KR20220050169A - Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device - Google Patents

Abstract

An object of the present invention is to provide a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device used for forming an optically anisotropic film having reverse wavelength dispersion and excellent amine resistance. The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a compound represented by the following formula (I-1) and a polymerizable smectic liquid crystal compound.

Description

Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device

The present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

Since the polymerizable liquid crystal compound exhibiting reverse wavelength dispersion has characteristics such as enabling accurate light wavelength conversion in a wide wavelength range, and being able to thin the retardation film because it has a high refractive index, is being actively studied.

In addition, as the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, a T-type molecular design guideline is generally adopted, and it is required to shorten the wavelength of the long axis of the molecule and increase the wavelength of the short axis located at the center of the molecule to a longer wavelength. there is.

In addition, from the viewpoint of increasing the wavelength of the short axis located at the center of the molecule to a longer wavelength, introducing a hydrophilic nitrogen atom, an oxygen atom, or a sulfur atom into the short axis skeleton (hereinafter also referred to as "reverse wavelength dispersion expression part") is It is known (for example, refer patent documents 1 - 3).

Patent Document 1: Japanese Patent Application Laid-Open No. 2010-031223 Patent Document 2: International Publication No. 2014/010325 Patent Document 3: Japanese Patent Laid-Open No. 2016-081035

The present inventors, with respect to Patent Documents 1 to 3, have a problem of durability (hereinafter also abbreviated as "amine resistance") that the birefringence of the optically anisotropic film to be formed is changed by ammonia, which is a basic nucleophilic substance. confirmed that

In addition, the present inventors have found that if a strong bond (for example, ether bond, etc.) is used for the connection between the short-axis backbone (reverse wavelength dispersion expression part) located in the center of the molecule, and the long-term axis of the molecule, the amine resistance is improved, The problem that liquid crystallinity is not shown and reverse wavelength dispersion property is lost was revealed.

Accordingly, it is an object of the present invention to provide a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device used for forming an optically anisotropic film having reverse wavelength dispersion and excellent amine resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the present inventors in order to achieve the said subject, the optical anisotropy formed by using the polymeric liquid crystal composition which mix|blended the polymerizable smectic liquid crystal compound with the compound represented by Formula (I-1) mentioned later. Reverse wavelength dispersion property was expressed in a film|membrane, and it discovered that amine resistance also became favorable, and completed this invention.

That is, it discovered that the said subject could be achieved with the following structures.

[One]

A polymerizable liquid crystal composition comprising a compound represented by Formula (I-1) to be described later and a polymerizable smectic liquid crystal compound.

[2]

The polymerizable liquid crystal composition according to [1], wherein Ar ¹ and Ar ² in Formula (I-1) described below represent an aromatic ring having a maximum absorption wavelength at 300 to 400 nm.

[3]

Ar ¹ and Ar ² in formula (I-1) to be described later represent any one aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7) described later, [1] or The polymerizable liquid crystal composition according to [2].

[4]

The polymerizable liquid crystal composition according to any one of [1] to [3], wherein X ¹ and X ² in Formula (I-1) described below represent a linking group represented by -O-.

[5]

In [1] to [4], in which P in formula (I-3) described later represents any one polymerizable group selected from the group consisting of groups represented by formulas (P-1) to (P-20) described later The polymerizable liquid crystal composition according to any one of them.

[6]

Any one of [1] to [5], wherein the content of the polymerizable smectic liquid crystal compound is 15 to 75 mass% with respect to the total mass of the polymerizable smectic liquid crystal compound and the compound represented by formula (I-1) to be described later. The polymerizable liquid crystal composition described in

[7]

An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [6].

[8]

The optically anisotropic film according to [7], which satisfies the following formula (III).

0.50<Re(450)/Re(550)<1.00… (III)

Here, in the formula (III), Re(450) represents in-plane retardation at a wavelength of 450 nm of the optically anisotropic film, and Re(550) represents in-plane retardation at a wavelength of 550 nm of the optically anisotropic film.

[9]

An optical film having the optically anisotropic film according to [7] or [8].

[10]

A polarizing plate having the optical film according to [9] and a polarizer.

[11]

An image display device having the optical film according to [9] or the polarizing plate according to [10].

ADVANTAGE OF THE INVENTION According to this invention, it has reverse wavelength dispersion property, and the polymeric liquid crystal composition used for formation of the optically anisotropic film excellent in amine resistance, an optically anisotropic film, an optical film, a polarizing plate, and an image display device can be provided.

1A is a schematic cross-sectional view showing an example of the optical film of the present invention.
1B is a schematic cross-sectional view showing an example of the optical film of the present invention.
1C is a schematic cross-sectional view showing an example of the optical film of the present invention.

Hereinafter, the present invention will be described in detail.

Although description of the structural requirements described below may be made based on the typical embodiment of this invention, this invention is not limited to such an embodiment.

In addition, in this specification, the numerical range shown using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in this specification, each component may use the substance corresponding to each component individually by 1 type, and may use 2 or more types together. Here, when using together 2 or more types of substances with respect to each component, content with respect to the component refers to content of the sum total of the substances used together, unless there is a special explanation.

In addition, in the present specification, the direction of bonding of the indicated divalent group (eg, -CO-NR-) is not particularly limited, except when the bonding position is specified. For example, When X ¹ in Formula (I-1) is -CO-NR-, the position bonded to the L ¹ side is *1, and the position bonded to the Ar ¹ side is *2, then X ¹ is *1 -CO-NR-*2 may be sufficient, and *1-NR-CO-*2 may be sufficient.

[Polymerizable liquid crystal composition]

The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition comprising a compound represented by the following formula (I-1) (hereinafter also abbreviated as “specific compound”) and a polymerizable smectic liquid crystal compound.

In the present invention, as described above, by using a polymerizable liquid crystal composition in which a polymerizable smectic liquid crystal compound is blended together with a specific compound, reverse wavelength dispersion property is expressed in the optically anisotropic film to be formed, and amine resistance is also good. becomes

Although this is not clear in detail, the present inventors guess as follows.

That is, a specific compound is a linking group (X 1 and X 2 ) bonded to an aromatic ring (Ar ¹ and Ar ² ) having a maximum absorption wavelength at 280 to 420 nm in Formula (I-1) to be described later (X ¹ and X ² ), an ester bond Since it has a strong bond which does not contain it, it is thought that amine resistance improved.

Moreover, when a specific compound and a polymerizable smectic liquid crystal compound are mixed, the structure represented by Formula (I-3), which will be described later, included in the molecular long axis of the specific compound, and the mesogenic skeleton of the polymerizable smectic liquid crystal compound interact By doing so, while liquid crystallinity was expressed also as a mixture, it is thought that the reverse wavelength dispersion property resulting from the structure of a specific compound was expressed.

Hereinafter, each component of the polymeric liquid crystal composition of this invention is demonstrated in detail.

[specific compound]

The specific compound contained in the polymeric liquid crystal composition of this invention is a compound represented by following formula (I-1).

[Formula 1]

In the formula (I-1), Ar ¹ and Ar ² each independently represent an aromatic ring having a maximum absorption wavelength of 280 to 420 nm.

In the formula (I-1), D ¹ is a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more of these, R ¹ to R ⁵ are each independently a hydrogen atom, a fluorine atom, or a carbon number of 1 to 4 represents an alkyl group.

Moreover, p represents 0 or 1 in said Formula (I-1).

In addition, in the formula (I-1), X ¹ and X ² each independently represent -O-, -S-, -CO-, -CO-NR ⁶ -, or a single bond, and R ⁶ Each independently represents a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group.

In the formula (I-1), p represents 0 or 1 as described above, but it is preferably 0, that is, D ¹ and Ar ² in the formula (I-1) do not exist. Do.

In the formula (I-1), as the divalent linking group represented by one aspect of D ¹ , for example, -CO-, -O-, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ¹ R ² -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ¹ R ² -, -CO-O-CR ¹ R ² - , -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ¹ R ² -, -CR ¹ R ² -CO-O-CR ¹ R ² -, -NR ⁵ -CR ¹ R ² -, and -CO-NR ⁵ -; and the like. R ¹ , R ² and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

Among these, any one of -CO-, -O-, and -CO-O- is preferable.

