CN114502607A

CN114502607A - Polymerizable liquid crystal composition, optically anisotropic layer, optical film, polarizing plate, and image display device

Info

Publication number: CN114502607A
Application number: CN202080066752.1A
Authority: CN
Inventors: 加藤考浩; 北村哲; 佐竹亮
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2019-09-25
Filing date: 2020-09-23
Publication date: 2022-05-13
Also published as: WO2021060288A1; JP7355835B2; JPWO2021060288A1; KR20220050161A

Abstract

The invention aims to provide a polymerizable liquid crystal composition with excellent storage stability, and an optically anisotropic layer, an optical film, a polarizing plate and an image obtained by using the polymerizable liquid crystal compositionA display device. The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a copolymer having at least a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II). A. the¹Represents a group represented by the following formula (1-1), and A2 represents a group represented by the following formula (2-1) or (2-2).

*‑C_nF_2nCF₂X(1‑1)

Description

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

Technical Field

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

Background

Optical films such as optical compensation sheets and retardation films are used in various image display devices from the viewpoint of eliminating image coloration and widening a viewing angle.

As the optical film, a stretched birefringent film is used, but in recent years, it has been proposed to use an optically anisotropic layer formed using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound instead of the stretched birefringent film.

For example, patent document 1 describes a liquid crystal film having at least an optically anisotropic layer formed from a liquid crystal composition containing a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer, and a support.

Prior art documents

Patent document

Patent document 1: international publication No. 2019/009255

Disclosure of Invention

Technical problem to be solved by the invention

As a result of studies on the optically anisotropic layer described in patent document 1, the present inventors have found a problem that a polymerizable liquid crystal compound contained in a polymerizable liquid crystal composition is decomposed with time, that is, a problem that the storage stability of the polymerizable liquid crystal composition is poor.

Accordingly, an object of the present invention is to provide a polymerizable liquid crystal composition having excellent storage stability, and an optically anisotropic layer, an optical film, a polarizing plate, and an image display device obtained using the same.

Means for solving the technical problem

As a result of intensive studies to achieve the above object, the present inventors have found that a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a copolymer having a repeating unit represented by formulae (1) and (2) described later is excellent in storage stability, and have completed the present invention.

That is, it is found that the above-mentioned problems can be achieved by the following configuration.

[1] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound and a copolymer having at least a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[ chemical formula 1]

Wherein in the above formulae (1) and (2),

R¹and R²Represents a hydrogen atom or a methyl group.

L¹And L²Represents a 2-valent linking group.

A¹Represents a group represented by the following formula (1-1), A²Represents a group represented by the following formula (2-1) or (2-2).

[ chemical formula 2]

*-C_nF_2nCF₂X (1-1)

Wherein, in the above formula (1-1),

is represented by¹The bonding position of (2).

n represents an integer of 1 to 6.

X represents a hydrogen atom or a fluorine atom.

[ chemical formula 3]

Wherein in the above formulae (2-1) and (2-2),

is represented by²The bonding position of (2).

Y represents-O-, -NH-or-NR^Y-，R^YRepresents a substituent.

X represents a halogen atom.

[2] The polymerizable liquid crystal composition according to [1], wherein the copolymer further has a repeating unit represented by the following formula (3).

[ chemical formula 4]

Wherein, in the above formula (3),

R³represents a hydrogen atom or a methyl group.

L³Represents a 2-valent linking group.

A³Represents a polymerizable group.

[3] The polymerizable liquid crystal composition according to [1] or [2], wherein the copolymer is a copolymer further having a repeating unit represented by the following formula (4).

[ chemical formula 5]

Wherein, in the above formula (4),

R⁴represents a hydrogen atom or a methyl group.

L⁴Represents a 2-valent linking group.

A⁴Represents an aromatic ring group which may have a substituent.

[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein the content of the repeating unit represented by the formula (2) is 0.001 to 60% by mass based on the total mass of all repeating units of the copolymer.

[5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein the content of the copolymer is 0.01 to 0.20 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

[6] An optically anisotropic layer obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [5 ].

[7] An optical film having the optically anisotropic layer according to [6 ].

[8] A polarizing plate having the optical film according to [7], and a polarizer.

[9] An image display device having the optical film of [7] or the polarizing plate of [8 ].

