1 were used instead of compound (F-3). liquid crystal mixtures (1) to (12) containing a polymerizable liquid crystal compound (2-1-1) and any of polymerizable liquid crystal compounds (1-1-2) to (1-1-10) prepared respectively. Note that the polymerizable liquid crystal compounds (1-1-2) to (1-1-10) are respectively -O-CO-(C ₃ H ₆ )-CO- in the above formula (1-1-1). The propylene group in the structure represented by O- is an aliphatic hydrocarbon group or alicyclic group derived from compounds (F-4) to (F-10), (F-1) or (F-2) has a structure replaced by

<Solubility evaluation>
Put 1.00 g of N-methylpyrrolidone (NMP) and a stirrer in a vial tube at 25° C., and while stirring with a magnetic stirrer (HS-30DN, AS ONE), each of the above synthetic compounds was visually dissolved. Injected until the rest was confirmed. When the undissolved residue is confirmed, the solubility of each liquid crystal mixture and polymerizable liquid crystal compound in NMP is calculated by (weight of each liquid crystal mixture and polymerizable liquid crystal compound) / (weight of each liquid crystal mixture and polymerizable liquid crystal compound + NMP). Weight) was calculated as a weight percent concentration. Table 3 shows the results.

<Preparation of polymerizable liquid crystal composition>
Example 1
A liquid crystal mixture (1) of the polymerizable liquid crystal compound (1-1-1) obtained in Synthesis Example 2 and the polymerizable liquid crystal compound (2-1-1) was put into a vial tube, and the composition shown in Table 2 was added. A polymerization initiator, a leveling agent, a polymerization inhibitor and a solvent were charged according to the above, and stirred at 80° C. for 30 minutes using a carousel to obtain a polymerizable liquid crystal composition (1).
The amount of the polymerization initiator, leveling agent and polymerization inhibitor shown in Table 2 is the amount charged per 100 parts by mass of the liquid crystal mixture (1). In addition, the blending amount of the solvent was set so that the mass % of the solid content was 13% with respect to the total amount of the polymerizable liquid crystal composition.

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 Chemical Co., Ltd.)

Example 2
As the polymerizable liquid crystal compound, 510 mg of the liquid crystal mixture (2) of the polymerizable liquid crystal compound (1-1-2) obtained in Synthesis Example 3 and the polymerizable liquid crystal compound (2-1-1), and the liquid crystal mixture (2) obtained in Synthesis Example 1 A polymerizable liquid crystal composition (2) was obtained in the same manner as in Example 1, except that 490 mg of the compound (2-1-1) was mixed and used. Using the obtained polymerizable liquid crystal composition (2), HPLC analysis was performed under the above measurement conditions, and the sum of the polymerizable liquid crystal compound (2-1-1) and the polymerizable liquid crystal compound (1-1-2) was determined. The area percentage value of the polymerizable liquid crystal compound (1-1-2) based on the amount was calculated.

Examples 3-8 and 10-12
Polymerizable liquid crystal compositions (3) to (8) and (10) to (12) were prepared in the same manner as in Example 1 except that the liquid crystal mixtures (2) to (10) were used instead of the liquid crystal mixture (1). ).

Example 9
As the polymerizable liquid crystal compound, 500 mg of the liquid crystal mixture (8) of the polymerizable liquid crystal compound (1-1-6) obtained in Synthesis Example 9 and the polymerizable liquid crystal compound (2-1-1), and the liquid crystal mixture (8) obtained in Synthesis Example 1 A polymerizable liquid crystal composition (9) was obtained in the same manner as in Example 1, except that 500 mg of the compound (2-1-1) was mixed and used. Using the obtained polymerizable liquid crystal composition (9), HPLC analysis was performed under the above measurement conditions, and the total of the polymerizable liquid crystal compound (2-1-1) and the polymerizable liquid crystal compound (1-1-6) The area percentage value of the polymerizable liquid crystal compound (1-1-6) based on the amount was measured.

Comparative example 1
A polymerizable liquid crystal composition (13) was obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 1 was used instead of the liquid crystal mixture (1).

Comparative Examples 2 and 3
A polymerizable liquid crystal composition (14 ) and (15) were obtained.