In said formula (I-1), it is preferable that it is -O- or -S-, and, as for X ¹ and X ² , it is more preferable that it is -O- from the reason that the amine resistance of the optically anisotropic film|membrane formed becomes more favorable. .

In the formula (I-1), Ar ¹ and Ar ² represent an aromatic ring having a maximum absorption wavelength of 280 to 420 nm as described above, but because the light resistance of the optically anisotropic film to be formed becomes better, 300 It is preferable to represent the aromatic ring which has a maximum absorption wavelength at -400 nm.

Here, a maximum absorption wavelength means the maximum absorption wavelength in the absorption spectrum measured by the following method using the compound which substituted ^the coupling group ( ^X1 and X2) with an aromatic ring by the methyl group.

<Measurement method>

The compound is dissolved in chloroform to prepare a solution having a concentration of 1% by mass.

Next, the prepared solution is put into a quartz cell (10 mm rectangular cell), and the absorbance of the solution in a wavelength range of 200 to 800 nm is measured using an ultraviolet-visible-infrared spectrophotometer U-3100PC (Shimadzu Corporation).

Next, in the obtained absorption spectrum, the maximum absorption wavelength is calculated|required.

In the formula (I-1), Ar ¹ and Ar ² are groups represented by the following formulas (Ar-1) to (Ar-7) from the reason that reverse wavelength dispersion is easily expressed in the optically anisotropic film to be formed. It is preferable to represent any one aromatic ring selected from the group which consists of. In addition, in the following formulas (Ar-1) to (Ar-7), * indicates a bonding position with X ¹ or D ¹ for Ar ¹ , and does not indicate a bonding position with D ¹ or X ² for Ar ² However, when p is 0, it represents a bonding position with X ¹ or X ² .

[Formula 2]

In the formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ is a hydrogen atom or A C1-C6 alkyl group is represented, Y< ¹ > represents a C6-C12 aromatic hydrocarbon group which may have a substituent, or a C3-C12 aromatic heterocyclic group.

Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁷ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, etc. are mentioned.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y ¹ include aryl groups such as phenyl group, 2,6-diethylphenyl group and naphthyl group.

Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y ¹ include heteroaryl groups such as thienyl group, thiazolyl group, furyl group and pyridyl group.

Moreover, as a substituent which Y< ¹ > may have, for example, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group, an alkenyl group, an alkynyl group , a halogen atom, a cyano group, a nitro group, an alkylthiol group, and an N-alkyl carbamate group. Among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a hal Rosen atoms are preferred.

As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group) tyl group, sec-butyl group, t-butyl group and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group or an ethyl group is particularly preferable.

As the alkoxy group, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) is more preferable, and carbon number An alkoxy group of 1-4 is more preferable, and a methoxy group or an ethoxy group is especially preferable.

Examples of the alkoxycarbonyl group include a group in which an oxycarbonyl group (-O-CO- group) is bonded to an alkyl group exemplified above, and among them, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group or an iso A propoxycarbonyl group is preferable, and a methoxycarbonyl group is more preferable.

Examples of the alkylcarbonyloxy group include groups in which a carbonyloxy group (-CO-O- group) is bonded to the alkyl group exemplified above, and among them, a methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, or An isopropylcarbonyloxy group is preferable, and a methylcarbonyloxy group is more preferable.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, Among these, a fluorine atom or a chlorine atom is preferable.

Further, in the formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. represents a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁸ , -NR ⁹ R ¹⁰ , or -SR ¹¹ , R ⁸ to R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.

The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, an isopropyl group, and a tert-pentyl group. (1,1-dimethylpropyl group), tert-butyl group and 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, ethyl group and tert-butyl group are particularly preferable.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a methylcyclohexyl group. , monocyclic saturated hydrocarbon groups such as ethylcyclohexyl group; Monocyclic groups such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodesenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodecadiene unsaturated hydrocarbon group; Bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2 .1.1 ^3,6 .0 ^2,7 ] polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group;

Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, 2,6-diethylphenyl group, naphthyl group, and biphenyl group, and an aryl group having 6 to 12 carbon atoms ( In particular, a phenyl group) is preferable.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Among these, it is preferable that they are a fluorine atom, a chlorine atom, and a bromine atom.

On the other hand, specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁸ to R ¹¹ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group etc. are mentioned.

In addition, in the formulas (Ar-2) and (Ar-3), A ¹ and A ² are each independently -O-, -N(R ¹² )-, -S-, and -CO- A group selected from the group consisting of is represented, and R ¹² represents a hydrogen atom or a substituent.

Examples of the substituent represented by R ¹² include the same substituents as the substituents Y ¹ in the formula (Ar-1) may have.

Moreover, in said Formula (Ar-2), X represents the nonmetallic atom of Groups 14-16 to which the hydrogen atom or the substituent may couple|bond.

Moreover, as a nonmetallic atom of Groups 14-16 represented by X, for example, an oxygen atom, a sulfur atom, a hydrogen atom, or a nitrogen atom to which a substituent is bonded [=NR ^N1 , R ^N1 represents a hydrogen atom or a substituent]. , a hydrogen atom or a carbon atom to which a substituent is bonded [=C-(R ^C1 ) ₂ , R ^C1 represents a hydrogen atom or a substituent.].

Specific examples of the substituent include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl carbo group. A nyl group, a sulfo group, a hydroxyl group, etc. are mentioned.

In addition, in the formula (Ar-3), D ⁴ and D ⁵ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, R ¹ to R ⁵ are each independently a hydrogen atom, a fluorine atom, Or a C1-C4 alkyl group is shown.

Here, as a divalent coupling group, the thing similar to what was demonstrated for D1 in said Formula (I- ¹ ) is mentioned.

In the formula (Ar-3), SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. At least one of -CH ₂ - constituting the alkylene group represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, Q is a substituent indicates As a substituent, the thing similar to the substituent which Y< ¹ > in said Formula (Ar-1) may have is mentioned.

Here, as the linear or branched alkylene group having 1 to 12 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, a heptylene group, etc. are suitable. can be heard

In addition, in the formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.

Examples of the monovalent organic group include an alkyl group, an aryl group, and a heteroaryl group. Although linear, branched, or cyclic|annular form may be sufficient as an alkyl group, linear is preferable. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are still more preferable. Moreover, although monocyclic or polycyclic may be sufficient as an aryl group, monocyclic is preferable. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable. Moreover, the heteroaryl group may be monocyclic or polycyclic may be sufficient as it. The number of hetero atoms constituting the heteroaryl group is preferably 1-3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. 6-18 are preferable and, as for carbon number of a heteroaryl group, 6-12 are more preferable. Moreover, unsubstituted may be sufficient as an alkyl group, an aryl group, and a heteroaryl group may have a substituent. As a substituent, the thing similar to the substituent which Y< ¹ > in said Formula (Ar-1) may have is mentioned.

In addition, in the formulas (Ar-4) to (Ar-7), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. .

In the formulas (Ar-4) to (Ar-7), Ay is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic heterocycle. It represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring.

Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may couple|bond together, and may form the ring.

Moreover, Q< ³ > represents a C1-C6 alkyl group which may have a hydrogen atom or a substituent.

Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 2 (International Publication No. 2014/010325).

Moreover, as a C1-C6 alkyl group represented by ^Q3 , specifically, for example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group A tyl group, n-pentyl group, and n-hexyl group etc. are mentioned, As a substituent, the thing similar to the substituent which Y< ¹ > in said Formula (Ar-1) may have is mentioned.

In addition, in said Formula (I-1), L< ¹ > and L< ² > respectively independently represent the alkylene group represented by following formula (I-2). In addition, in the following formula (I-2), * represents a bonding position with Mes ¹ or X ¹ with respect to L ¹ , and indicates a bonding position with Mes ² or X ² with respect to L ² .

[Formula 3]

In said formula (I-2), m represents an integer of 1 or more, It is preferable that it is an integer of 2-20, It is more preferable that it is an integer of 2-15, It is especially preferable that it is an integer of 2-10.

Moreover, the hydrogen atom contained in the alkylene group represented by said Formula (I-2) is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, iso It may be substituted with a cyano group, a thioisocyano group, or a C1-C20 alkyl group.

Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl group, amyl group, 2-ethylhexyl group, nonyl group. , a decanyl group, a lauryl group, a cetyl group, a stearyl group, and a cyclohexyl group.