Effects of the invention

The present invention can provide a polymerizable liquid crystal composition having excellent storage stability, and an optically anisotropic layer, an optical film, a polarizing plate, and an image display device obtained using the same.

Drawings

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

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

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

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value.

In the present specification, one kind of substance corresponding to each component may be used alone for each component, or two or more kinds may be used in combination. Here, when 2 or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination unless otherwise specified.

Also, in this specificationThe bonding direction of the divalent group to be labeled (for example, -CO-NR-) is not particularly limited except for the case where the bonding position is clearly labeled, and for example, when D in the formula (I) described later¹In the case of-CO-NR-, when bonded to G¹Side position set as 1, bonded to Ar¹When the position of the side is set to 2, D¹May be 1-CO-NR-2 or 1-NR-CO-2.

In the present specification, "(meth) acrylate" is a label indicating acrylate or methacrylate, "(meth) acrylic acid" is a label indicating acrylic acid or methacrylic acid, and "(meth) acryloyl group" is a label indicating methacryloyl group or acryloyl group.

In the present specification, the kind of the substituent, the position of the substituent and the number of the substituents in the case of "optionally having a substituent" are not particularly limited. The number of the substituents may be, for example, 1, 2, 3 or more. Examples of the substituent include a 1-valent nonmetal atomic group other than a hydrogen atom, and specifically, the substituent can be selected from the following substituents T.

< substituent T >)

Examples of the substituent T include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and oxalyl; alkylsulfanyl groups such as methylsulfanyl and t-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; a carboxyl group; a formyl group; a sulfo group; a cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a sulfonamide group; an amino group; a monoalkylamino group; a dialkylamino group; an arylamino group; and combinations thereof.

[ polymerizable liquid Crystal composition ]

The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a copolymer having at least a repeating unit represented by formula (1) described later and a repeating unit represented by formula (2) described later.

In the present invention, as described above, by blending the polymerizable liquid crystal compound and the copolymer having the repeating units represented by the formulae (1) and (2) described later, the storage stability of the polymerizable liquid crystal composition becomes good.

The present inventors speculate as follows, although the detailed reason is not clear.

First, the present inventors speculate that the reason why the storage stability of the conventionally known polymerizable liquid crystal composition is poor is that the polymerizable liquid crystal composition inevitably contains an alkaline substance.

The present inventors have also confirmed that the repeating unit represented by formula (2) described later in the copolymer decomposes with time to release an acid (e.g., HCl).

Therefore, in the present invention, it is considered that the storage stability is improved by trapping the basic substance inevitably contained in the acid-trapping polymerizable liquid crystal composition released from the repeating unit represented by the formula (2) described later.

Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

[ copolymer ]

The copolymer contained in the polymerizable liquid crystal composition of the present invention (hereinafter, also referred to as "copolymer of the present invention" in the present specification) is a copolymer having at least a repeating unit represented by the following formula (1) (hereinafter, also referred to as "fluorine moiety") and a repeating unit represented by the following formula (2) (hereinafter, also referred to as "halogen moiety").

[ chemical formula 6]

< fluorine moiety >

The copolymer of the present invention has a fluorine moiety represented by the following formula (1).

[ chemical formula 7]

In the above formula (1), R¹Represents a hydrogen atom or a methyl group.

And, in the above formula (1), L¹Represents a 2-valent linking group.

In the above formula (1), A¹Represents a group represented by the following formula (1-1).

[ chemical formula 8]

*-C_nF_2nCF₂X (1-1)

In the above formula (1-1), represents¹The bonding position of (2).

In the formula (1-1), n represents an integer of 1 to 6.

In the formula (1-1), X represents a hydrogen atom or a fluorine atom.

L in the above formula (1)¹Examples of the 2-valent linking group include-O-, -NR^a11- (wherein, R)^a11Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. ) -S-, -CO-, -SO₂A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a 2-valent linking group selected from a group consisting of groups obtained by linking 2 or more of them.

Examples of the linking group having a valence of 2 formed by connecting at least 2 include-CO-O-, -O-CO-O-, -CO-NH-, -CO-O- (CH)₂)_maO- (where ma represents an integer of 1 to 20), and the like.

Among these, the 2-valent linking group is preferably-O-, -CO-NH-, or a combination of 1 or more of these groups and an alkylene group, and more preferably a group represented by the following formulae (L-1) to (L-5).