<Measurement of phase transition temperature>
1000 mg of each of the liquid crystal mixtures used for the polymerizable liquid crystal compositions (1) to (15) was weighed into a vial tube, and 2 g of chloroform was added to dissolve. The resulting 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 Co., Ltd.), heated from room temperature to 180° C., and then cooled to room temperature. The state at the time of temperature change was observed with a polarizing microscope (LEXT, manufactured by Olympus Corporation), and the temperature at which the nematic phase was reached was measured and taken as the nematic phase transition temperature.
Table 3 shows the results.

<Measurement of optical properties (α value)>
Polymerizable liquid crystal compositions (1), (3), (4), (6), (8), (10) to (12) and (15) in which M in formula (1) is an aliphatic hydrocarbon group ), an optical film (retardation film) was produced and the optical properties were evaluated. The results are listed in Table 4.
[Preparation of Composition for Forming Photo-Alignment Film]
A composition for forming a photo-alignment film was obtained by mixing the following components and stirring the resulting mixture at 80° C. for 1 hour.
A photo-orientable material (5 parts) having the following formula:

(Number average molecular weight: about 28000)
Solvent (95 parts): Cyclopentanone

[Manufacture of optical film (retardation film)]
An optical film was produced as follows. A cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Zeon Co., Ltd.) was treated with 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 to the corona-treated surface using a bar coater, dried at 80° C. for 1 minute, and then irradiated with a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.). , and an integrated light dose of 100 mJ/cm ² for polarized UV exposure. The film thickness of the resulting alignment film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 100 nm.

Polymerizable liquid crystal compositions (1), (3), (4), (6), (8), (10) to (12) and (15) are each applied onto the alignment film using a bar coater. After drying at 120 ° C. for 1 minute, using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.), UV irradiation (under nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: 1000 mJ/cm ² ) to prepare an optical film.

The optical film prepared above is used as a measurement sample, and the front retardation value for light with a wavelength of 450 nm and a wavelength of 550 nm is measured using a measuring device ("KOBRA-WR" manufactured by Oji Keisokuki Co., Ltd.), α value = Re ( 450)/Re(550) was calculated.

Claims

A polymerizable liquid crystal compound represented by formula (1).

[In formula (1),
k11, k12 and l each independently represent an integer of 1 or more;
B 11 and B 12 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S—, or a single bond, and R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or represents an alkyl group having 1 to 4 carbon atoms;
E 11 and E 12 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S—, or a single bond; G 11 and G 12 each independently represent a C 3-16 represents a divalent alicyclic hydrocarbon group, hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, -R 3 , -OR 3 , a cyano group or a nitro group, —CH 2 — contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—, R 3 represents an alkyl group having 1 to 4 carbon atoms, A hydrogen atom contained in the alkyl group may be substituted with a fluorine atom;
A 11 and A 12 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; A hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a halogen atom, —R 3 , —OR 3 , a cyano group or a nitro group;
F 11 and F 12 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 3 or a halogen atom, and the alkane —CH 2 — contained in the diyl group may be replaced with —O— or —CO—;
P 11 and P 12 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 11 and P 12 is a polymerizable group);
each M independently represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms which may have a substituent;
Ar 11 and Ar 12 each independently represent a divalent aromatic group which may have a substituent. ]
M in formula (1) is a divalent aliphatic hydrocarbon group having 2n carbon atoms (n represents an integer of 2 to 4) optionally having a substituent, according to claim 1 Polymerizable liquid crystal compound.
The polymerization according to claim 1 or 2, wherein Ar 11 and Ar 12 in formula (1) are each independently a group represented by any one of the following formulas (Ar-1) to (Ar-5) liquid crystal compound.