In addition, one of -CH ₂ - constituting the alkylene group represented by the formula (I-2) and not directly bonded to X ¹ or X ² in the formula (I-1) is one or adjacent At least two -CH ₂ -, -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, It may be substituted with -CO-NH-, -NH-CO-, or -C≡C-.

In addition, in said Formula (I- ¹ ), Mes1 and Mes2 ^respectively independently represent the polymeric group containing group represented by following formula (I-3). In addition, in the following formula (I-3), * represents a bonding position with L ¹ for Mes ¹ and a bonding position with L ² for Mes ² .

[Formula 4]

In the formula (I-3), M is 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 ,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,3-dioxane-2,5- represents the diary.

However, the hydrogen atom contained in these groups is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group. , or may be substituted with an alkyl group having 1 to 20 carbon atoms.

In addition, in the formula (I-3), D ² and D ³ are each independently -O-, -S-, -OCH ₂ -, -CH ₂ CH ₂ -, -CO-, -COO-, -CO-S-, -OCO-O-, -CO-NH-, -SCH ₂ -, -CF ₂ O-, -CF ₂ S-, -CH=CH-COO-, -CH=CH-OCO- , -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -COO-CH ₂ -, -OCO-CH ₂ -, -CH=CH-, -N=N-, -CH=N- , -CH=NN=CH-, -CF=CF-, -C≡C-, or a single bond.

Moreover, in said formula (I-3), SP is -CH ₂ which comprises a single bond, a C1-C12 linear or branched alkylene group, or a C1-C12 linear or branched alkylene group. - represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent. As a substituent, the thing similar to the substituent which Y< ¹ > in said Formula (Ar-1) may have is mentioned.

Here, as the linear or branched alkylene group having 1 to 12 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, a heptylene group, etc. are suitable. can be heard

Moreover, in said Formula (I-3), P represents a polymeric group.

As the polymerizable group, a polymerizable group capable of radical polymerization or cationic polymerization is preferable.

As a radically polymerizable group, a well-known radically polymerizable group can be used, As a suitable thing, an acryloyloxy group or a methacryloyloxy group is mentioned. In this case, it is known that an acryloyloxy group is generally fast as for a polymerization rate, and although an acryloyloxy group is preferable from a viewpoint of productivity improvement, methacryloyloxy group can be used similarly as a polymeric group.

As the cationically polymerizable group, a known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spirothoester group, and a vinyloxy group, etc. can be heard Among them, an alicyclic ether group or a vinyloxy group is suitable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.

As an example of a especially preferable polymeric group, any one polymeric group chosen from the group which consists of groups represented by following formula (P-1) - (P-20) is mentioned. Especially, it is more preferable that they are an acryloyloxy group or a methacryloyloxy group. In addition, in the following formulas (P-1) to (P-20), * represents a bonding position with SP.

[Formula 5]

Moreover, in said Formula (I-3), n represents an integer of 2 or more, It is preferable that it is an integer of 2-5, It is more preferable that it is an integer of 2-4, It is still more preferable that it is 2 or 3.

In addition, a plurality of M may be the same or different, respectively, a plurality of D ² may be the same or different, respectively, a plurality of D ³ may be the same or different, respectively, and a plurality of SP is the same, respectively It can be done or it can be different.

As a specific compound, specifically, the compound represented by following formula (1) - (22) is mentioned suitably, for example, Specifically, K (side chain structure) in following formula (1) - (22) As such, compounds each having a side chain structure shown in Tables 1 and 2 below are exemplified.

In addition, in Table 1 and Table 2 below, "*" shown in the side chain structure of K represents the bonding position with an aromatic ring.

In addition, in the side chain structures shown by 1-9 in Table 1 and 2-9 in Table 2 below, the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively, are propylene groups (groups in which a methyl group is substituted with an ethylene group) and represents a mixture of positional isomers having different positions of methyl groups.

[Formula 6]

[Table 1]

[Table 2]

[Polymerizable Smectic Liquid Crystal Compound]

The polymerizable smectic liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is a compound having a polymerizable group and exhibiting a liquid crystal state of a smectic phase.

Here, as a polymeric group, the thing similar to what was demonstrated for P in Formula (I-3) mentioned above is mentioned. Especially, it is preferable that it is any one polymeric group chosen from the group which consists of group represented by Formula (P-1) - (P-20) mentioned above, and it is more preferable that it is an acryloyloxy group or a methacryloyloxy group.

Moreover, it is preferable that the liquid-crystal state shown by a polymerizable smectic liquid crystal compound is a high-order smectic phase. The high-order smectic phase as used herein refers to Smectic A phase, Smectic B phase, Smectic D phase, Smectic E phase, Smectic F phase, Smectic G phase, Smectic H phase, Smectic I phase, Smectic J-phase, Smectic K-phase and Smectic L-phase, among others, Smectic A-phase, Smectic B-phase, Smectic F-phase, Smectic I-phase, inclined smectic F-phase and inclined smectic I Phase is preferable, and Smectic A phase and Mectic B phase are more preferable.

As such a polymerizable smectic liquid crystal compound, various literatures (C. Destrade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981); Japanese Chemical Society edition, Quarterly Chemical Review, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994) B. Kohne et al., Angew. Chem. Soc. Chem. Comm., page 1794 (1985); J. Zhang et al. , J. Am. Chem. Soc., vol. 116, page 2655 (1994)).

In the present invention, the polymerizable smectic liquid crystal compound may be a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, but is preferably a polymerizable liquid crystal compound exhibiting forward wavelength dispersibility.

Here, the term "polymerizable liquid crystal compound exhibiting reverse wavelength dispersion" as used herein means when the in-plane retardation (Re) value at a specific wavelength (visible light range) of the retardation film produced using this is measured. , means that the Re value becomes equal or increases as the measurement wavelength increases.

On the other hand, the "polymerizable liquid crystal compound exhibiting reverse wavelength dispersion" refers to a measurement wavelength when the in-plane retardation (Re) value at a specific wavelength (visible light range) of the retardation film produced using this is measured. As a result, the Re value decreases.

In the present invention, the content of the polymerizable smectic liquid crystal compound is determined from the reason that liquid crystallinity is easily expressed as a mixture due to the interaction between the side chain of the long molecular axis of the specific compound and the mesogenic skeleton of the polymerizable smectic liquid crystal; It is preferable that it is 15-75 mass % with respect to the total mass of a polymerizable smectic liquid crystal compound and the above-mentioned specific compound, and it is more preferable that it is 30-60 mass %.

[Other Polymerizable Compounds]

The polymerizable liquid crystal composition of the present invention may contain other polymerizable compounds having one or more polymerizable groups in addition to the polymerizable smectic liquid crystal compound described above.

Here, the polymeric group which other polymeric compound has is not specifically limited, For example, an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned. Among these, it is preferable to have an acryloyl group and a methacryloyl group.

As another polymeric compound, it is preferable that it is another polymeric compound which has 1-4 polymeric groups from the reason that the durability of the optically anisotropic film|membrane formed improves, and it is more preferable that it is another polymeric compound which has two polymerizable groups. Do.

The other polymerizable compound is preferably a non-liquid crystalline polymerizable compound, and specific examples thereof include the compounds described in paragraphs [0073] to [0074] of Japanese Patent Application Laid-Open No. 2016-053709.

In the case of containing such other polymerizable compounds, the content is preferably less than 50 mass%, more preferably 40 mass% or less, more preferably 2-30 mass%, with respect to the mass of the above-mentioned polymerizable liquid crystal compound. desirable.

[Polymerization Initiator]

It is preferable that the polymeric liquid crystal composition of this invention contains the polymerization initiator.

It is preferable that the polymerization initiator to be used is a photoinitiator which can start a polymerization reaction by ultraviolet irradiation.

Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Patent Publication Nos. 2367661 and 2367670), acyl ether (described in US Patent Publication No. 2448828), α-hydrocarbon-substituted aromatic Combination of an acyloin compound (described in U.S. Patent Publication No. 2722512), a polynuclear quinone compound (described in each specification of U.S. Patent Publication Nos. 3046127 and 2951758), a triarylimidazole dimer and p-aminophenylketone (U.S. Patent No. 3046127) Publication No. 3549367 described), acridine and phenazine compounds (described in Japanese Patent Application Laid-Open No. 60-105667 and US Patent No. 4239850) and oxadiazole compounds (described in U.S. Patent Publication No. 4212970), acylphos and fin oxide compounds (described in Japanese Patent Application Laid-Open No. 63-40799, Japanese Unexamined Patent Publication No. Hei 5-29234, Japanese Unexamined Patent Publication No. Hei 10-95788, and Japanese Unexamined Patent Publication No. 10-29997). .

Moreover, in the present invention, it is also preferable that the polymerization initiator is an oxime-type polymerization initiator, and specific examples thereof include the initiators described in paragraphs [0049] to [0052] of International Publication No. 2017/170443.

〔menstruum〕

It is preferable that the polymeric liquid crystal composition of this invention contains a solvent from viewpoints, such as workability|operativity for forming an optically anisotropic film|membrane.

Specifically as the solvent, for example, a ketone solvent (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), an ether solvent (eg, dioxane) Sein, tetrahydrofuran, etc.), cyclic amide solvents (eg, N-methylpyrrolidone, N-ethylpyrrolidone, N,N'-dimethylimidazolinone, etc.), aliphatic hydrocarbon solvents (For example, hexane), an alicyclic hydrocarbon solvent (for example, cyclohexane, etc.), an aromatic hydrocarbon solvent (for example, toluene, xylene, trimethylbenzene, etc.), halogen Carbonated solvents (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), ester solvents (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols Solvents (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolve solvents (e.g. methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetate solvents, sulfoxide solvents solvents (eg, dimethyl sulfoxide), chain amide solvents (eg, dimethylformamide, dimethylacetamide, etc.), etc., may be used alone or two types You may use the above together.

In the present invention, among the solvents described above, at least one solvent selected from the group consisting of ketone solvents, ether solvents and cyclic amide solvents because the effect of the present invention for suppressing increase in filtration pressure becomes remarkable. It is preferable to be

[Leveling agent]

It is preferable that the polymeric liquid crystal composition of this invention maintains the surface of an optically anisotropic film|membrane smooth and contains a leveling agent from a viewpoint of making orientation control easy.

As such a leveling agent, since the leveling effect with respect to the addition amount is high, it is preferable that it is a fluorine-type leveling agent or a silicon-type leveling agent, and it is more preferable that it is a fluorine-type leveling agent from a viewpoint that exudation (bloom, bleed) does not easily occur.

Specific examples of the leveling agent include compounds described in paragraphs [0079] to [0102] of Japanese Patent Application Laid-Open No. 2007-069471, and general formula (I) described in Japanese Patent Application Laid-Open No. 2013-047204. The compound represented (especially the compound described in paragraphs [0020] to [0032]), the compound represented by the general formula (I) described in Japanese Patent Application Laid-Open No. 2012-211306 (especially the compound described in the paragraphs [0022] to [0029]), Liquid crystal alignment promoter represented by the general formula (I) described in Japanese Patent Application Laid-Open No. 2002-129162 (especially the compounds described in paragraphs [0076] to [0078] and [0082] to [0084]), Japanese Patent Application Laid-Open No. 2005-099248 and compounds represented by the general formulas (I), (II) and (III) described in the preceding paragraph (especially those described in paragraphs [0092] to [0096]) and the like. Moreover, you may combine the function as an orientation control agent mentioned later.

[Orientation controlling agent]

The polymerizable liquid crystal composition of the present invention can contain an orientation controlling agent as needed.

With the orientation controlling agent, in addition to homogeneous orientation, various orientation states such as homeotropic orientation (vertical orientation), oblique orientation, hybrid orientation, and cholesteric orientation can be formed, and a specific orientation state can be made more uniform and In addition, it can be realized by controlling more precisely.

As an orientation control agent which accelerates|stimulates a homogeneous orientation, a low molecular orientation control agent and a polymeric orientation control agent can be used, for example.

As a low molecular weight orientation control agent, For example, Paragraphs [0009] - [0083] of Unexamined-Japanese-Patent No. 2002-20363, Paragraphs [0111] - [0120] of Unexamined-Japanese-Patent No. 2006-106662, and Unexamined-Japanese-Patent No. Reference may be made to the description of paragraphs [0021] to [0029] of Publication No. 2012-211306, the contents of which are incorporated herein by reference.

In addition, as a polymeric orientation controlling agent, see, for example, paragraphs [0021] to [0057] of Japanese Patent Application Laid-Open No. 2004-198511, and paragraphs [0121] to [0167] of Japanese Patent Application Laid-Open No. 2006-106662 can be, the contents of which are incorporated herein by reference.

Moreover, as an orientation control agent which forms or accelerates|stimulates a homeotropic orientation, a boronic acid compound and an onium salt compound are mentioned, for example, Specifically, Unexamined-Japanese-Patent No. 2008-225281 [0023] - [0032] ] Paragraph, [0052] to [0058] of Japanese Patent Application Laid-Open No. 2012-208397, [0024] to [0055] of Japanese Unexamined Patent Publication No. 2008-026730, [0043] to [0043] of Japanese Unexamined Patent Publication No. 2016-193869 Reference may be made to the compounds described in paragraph 0055, etc., the contents of which are incorporated herein by reference.

On the other hand, the cholesteric alignment can be realized by adding a chiral agent to the polymerizable liquid crystal composition of the present invention, and the direction of rotation of the cholesteric alignment can be controlled by the direction of the chirality. In addition, the pitch of the cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.

It is preferable that it is 0.01-10 mass % with respect to the total solid mass in a polymeric liquid crystal composition, and, as for content in the case of containing an orientation control agent, it is more preferable that it is 0.05-5 mass %. If the content is within this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without precipitation, phase separation, orientation defects, or the like while realizing a desired orientation state.

These orientation control agents can also provide a polymerizable functional group, especially a polymerizable functional group which can superpose|polymerize with the polymeric liquid crystal compound which comprises the polymeric liquid crystal composition of this invention.

[Other ingredients]

The polymerizable liquid crystal composition of the present invention may contain components other than the above-mentioned components, for example, liquid crystal compounds other than the above-mentioned polymerizable smectic liquid crystal compound, surfactant, tilt angle control agent, and alignment aid. ), a plasticizer, and a crosslinking agent.

[Optical Anisotropic Film]

The optically anisotropic film of this invention is an optically anisotropic film|membrane obtained by superposing|polymerizing the polymeric liquid crystal composition of this invention mentioned above.

As a formation method of an optically anisotropic film, after setting it as a desired orientation state using the polymeric liquid crystal composition of this invention mentioned above, the method of immobilization by superposition|polymerization, etc. are mentioned, for example. In particular, in this invention, the aspect which forms an optically anisotropic film after going through the process of storing after preparing the polymeric liquid crystal composition of this invention mentioned above is preferable.

Although polymerization conditions are not specifically limited here, In superposition|polymerization by light irradiation, it is preferable to use an ultraviolet-ray. The irradiation amount, 10mJ/cm ² ~ 50J/cm ² It is preferable that it is, 20mJ/cm ² ~ 5J/cm ² It is more preferable, It is more preferably 30mJ/cm ² ~ 3J/cm ² It is more preferably, 50 ~ 1000mJ It is particularly preferred that it is /cm ² . Moreover, in order to accelerate|stimulate a polymerization reaction, you may carry out on heating conditions.

In addition, in this invention, an optically anisotropic film can be formed on the arbitrary support body in the optical film of this invention mentioned later, or on the polarizer in the polarizing plate of this invention mentioned later.

It is preferable that the optically anisotropic film|membrane of this invention satisfy|fills following formula (III).

0.50<Re(450)/Re(550)<1.00… (III)

Here, in the formula (III), Re(450) represents in-plane retardation at a wavelength of 450 nm of the optically anisotropic film, and Re(550) represents in-plane retardation at a wavelength of 550 nm of the optically anisotropic film. In addition, in this specification, when the measurement wavelength of retardation is not specified, let the measurement wavelength be 550 nm.

In addition, the value of in-plane retardation and the retardation of thickness direction says the value measured using the light of a measurement wavelength using AxoScan OPMF-1 (made by Optoscience Corporation).