[ chemical formula 9]

In the above formulae (L-1) to (L-5), 1 represents R in the above formula (1)¹The bonding position of the bonded carbon atom,. 2 represents a position bonded to A in the above formula (1)¹The bonding position of (2).

In the formulae (L-1) to (L-5), m represents an integer of 1 to 20, preferably an integer of 2 to 16, more preferably an integer of 2 to 12, and further preferably an integer of 2 to 6.

In the formulae (L-1) to (L-5), n represents an integer of 1 to 20, preferably an integer of 2 to 16, more preferably an integer of 2 to 12, and still more preferably an integer of 2 to 6.

As the repeating unit represented by the above formula (1), for example, repeating units represented by the following formulae (F-1) to (F-12) can be preferably mentioned.

[ chemical formula 10]

In the present invention, the content of the repeating unit represented by the above formula (1) is preferably 20 to 90% by mass, more preferably 20 to 60% by mass, and further preferably 25 to 45% by mass, based on the total mass of all repeating units of the copolymer of the present invention, from the viewpoints that the coating property of the polymerizable liquid crystal composition of the present invention is good, and the unevenness in film thickness due to drying air during drying after coating (hereinafter, also simply referred to as "wind unevenness") is alleviated.

< halogen moiety >

The copolymer of the present invention has a halogen moiety represented by the following formula (2).

[ chemical formula 11]

In the above formula (2), R²Represents a hydrogen atom or a methyl group.

In the above formula (2), L²Represents a 2-valent linking group. Further, as the linking group having a valence of 2, there may be mentioned a linking group to L in the above formula (1)¹Among the same linking groups, preferred are those represented by the above formula (L-1) or (L-5).

In the above formula (2), A²Represents a group represented by the following formula (2-1) or (2-2).

[ chemical formula 12]

In the above formulae (2-1) and (2-2), R represents and L²The bonding position of (2).

And, in the above formulae (2-1) and (2-2), Y represents-O-, -NH-or-NR-^Y-，R^YRepresents a substituent. Examples of the substituent include the substituents described as the above-mentioned substituent T.

In the above formulae (2-1) and (2-2), X represents a halogen atom.

Y in the above formulae (2-1) and (2-2) is preferably-O-or-NH-, more preferably-O-.

Examples of the halogen atom represented by X in the above formulae (2-1) and (2-2) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable.

As the repeating unit represented by the above formula (2), for example, repeating units represented by the following formulas (X-1) to (X-17) can be preferably mentioned.

[ chemical formula 13]

In the present invention, the content of the repeating unit represented by the above formula (2) is preferably 0.001 to 60% by mass, more preferably 0.005 to 30% by mass, and further preferably 0.01 to 20% by mass, based on the total mass of all the repeating units of the copolymer of the present invention, from the viewpoint of improving the storage stability of the polymerizable liquid crystal composition of the present invention.

< polymeric moiety >

In the present invention, the copolymer of the present invention preferably further has a repeating unit represented by the following formula (3) (hereinafter, also simply referred to as "polymerizable portion") from the viewpoint of the reason that the adhesiveness to the layer provided on the upper layer of the optically anisotropic layer obtained by polymerizing the polymerizable liquid crystal composition of the present invention is good.

[ chemical formula 14]

In the above formula (3), R³Represents a hydrogen atom or a methyl group.

In the above formula (3), L³Represents a 2-valent linking group. Further, as the linking group having a valence of 2, there may be mentioned a linking group to L in the above formula (1)¹The same linking group.

In the above formula (3), A³Represents a polymerizable group.

A in the above formula (3)³The polymerizable group represented is preferably a polymerizable group capable of radical polymerization or cationic polymerization.

As the radical polymerizable group, a known radical polymerizable group can be used, and as a preferred radical polymerizable group, an acryloyloxy group or a methacryloyloxy group can be mentioned. In this case, it is known that an acryloyloxy group generally has a high polymerization rate, and is preferably an acryloyloxy group from the viewpoint of improving productivity, but a methacryloyloxy group can be similarly used as a polymerizable group.

As the cationically polymerizable group, a known cationically polymerizable group can be used, and specific examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and a vinyloxy group. Among them, an alicyclic ether group or an ethyleneoxy group is preferable, and an epoxy group, an oxetanyl group or an ethyleneoxy group is particularly preferable.