[In the formulas (Ar-1) to (Ar-5),
* represents a bond;
Q 1 represents -S-, -O- or -NR 11 -, R 11 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms,
Q 2 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms;
W 1 and W 2 each independently represent —O—, —S—, —CO—, —NR 11 —, and R 11 is a hydrogen atom or an optionally substituted C 1-6 represents an alkyl group;
Y 1 represents an alkyl group having 1 to 6 carbon atoms, an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group,
Y 2 represents a CN group or an optionally substituted alkyl group having 1 to 12 carbon atoms, 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 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon number 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, —NR 11 R 12 or —SR 11 ; may be formed, and R 11 and R 12 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 having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; Ay represents a hydrogen atom; an alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; may be joined to form a ring;
Y 3 and Y 4 each independently represent the following formula (Y-1):

[In formula (Y-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 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 - are 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- which may be replaced by a straight chain having 1 to 20 carbon atoms or represents a branched alkyl group, any hydrogen atom in which may be substituted with a fluorine atom, or may be a group represented by -B 31 -F 31 -P 31 , and B 31 , F 31 and P 31 are defined in the same manner as B 11 , F 11 and P 11 in formula (1) above, and are the same as B 11 , F 11 and P 11 in formula (1) respectively. may be different;
U 1 represents 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, and the aromatic hydrocarbon group is , optionally substituted by one or more of said substituents X 3 ;
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, 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 heteroatom) or an organic group having 2 to 30 carbon atoms, or (E 31 -A 31 ) q -B 32 -F 32 - P 32 , the alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group may each be unsubstituted or substituted by one or more substituents X 3 , the alkyl group may be substituted by said cycloalkyl group or cycloalkenyl group, and one —CH 2 — or two or more non-adjacent —CH 2 — in said 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 - may be replaced by C≡C-, and one —CH 2 — or two or more non-adjacent —CH 2 — in the cycloalkyl group or cycloalkenyl group are each independently —O—, —CO—, —COO—, —OCO— or O—CO—O—, and E 31 , A 31 , B 32 , F 32 and P 32 are each E in formula (1) 11 , A 11 , B 11 , F 11 and P 11 , which may be the same as or different from E 11 , A 11 , B 11 , F 11 and P 11 , respectively, q is 0 represents an integer of to 4, and when there are a plurality of 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 ]
A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of claims 1 to 3 and a polymerizable liquid crystal compound represented by formula (2).

[In formula (2),
k21 and k22 each independently represent an integer of 1 or more;
B 21 and B 22 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S—, or a single bond, and R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or It represents an alkyl group having 1 to 4 carbon atoms.
E 21 and E 22 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO -O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S—, or a single bond; G 21 and G 22 each independently represent a C 3-16 represents a divalent alicyclic hydrocarbon group, hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, -R 3 , -OR 3 , a cyano group or a nitro group, —CH 2 — contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—, R 3 represents an alkyl group having 1 to 4 carbon atoms, A hydrogen atom contained in the alkyl group may be substituted with a fluorine atom;
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; A hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a halogen atom, —R 3 , —OR 3 , a cyano group or a nitro group;
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 3 or a halogen atom, and the alkane —CH 2 — contained in the diyl group may be replaced with —O— or —CO—;
P21 and P22 each independently represent a hydrogen atom or a polymerizable group ( provided that at least one of P21 and P22 is a polymerizable group);
Ar 21 each independently represents a divalent aromatic group which may have a substituent. ]
The ratio of the peak area of the polymerizable liquid crystal compound (1) to the total peak area of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) measured by liquid chromatography is 0.1% or more and 50% or less. 5. The polymerizable liquid crystal composition according to claim 4, wherein
The groups represented by A 11 , A 12 , B 11 , B 12 , E 11 , E 12 , F 11 , F 12 , G 11 , G 12 , P 11 and P 12 in formula (1) are each is the same as the groups represented by A 21 , A 22 , B 21 , B 22 , E 21 , E 22 , F 21 , F 22 , G 21 , G 22 , P 21 and P 22 in formula (2); 6. The polymerizable liquid crystal according to claim 4 or 5, wherein the groups represented by Ar 11 and Ar 12 in formula (1) are the same as the groups represented by Ar 21 in formula (2). Composition.
The polymerizable liquid crystal composition according to any one of claims 4 to 6, further comprising a photopolymerization initiator and an organic solvent.
A retardation film formed from the polymerizable liquid crystal composition according to any one of claims 4 to 7.
A polarizing plate comprising the retardation film according to claim 8.
An optical display comprising the polarizing plate according to claim 9.