Specifically, by inputting the average refractive index ((Nx+Ny+Nz)/3) and the film thickness (d(μm)) in AxoScan OPMF-1,

Slow axis direction (°)

Re(λ)=R0(λ)

Rth(λ)=((nx+ny)/2-nz)×d

is calculated

In addition, R0(λ) is expressed as a numerical value calculated by AxoScan OPMF-1, and means Re(λ).

It is preferable that it is a positive A plate or a positive C plate, and, as for the optically anisotropic film|membrane of this invention, it is more preferable that it is a positive A plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.

Let nx be the refractive index in the direction of the slow axis in the film plane (the direction in which the in-plane refractive index is maximized), ny the refractive index in the direction orthogonal to the in-plane slow axis and in-plane, and nz the refractive index in the thickness direction. , a positive A plate satisfies the relationship of formula (A1), and a positive C plate satisfies the relationship of formula (C1). In addition, in the positive A plate, Rth shows a positive value, and in the positive C plate, Rth shows a negative value.

Formula (A1) nx>ny≒nz

Formula (C1) nz>nx≒ny

In addition, the above "≒" includes not only the case where both are completely the same, but also the case where both are substantially the same.

"Substantially the same" means, in a positive A plate, for example, (ny-nz) x d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≒nz", and (nx-nz)xd is included in "nx≈nz" also when it is -10-10 nm, Preferably -5-5 nm. In the case of a positive C plate, for example, (nx-ny)×d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, also included in “nx≒ny” do.

When the optically anisotropic film of the present invention is a positive A plate, from the viewpoint of functioning as a λ/4 plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, more preferably 130 to 150 nm It is preferable, and it is especially preferable that it is 130-140 nm.

Here, "λ/4 plate" is a plate having a λ/4 function, specifically, a plate having a function of converting linearly polarized light of a predetermined specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). .

[optical film]

The optical film of the present invention is an optical film having the optically anisotropic film of the present invention.

1A, 1B, and 1C (hereinafter, when these drawings do not require special distinction, they are abbreviated as "Fig. 1") are schematic cross-sectional views each showing an example of the optical film of the present invention.

In addition, FIG. 1 is a schematic diagram, and the relationship of the thickness of each layer, a positional relationship, etc. do not necessarily correspond with an actual thing, and the support body, orientation film, and hard-coat layer shown in FIG. 1 are all arbitrary structural members.

The optical film 10 shown in FIG. 1 has the support body 16, the orientation film 14, and the optically anisotropic film 12 in this order.

Moreover, as shown in FIG. 1B, the optical film 10 may have the hard-coat layer 18 on the opposite side to the side in which the orientation film 14 of the support body 16 was provided, as shown in FIG. 1C. , you may have the hard-coat layer 18 on the side opposite to the side in which the orientation film 14 of the optically anisotropic film|membrane 12 was provided.

Hereinafter, the various members used for the optical film of this invention are demonstrated in detail.

[Optical Anisotropic Film]

The optically anisotropic film which the optical film of this invention has is the optically anisotropic film of this invention mentioned above.

In the optical film of this invention, although it does not specifically limit about the thickness of the said optically anisotropic film, It is preferable that it is 0.1-10 micrometers, and it is more preferable that it is 0.5-5 micrometers.

[Support]

As mentioned above, the optical film of this invention may have a support body as a base material for forming an optically anisotropic film|membrane.

It is preferable that such a support body is transparent, and, specifically, it is preferable that the light transmittance is 80 % or more.

As such a support body, a glass substrate and a polymer film are mentioned, for example, As a material of a polymer film, Cellulose polymer; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; Thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene/propylene copolymer; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamide; imide-based polymers; sulfone-based polymers; polyether sulfone-based polymer; polyetheretherketone-based polymers; polyphenylene sulfide-based polymer; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymer; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; Or the polymer which mixed these polymers is mentioned.

Moreover, the aspect which serves also as such a support body may be sufficient as the polarizer mentioned later.

In this invention, although it does not specifically limit about the thickness of the said support body, It is preferable that it is 5-60 micrometers, and it is more preferable that it is 5-30 micrometers.

[Orientation film]

When the optical film of this invention has the arbitrary support bodies mentioned above, it is preferable to have an orientation film between a support body and an optically anisotropic film. Moreover, the aspect which the above-mentioned support body also serves as an orientation film may be sufficient.

An alignment film generally has a polymer as a main component. As a polymer material for alignment films, there are descriptions in many documents, and many commercial items can be obtained.

As for the polymer material used in this invention, polyvinyl alcohol or a polyimide, and its derivative(s) are preferable. In particular, modified or unmodified polyvinyl alcohol is preferable.

Regarding the alignment film usable in the present invention, for example, the alignment film described in International Publication No. 01/088574, page 43, line 24 to page 49, line 8; Modified polyvinyl alcohol described in paragraphs [0071] to [0095] of Japanese Patent Publication No. 3907735; The liquid crystal aligning film etc. which are formed with the liquid crystal aligning agent of Unexamined-Japanese-Patent No. 2012-155308 are mentioned.

In this invention, it is also preferable to use a photo-alignment film as an alignment film from the reason that it becomes possible to prevent planar deterioration by not contacting the alignment film surface at the time of formation of an alignment film.

Although it does not specifically limit as a photo-alignment film, Polymer materials, such as a polyamide compound and a polyimide compound, described in paragraphs [0024] - [0043] of International Publication No. 2005/096041; A liquid crystal aligning film formed of the liquid crystal aligning agent which has a photo-alignment group of Unexamined-Japanese-Patent No. 2012-155308; The brand name LPP-JP265CP by Rolic Technologies, etc. can be used.

Further, in the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating surface irregularities that may exist in the support to form an optically anisotropic film of a uniform film thickness, it is preferably 0.01 to 10 μm, and 0.01 to It is more preferable that it is 1 micrometer, and it is still more preferable that it is 0.01-0.5 micrometer.

[hard coat layer]

It is preferable that the optical film of this invention has a hard-coat layer in order to provide the physical strength of a film. Specifically, you may have a hard-coat layer on the side opposite to the side on which the orientation film of the support body was provided (refer FIG. 1B), and you may have a hard-coat layer on the side opposite to the side on which the orientation film of an optically anisotropic film was provided (FIG. 1c). reference).

As a hard-coat layer, the thing of Paragraph [0190] - [0196] of Unexamined-Japanese-Patent No. 2009-98658 can be used.

[Other optically anisotropic films]

The optical film of the present invention may have another optically anisotropic film separately from the optically anisotropic film of the present invention.

That is, the optical film of the present invention may have a laminated structure of the optically anisotropic film of the present invention and another optically anisotropic film.

Such other optically anisotropic film is not particularly limited as long as it is an optically anisotropic film obtained by using the above-described polymerizable smectic liquid crystal compound or another polymerizable compound (especially a liquid crystal compound) without blending the specific compound described above.

Here, in general, the liquid crystal compound can be classified into a rod-shaped type and a disk-shaped type from the shape thereof. There are also low molecular weight and high molecular weight types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (Physical/Phase Change Dynamics of Polymers, Masaoser Doi, p. 2, Iwanami Shoten, 1992). In the present invention, although any liquid crystal compound can be used, it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound). Two or more types of rod-shaped liquid crystal compounds, two or more types of disk-shaped liquid crystal compounds, or a mixture of rod-shaped liquid crystal compounds and disk-shaped liquid crystal compounds may be used. For immobilization of the above-mentioned liquid crystal compound, it is more preferable to use a rod-shaped liquid crystal compound having a polymerizable group or a disk-shaped liquid crystal compound, and it is more preferable that the liquid crystal compound has two or more polymerizable groups in one molecule. When the liquid crystal compound is a mixture of two or more types, it is preferable that at least one type of liquid crystal compound has two or more polymerizable groups in one molecule.

As the rod-shaped liquid crystal compound, for example, those described in paragraphs [0026] to [0098] of Japanese Patent Application Laid-Open No. 11-513019 or 2005-289980 can be preferably used, and discotic liquid crystal compounds As, for example, Paragraphs [0020] to [0067] of Japanese Patent Application Laid-Open No. 2007-108732 and Paragraphs [0013] to [0108] of Japanese Patent Application Laid-Open No. 2010-244038 can be preferably used, but these not limited

[Ultraviolet absorber]

It is preferable that the optical film of this invention considers the influence of external light (especially ultraviolet-ray), and contains an ultraviolet-ray (UV) absorber.