Examples of particularly preferred polymerizable groups include polymerizable groups represented by any one of the following formulas (P-1) to (P-20).

[ chemical formula 15]

As the repeating unit represented by the above formula (3), for example, repeating units represented by the following formulae (J-1) to (J-10) can be preferably mentioned.

[ chemical formula 16]

When the repeating unit represented by the above formula (3) is contained, the content of the repeating unit represented by the above formula (3) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 2 to 10% by mass, based on the total mass of all the repeating units of the copolymer of the present invention, from the viewpoint of the reason that the adhesiveness with the layer provided on the upper layer of the optically anisotropic layer obtained by polymerizing the polymerizable liquid crystal composition of the present invention becomes better.

< aromatic Ring moiety >

In the present invention, the copolymer of the present invention preferably further has a repeating unit represented by the following formula (4) (hereinafter, also simply referred to as "aromatic ring moiety") from the viewpoint of the reason that the polymerizable liquid crystal composition of the present invention is excellent in alignment properties.

[ chemical formula 17]

In the above formula (4), R⁴Represents a hydrogen atom or a methyl group.

In the above formula (4), L⁴Represents a 2-valent linking group. In addition, asThe 2-valent linking group may be represented by the group represented by the formula (1)¹The same linking group.

In the above formula (4), A⁴Represents an aromatic ring group which may have a substituent. Examples of the substituent include the substituents described as the above-mentioned substituent T.

A in the above formula (4)⁴The aromatic ring group includes, for example, a 1-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, specifically, a phenyl group, a2, 6-diethylphenyl group, a naphthyl group, a biphenyl group, and the like, and among them, a phenyl group, a naphthyl group, or a biphenyl group is preferable.

Examples of the repeating unit represented by the above formula (4) include repeating units represented by the following formulae (H-1) to (H-6).

[ chemical formula 18]

When the repeating unit represented by the above formula (4) is contained, the content of the repeating unit represented by the above formula (4) is preferably 20 to 80% by mass, more preferably 40 to 80% by mass, and further preferably 50 to 70% by mass, based on the total mass of all the repeating units of the copolymer of the present invention, from the viewpoint of improving the alignment property of the polymerizable liquid crystal composition of the present invention.

< other part >)

The copolymer of the present invention may have, if necessary, other repeating units than the repeating units represented by the above formulas (1) to (4).

As monomers forming other repeating units, monomers described in Polymer handbook 2nd ed., J.Brandrup, Wiley lnterscience (1975) Chapter 2 pages 1 to 483 can be used.

Examples thereof include compounds having 1 addition polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

Specifically, the following monomers can be mentioned.

(acrylic esters)

Specific examples of the acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

(methacrylic acid esters)

Specific examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and ethylene glycol monoacetoacetate monomethacrylate.

(acrylamides)

Specific examples of the acrylamide include acrylamide, N-alkylacrylamide (as an alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N-dialkylacrylamide (as an alkyl group having 1 to 6 carbon atoms), N-hydroxyethyl-N-methacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, and the like.

(methacrylamide)

Specific examples of the methacrylamide include methacrylamide, N-alkylmethacrylamide (an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, and a propyl group), N-dialkylmethacrylamide (an alkyl group having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, and N-2-acetamidomethyl-N-acetylmethacrylamide.

(allyl Compound)

Specific examples of the allyl compound include allyl esters (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, and the like.

(vinyl ethers)

Specific examples of the vinyl ether include alkyl vinyl ethers (e.g., hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.).

(vinyl esters)

Specific examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl- β -phenylbutyrate, and vinyl cyclohexylcarboxylate.

(itaconic acid dialkyl)

Examples of the dialkyl itaconate include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(others)

Other examples include dialkyl esters or alkyl esters of fumaric acid; dibutyl fumarate; crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleonitrile, styrene, a styrene macromonomer (TOAGOSEI co., ltd., product AS-6S), a methacrylate macromonomer (TOAGOSEI co., ltd., product AA-6), and the like.

In the present invention, the content of the other repeating units is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 20% by mass, based on the total mass of all repeating units in the copolymer of the present invention.

The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 10000 to 300000, preferably 12000 to 100000, and more preferably 15000 to 50000.

The number average molecular weight (Mn) of the copolymer of the present invention is preferably 3000 to 100000, more preferably 5000 to 50000, and further preferably 7000 to 30000.