The ultraviolet absorber may be contained in the optically anisotropic film of this invention, and may be contained in members other than the optically anisotropic film which comprises the optical film of this invention. As a member other than an optically anisotropic film|membrane, a support body is mentioned suitably, for example.

As the ultraviolet absorber, any conventionally known ultraviolet absorber capable of exhibiting ultraviolet absorbency can be used. Among such ultraviolet absorbers, it is preferable to use a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber from the viewpoint of having high ultraviolet absorbing properties and obtaining ultraviolet absorbing power (ultraviolet blocking ability) used in an image display device.

Moreover, in order to widen the absorption width of an ultraviolet-ray, 2 or more types of ultraviolet absorbers from which a maximum absorption wavelength differs can be used together.

As the ultraviolet absorber, specifically, for example, the compounds described in paragraphs [0258] to [0259] of Japanese Patent Application Laid-Open No. 2012-18395, and paragraphs [0055] to [0105] of Japanese Patent Application Laid-Open No. 2007-72163 compounds, and the like.

Moreover, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, and Tinuvin1577 (all made by BASF Corporation) etc. can be used as a commercial item.

[Polarizer]

The polarizing plate of this invention has the optical film of this invention mentioned above, and a polarizer.

Further, the polarizing plate of the present invention can be used as a circularly polarizing plate when the optically anisotropic film of the present invention described above is a λ/4 plate (positive A plate).

Further, in the polarizing plate of the present invention, when the optically anisotropic film of the present invention described above is a λ/4 plate (positive A plate), the angle between the slow axis of the λ/4 plate and the absorption axis of the polarizer to be described later is 30 to 60° It is preferable that it is, It is more preferable that it is 40-50 degrees, It is still more preferable that it is 42-48 degrees, It is especially preferable that it is 45 degrees.

Here, the "slow axis" of the λ/4 plate means the direction in which the refractive index is maximized in the plane of the λ/4 plate, and the "absorption axis" of the polarizer means the direction with the highest absorbance.

[Polarizer]

The polarizer of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption type polarizer and reflection type polarizer can be used.

As the absorption-type polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer are used. The iodine-based polarizer and the dye-based polarizer include an application-type polarizer and a stretch-type polarizer, and both can be applied. A polarizer produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching is preferable.

Moreover, as a method of obtaining a polarizer by extending|stretching and dyeing in the state of the laminated|multilayer film in which the polyvinyl alcohol layer was formed on the base material, Japanese Patent Publication No. 5048120, Japanese Patent No. 5143918, Japanese Patent Publication Nos. 4691205, Japanese Patent Publication No. 4751481 and Japanese Patent Publication No. 4751486 are mentioned, and the well-known technique regarding these polarizers can also be used preferably.

As the reflective polarizer, a polarizer in which thin films having different birefringence are laminated, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wave plate are combined, and the like are used.

Among them, in view of better adhesion, polyvinyl alcohol-based resins (a polymer containing -CH ₂ -CHOH- as a repeating unit, in particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer) It is preferable that it is a polarizer containing a.

In this invention, although the thickness of a polarizer is not specifically limited, It is preferable that they are 3 micrometers - 60 micrometers, It is more preferable that they are 5 micrometers - 30 micrometers, It is more preferable that they are 5 micrometers - 15 micrometers.

[Adhesive layer]

As for the polarizing plate of this invention, the adhesive layer may be arrange|positioned between the optically anisotropic film in the optical film of this invention, and a polarizer.

As the pressure-sensitive adhesive layer used for lamination of the optically anisotropic film and the polarizer, for example, the ratio of the storage elastic modulus G' to the loss elastic modulus G" (tanδ = G"/G') measured by a dynamic viscoelasticity measuring device is 0.001 to 1.5 A phosphorus substance is shown and what is called an adhesive, the substance which creeps easily, etc. are contained. As an adhesive which can be used for this invention, although polyvinyl alcohol-type adhesive is mentioned, for example, it is not limited to this.

[Image display device]

The image display apparatus of this invention is an image display apparatus which has the optical film of this invention, or the polarizing plate of this invention.

The display element used in the image display apparatus of this invention is not specifically limited, For example, a liquid crystal cell, an organic electroluminescence (hereafter abbreviated as "EL") display panel, a plasma display panel, etc. are mentioned. there is.

Among these, it is preferable that they are a liquid crystal cell and an organic electroluminescent display panel, and it is more preferable that they are a liquid crystal cell. That is, as an image display device of this invention, it is preferable that it is a liquid crystal display device using a liquid crystal cell as a display element, and it is preferable that it is an organic electroluminescence display using an organic electroluminescence display panel as a display element, and it is more preferable that it is a liquid crystal display device.

[Liquid crystal display device]

The liquid crystal display device which is an example of the image display device of this invention is a liquid crystal display device which has the polarizing plate of this invention mentioned above, and a liquid crystal cell.

In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the polarizing plate of the present invention as the polarizing plate on the front side, and it is more preferable to use the polarizing plate of the present invention as the polarizing plate on the front side and the rear side. .

Below, the liquid crystal cell which comprises a liquid crystal display device is demonstrated in detail.

<Liquid crystal cell>

The liquid crystal cell used for a liquid crystal display device is a VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode, or TN (Twisted Nematic) mode. ) mode, but is not limited thereto.

In the liquid crystal cell of TN mode, the rod-shaped liquid crystalline molecules are substantially horizontally oriented at the time of no voltage application, and are twisted at 60-120 degrees. The liquid crystal cell of TN mode is most used as a color TFT liquid crystal display device, and there exists description in many documents.

In the liquid crystal cell of the VA mode, rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied. In the liquid crystal cell of VA mode, (1) the liquid crystal cell of VA mode in the narrow sense in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when voltage is applied (Japanese Patent Application Laid-Open No. In addition to (described in No. 2-176625), (2) a liquid crystal cell (SID97, Digest of tech. Papers) in which the VA mode is multi-domained (in MVA mode) 28 ( 1997) 845), (3) liquid crystal cell in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically aligned when no voltage is applied, and torsional multi-domain aligned when voltage is applied (Preview of the Japanese Liquid Crystal Conference) 58-59 (1998)) and (4) liquid crystal cells in SURVIVAL mode (presented by LCD International 98). Moreover, any of PVA(Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA(Polymer-Sustained Alignment) may be sufficient. About the details of these modes, there exist detailed description in Unexamined-Japanese-Patent No. 2006-215326 and Unexamined-Japanese-Patent No. 2008-538819.

In the liquid crystal cell of the IPS mode, rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and an electric field parallel to the substrate surface is applied so that the liquid crystal molecules respond in a planar manner. In the IPS mode, black display is performed in a state in which no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other. A method of improving a viewing angle by reducing leakage light during black display in an oblique direction using an optical compensatory sheet It is disclosed in Patent Publication No. 9-292522, Japanese Patent Application Laid-Open No. Hei 11-133408, Japanese Unexamined Patent Publication No. Hei 11-305217, and Japanese Unexamined Patent Publication No. Hei 10-307291.

[Organic EL display device]

As an organic EL display device which is an example of the image display device of the present invention, for example, from the viewer side, a λ/4 plate (positive A plate) made of a polarizer, an optically anisotropic film of the present invention, and an organic EL display panel The aspect having in this order is mentioned suitably.

Moreover, an organic electroluminescent display panel is a display panel comprised using the organic electroluminescent element formed by pinching|interposing an organic light emitting layer (organic electroluminescent layer) between electrodes (between a cathode and an anode). The structure in particular of an organic electroluminescent display panel is not restrict|limited, A well-known structure is employ|adopted.

Example

The present invention will be described in more detail below based on examples. Materials, amounts of use, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the Examples shown below.

[Synthesis of specific compound (I-g)]

[Formula 7]

As shown in the above scheme, compound (I-a: 4-hydroxybutyl acrylate) 60.0 g, triethylamine 49.3 g, and BHT (dibutylhydroxytoluene) 0.9 g, DMAc (dimethylacetamide) 120.1 mL, and 114.1 mL of toluene were mixed. Then, it cooled to 0 degreeC of internal temperature, and 50.6 g of methyl chlorides were dripped slowly. After completion|finish of dripping, it stirred at 0 degreeC of internal temperature for 1 hour. Then, it returned to room temperature (23 degreeC), liquid-separated with diluted hydrochloric acid, the 2nd time liquid separation was performed with brine, and compound (I-b) was obtained.

Toluene solution of compound (I-b) obtained above, 1,1'-bicyclohexyl-4,4'-dicarboxylic acid 91.40 g, triethylamine 72.73 g, and dibutylhydroxytoluene 0.8 g, DMAc 274.2 mL, and 69.7 mL of toluene were mixed. Then, it heated to 90 degreeC internal temperature, and made it react for 5 hours. Then, it returned to room temperature, diluted hydrochloric acid was added, and it heated at 42 degreeC and liquid-separated. Next, 0.5 g of TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and 164.5 mL of toluene were added, and the solution was separated twice with an aqueous sodium hydrogen carbonate solution after that. The resulting solution was concentrated with an evaporator, the toluene concentration was adjusted to 50%, and 25.7 g of N,N-dimethylformamide (DMF) was added to obtain a compound (I-c).

235.0 g of the toluene solution of the compound (I-c) obtained above and 0.2 g of dibutylhydroxytoluene were mixed with 41.9 mL of toluene. Then, it cooled to 0 degreeC internal temperature, and 21.0 g of thionyl chloride was dripped slowly. After completion|finish of dripping, it returned to room temperature and stirred for 30 minutes. Thereafter, it was allowed to stand to remove the emulsion that precipitated at the bottom of the reaction vessel. Then, it cooled to the internal temperature of 0 degreeC, and the mixed solution of 26.5 g of trans-4-hydroxycyclohexanecarboxylic acids and 56.0 mL of DMAc was dripped slowly. After completion|finish of dripping, it returned to room temperature and stirred for 5 hours. Then, 300 ml of 5% sodium hydrogencarbonate aqueous solution and 300 mL of hexane were added, and the precipitated solid was extracted by filtration. The resulting solid was mixed with 300 mL of ethyl acetate, heated to 60° C. and stirred for 1 hour, and then the solid was extracted by filtration to obtain compound (I-d).

10 g of the compound (I-d) obtained above was weighed, 3.7 g of DMF and 0.02 g of dibutylhydroxytoluene were added, and it mixed with 50.0 mL of toluene. Then, it cools to 0 degreeC internal temperature, and 2.8 g of thionyl chloride is dripped slowly. After completion of the dropwise addition, the temperature is returned to room temperature and stirred for 30 minutes. Then, it cooled to the internal temperature of 0 degreeC, and the mixed solution of 5.8 g of 7-bromo-1-heptanol and 10.0 mL of DMAc was dripped slowly. After completion|finish of dripping, it returned to room temperature and stirred for 5 hours. Then, 120 ml of water and 120 mL of hexane were added, and the precipitated solid was extracted by filtration. The obtained solid was purified by column chromatography to obtain compound (I-e).

1.7 g of compound (I-e) obtained above was weighed, 0.24 g of compound (I-f), 0.34 g of potassium carbonate, and 0.01 g of dibutylhydroxytoluene were added and mixed with 1.0 mL of THF and 1.4 mL of DMAc. It heated to 60 degreeC internal temperature, and stirred for 2 hours. Then, it returned to room temperature, 35 mL of water was added, and the precipitated solid was extracted by filtration. The obtained solid was purified by column chromatography to obtain 1.05 g (yield 76%) of compound (I-g).

¹ H-NMR (Nuclear Magnetic Resonance) data of the obtained compound (Ig) is shown below.

¹ HNMR (CDCl ₃ ) δ (ppm) = 0.91 (m, 8H), 1.20-1.29 (m, 12H), 1.43 (m, 8H), 1.61 (m, 12H), 1.75 (m, 16H), 2.20 ( m, 6H), 2.75 (m, 12H), 3.88-4.16 (30H), 5.83 (d, 2H), 6.12 (q, 2H), 6.41 (d, 2H), 6.94 (s, 2H)

[Synthesis of specific compound (II-g)]

By the method described in paragraphs [0252] to [0254] of Unexamined-Japanese-Patent No. 2011-162678, the compound (II-f) represented by a following formula (II-f) was synthesize|combined.

Thereafter, the specific compound (II-g) represented by the following formula (II-g) was synthesized in the same manner as the specific compound (I-g) except that the compound (II-f) was used instead of the compound (I-f). .

[Formula 8]

¹ H-NMR data of the obtained specific compound (II-g) are shown below.

¹ H-NMR (CDCl ₃ )δ (ppm) = 0.91 (m, 8H), 1.20-1.29 (m, 12H), 1.43 (m, 8H), 1.61 (m, 12H), 1.75 (m, 16H), 2.20(m, 6H), 2.43(s, 3H), 2.75(m, 12H), 3.88-4.16(30H), 5.83(d, 2H), 6.12(q, 2H), 6.41(d, 2H), 7.01 (s, 2H), 7.13 (s, 1H), 7.25 (s, 2H), 7.81 (d, 1H)

[Synthesis of Reverse Wavelength Dispersible Liquid Crystal Compound (II-a)]

In accordance with the method described in paragraph [0122] (Example 4) of Japanese Patent Application Laid-Open No. 2016-081035, a reverse wavelength dispersible liquid crystal compound (II-a) represented by the following formula (II-a) was synthesized. In addition, in the following formula (II-a), the group adjacent to the acryloyloxy group represents a propylene group (group in which a methyl group is substituted with an ethylene group), and represents a mixture of positional isomers having different positions of the methyl group.

[Formula 9]

[Example 1]

[Production of optical film]

A polymerizable liquid crystal composition having the following composition was prepared and applied to a rubbing-treated glass substrate with a polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.) by spin coating.

The coating film was orientation-processed at the temperature shown in following Table 5, and the liquid crystal layer was formed.

Thereafter, it was cooled to the exposure temperature described in Table 5 below, and alignment was fixed by UV irradiation of 1000 mJ/cm ² , an optically anisotropic film was formed, and an optical film was produced.

------------------------------------------------------------ ----------------

Optical anisotropic layer coating solution

------------------------------------------------------------ ----------------

・Specific compounds (I-g) 50 parts by mass

The following polymerizable smectic liquid crystal compound (Sm-1) 50 parts by mass

・Photoinitiator (Irgacure 819, manufactured by BASF) 2 parts by mass

・The following fluorine-containing compound A 1 part by mass

・Chloroform 521 parts by mass

------------------------------------------------------------ ----------------

Polymerizable Smectic Liquid Crystal Compound (Sm-1)

[Formula 10]

Fluorinated compound A

[Formula 11]

[Example 2]

An optical film was produced in the same manner as in Example 1, except that the specific compound was changed to the compound shown in Table 3 below.

[Comparative Example 1]

An optical film was produced in the same manner as in Example 1 except that the following polymerizable nematic liquid crystal compound (Ne-1) was used instead of the polymerizable smectic liquid crystal compound (Sm-1).

Polymerizable Nematic Liquid Crystal Compound (Ne-1)

[Formula 12]

[Comparative Example 2]

An optical film was produced in the same manner as in Example 1, except that the reverse wavelength dispersible liquid crystal compound (II-a) was blended instead of the specific compound, and the polymerizable smectic liquid crystal compound (Sm-1) was not blended. .

[Comparative Example 3]

An optical film was produced in the same manner as in Example 1 except that the polymerizable smectic liquid crystal compound (Sm-1) was not blended.

<Retardation>

About the produced optical film, the retardation value (Re(450)) of wavelength 450nm and the retardation value (Re(550)) of wavelength 550nm were measured using Axo Scan (OPMF-1, Optoscience company make). Thus, Re(450)/Re(550) was calculated. These results are shown in Table 5 below.

<Moist heat durability>

The test conditions of wet heat durability performed the test left to stand for 500 hours in the environment of 85 degreeC relative humidity of 85%.

Re (550) of the optical film before the test and Re (550) of the optical film after the test were measured, and the following references|standards evaluated wet-heat durability. The results are shown in Table 3 below.

A: The amount of change of Re (550) after the test with respect to Re (550) before the test is less than 10% of the Re (550) before the test

B: The amount of change of Re (550) after the test with respect to Re (550) before the test is 10% or more and less than 30% of Re (550) before the test

C: The amount of change in Re (550) after the test with respect to Re (550) before the test is 30% or more of the Re (550) before the test

<Amine resistance>

Test conditions for amine resistance were tested by putting a 2 mol% solution of NH ₃ /MeOH in a vial, placing an optical film at the outlet, and leaving it to stand for 10 hours.

Re (550) of the optical film before a test and Re (550) of the optical film after a test were measured, and the following references|standards evaluated amine resistance. The results are shown in Table 3 below.

A: The amount of change of Re (550) after the test with respect to Re (550) before the test is less than 10% of the Re (550) before the test

B: The amount of change of Re (550) after the test with respect to Re (550) before the test is 10% or more and less than 30% of Re (550) before the test

C: The amount of change in Re (550) after the test with respect to Re (550) before the test is 30% or more of the Re (550) before the test

<Light resistance>

With respect to the produced optical film, a glass substrate was set in a xenon irradiator (SX75 manufactured by Suga Shikenki Co., Ltd.) so that the coating film of the polymerizable liquid crystal composition became an irradiated surface, and the test was performed using #275 filter and irradiated for 200 hours.

Re (550) of the optical film before the test and Re (550) of the optical film after the test were measured, and the following references|standards evaluated light resistance. The results are shown in Table 3 below.

A: The amount of change of Re (550) after the test with respect to Re (550) before the test is less than 5% of the Re (550) before the test

B: The amount of change in Re (550) after the test with respect to Re (550) before the test is 5% or more and less than 15% of Re (550) before the test

C: The amount of change in Re (550) after the test with respect to Re (550) before the test is 15% or more of the Re (550) before the test

[Table 3]

From the results shown in Table 3, it was found that when a polymerizable nematic liquid crystal compound was blended with a specific compound, the amine resistance of the optically anisotropic film formed was inferior (Comparative Example 1).

In addition, it was found that when the reverse wavelength dispersible liquid crystal compound (II-a) was blended instead of the specific compound and the polymerizable smectic liquid crystal compound was not blended, the amine resistance of the optically anisotropic film formed was inferior (comparison). Example 2).

In addition, it was found that when a specific compound is blended and neither the polymerizable smectic liquid crystal compound nor the polymerizable nematic liquid crystal compound is blended, reverse wavelength dispersion is not expressed in the optically anisotropic film formed (Comparative Example). 3).

On the other hand, when a polymerizable smectic liquid crystal compound was mix|blended with a specific compound, reverse wavelength dispersion property was expressed in the optically anisotropic film|membrane formed, and it turned out that amine resistance also becomes favorable (Example 1 and 2).

10 optical film
12 Optically anisotropic film
14 alignment layer
16 support
18 hard coat layer

Claims (11)

A polymerizable liquid crystal composition comprising a compound represented by the following formula (I-1) and a polymerizable smectic liquid crystal compound.
[Formula 1]

Here, in the formula (I-1),
Ar ¹ and Ar ² each independently represent an aromatic ring having a maximum absorption wavelength of 280 to 420 nm.
D ¹ is a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or , a divalent linking group composed of a combination of two or more of these, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
p represents 0 or 1.
X ¹ and X ² each independently represent -O-, -S-, -CO-, -CO-NR ⁶ -, or a single bond, and R ⁶ is each independently a hydrogen atom or a fluorine atom. , or an alkyl group having 1 to 4 carbon atoms.
L ¹ and L ² each independently represent an alkylene group represented by the following formula (I-2).
Mes ¹ and Mes ² each independently represent a polymerizable group-containing group represented by the following formula (I-3).
[Formula 2]

Here, in the formula (I-2),
* indicates a bonding position with Mes ¹ or X ¹ for L ¹ , and indicates a bonding position with Mes ² or X ² for L ² .
m represents an integer of 1 or more.
However, the hydrogen atom included in the alkylene group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, thioisocyan. It may be substituted with an ano group or a C1-C20 alkyl group.
In addition, among -CH ₂ - constituting the alkylene group and not directly bonded to X ¹ or X ² , one or two or more -CH ₂ - not adjacent to each other are -O-, -S -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, or -C It may be substituted with ≡C-.
[Formula 3]

Here, in the formula (I-3),
* indicates a bonding position with L ¹ for Mes ¹ , and indicates a bonding position with L ² for Mes ² .
M is 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1 , a 4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group. However, the hydrogen atom contained in these groups is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group. , or may be substituted with an alkyl group having 1 to 20 carbon atoms.
D ² and D ³ are each independently, -O-, -S-, -OCH ₂ -, -CH ₂ CH ₂ -, -CO-, -COO-, -CO-S-, -OCO-O- , -CO-NH-, -SCH ₂ -, -CF ₂ O-, -CF ₂ S-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH ₂ CH ₂ -, - OCO-CH ₂ CH ₂ -, -COO-CH ₂ -, -OCO-CH ₂ -, -CH=CH-, -N=N-, -CH=N-, -CH=NN=CH-, -CF =CF-, -C≡C-, or a single bond.
SP is a single bond, at least one of -CH ₂ - constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms -O-, -S -, -NH-, -N(Q)-, or the divalent coupling group substituted by -CO- is represented, and Q represents a substituent.
P represents a polymerizable group.
n represents an integer of 2 or more, a plurality of M may be the same or different, respectively, a plurality of D ² may be the same or different, respectively, a plurality of D ³ may be the same or different, respectively, A plurality of SPs may be the same or different, respectively. The method according to claim 1,
The polymerizable liquid crystal composition wherein Ar ¹ and Ar ² in the formula (I-1) represent an aromatic ring having a maximum absorption wavelength in 300 to 400 nm. The method according to claim 1 or 2,
The polymerizable liquid crystal composition wherein Ar ¹ and Ar ² in the formula (I-1) represent any one aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7).
[Formula 4]

Here, in the formulas (Ar-1) to (Ar-7),
* indicates a bonding position with X ¹ or D ¹ for Ar ¹ , and indicates a bonding position with D ¹ or X ² for Ar ² .
Q ¹ represents N or CH.
Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have a substituent, or an aromatic heterocyclic group having 3 to 12 carbon atoms.
Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. represents a hydrocarbon group, a halogen atom, a cyano group, a nitro group, -OR ⁸ , -NR ⁹ R ¹⁰ , or -SR ¹¹ , R ⁸ to R ¹¹ are each independently a hydrogen atom or 1 carbon atom - 6 represents an alkyl group, Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -N(R ¹² )-, -S-, and -CO-, R ¹² represents a hydrogen atom or a substituent indicates.
X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.
D ⁴ and D ⁵ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ - , -NR ⁵ -, or a divalent linking group composed of a combination of two or more of these, R ¹ to R ⁵ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
SP ¹ and SP ² are each independently one of -CH ₂ - constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms The above represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent.
L ³ and L ⁴ each independently represent a monovalent organic group.
Ax represents a C2-C30 organic group which has at least 1 aromatic ring chosen from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, 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 heterocycle .
The aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may couple|bond together, and may form the ring.
Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. 4. The method according to any one of claims 1 to 3,
The polymerizable liquid crystal composition in which X ¹ and X ² in the formula (I-1) represent a linking group represented by -O-. 5. The method according to any one of claims 1 to 4,
The polymerizable liquid crystal composition wherein P in the formula (I-3) represents any one polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-20).
[Formula 5]

Here, in the formulas (P-1) to (P-20), * represents a bonding position with SP. 6. The method according to any one of claims 1 to 5,
The polymerizable liquid crystal composition, wherein the content of the polymerizable smectic liquid crystal compound is 15 to 75 mass% with respect to the total mass of the polymerizable smectic liquid crystal compound and the compound represented by the formula (I-1). An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 6. 8. The method of claim 7,
An optically anisotropic film satisfying the following formula (III).
0.50<Re(450)/Re(550)<1.00… (III)
Here, in formula (III), Re(450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. . The optical film which has the optically anisotropic film|membrane of Claim 7 or 8. The polarizing plate which has the optical film of Claim 9, and a polarizer. The image display device which has the optical film of Claim 9, or the polarizing plate of Claim 10.

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