The weight average molecular weight and the number average molecular weight are values measured by Gel Permeation Chromatography (GPC) under the following conditions.

< measurement Condition >

Solvent: tetrahydrofuran (THF)

Flow rate (sample injection amount): 10 μ L

Pipe column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION

Temperature of the pipe column: 40 deg.C

Flow rate: 1.0 mL/min

A detector: polystyrene equivalent based on differential Index Detector (Refractive Index Detector))

Examples of the copolymer of the present invention include copolymers in which the above-mentioned fluorine moiety and halogen moiety, and optional polymerizable moiety, aromatic ring moiety, and repeating units exemplified as other moieties are selected and combined.

The content of the copolymer of the present invention is preferably 0.01 to 0.20 parts by mass, and more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of a polymerizable liquid crystal compound described later.

[ polymerizable liquid Crystal Compound ]

The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is not particularly limited as long as it is a liquid crystal compound having a polymerizable group, and a liquid crystal compound having 2 or more polymerizable groups is preferable.

The polymerizable group of the polymerizable liquid crystal compound is preferably the same polymerizable group as the polymerizable group capable of radical polymerization or cationic polymerization described in the polymerizable moiety of the copolymer, and among them, the polymerizable group represented by any one of the above formulae (P-1) to (P-20) is preferably used.

Here, generally, liquid crystal compounds can be classified into rod-like types and disk-like types according to their shapes. Furthermore, there are low molecular and high molecular types, respectively. The polymer is a substance having a polymerization degree of usually 100 or more (polymer physical/phase transition kinetics, edited by Otto-Douglas, 2 pp., Shibo bookshop, 1992).

In the present invention, any liquid crystal compound can be used, and preferably, a rod-like liquid crystal compound or a discotic liquid crystal compound (discotic liquid crystal compound) is used. It is also possible to use 2 or more kinds of rod-like liquid crystal compounds, 2 or more kinds of discotic liquid crystal compounds, or a mixture of rod-like liquid crystal compounds and discotic liquid crystal compounds.

As the rod-like liquid crystal compound, for example, the compounds described in claim 1 of Japanese patent application laid-open No. 11-513019 or paragraphs [0026] to [0098] of Japanese patent application laid-open No. 2005-289980 can be preferably used, and as the disk-like liquid crystal compound, for example, the compounds described in paragraphs [0020] to [0067] of Japanese patent application laid-open No. 2007-laid-open No. 108732 or paragraphs [0013] to [0108] of Japanese patent application laid-open No. 2010-laid-open No. 244038 can be preferably used, but not limited thereto.

In the present invention, the polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having reverse wavelength dispersibility (hereinafter, also referred to as "a reverse dispersion liquid crystal compound") from the viewpoint of improving optical compensation properties.

Here, in the present specification, the phrase "polymerizable liquid crystal compound having reverse wavelength dispersibility" means that when the retardation (Re) value in a plane at a specific wavelength (visible light range) of a retardation film produced using the same is measured, the Re value becomes equal or higher as the measured wavelength increases.

Examples of the inverse-dispersion liquid crystal compound include compounds represented by the following formula (I).

L¹-SP¹-D⁵-(A¹)_a1-D³-(G¹)_g1-D¹-〔Ar-D²〕_q1-(G²)_g2-D⁴-(A²)_a2-D⁶-SP²-L²…(I)

In the formula (I), a1, a2, g1 and g2 each independently represent 0 or 1. Wherein at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.

In the formula (I), q1 represents 1 or 2.

And, in the above formula (I), D¹、D²、D³、D⁴、D⁵And D⁶Each independently represents a single bond, or a group consisting of-CO-, -O-, -S-, -C (═ S) -, -CR¹R²-、-CR³＝CR⁴-、-NR⁵-or a combination of 2 or more thereof, R¹～R⁵Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 12 carbon atoms. Wherein when q1 is 2, a plurality of D' s²Each may be the same or different.

And, in the above formula (I), G¹And G²Each independently represents an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a 2-valent alicyclic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent, and-CH constituting the alicyclic hydrocarbon group₂More than 1 of-may be substituted by-O-, -S-or-NH-.

In the above formula (I), A¹And A²Each independently represents an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a 2-valent alicyclic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent, and-CH constituting the alicyclic hydrocarbon group₂More than 1 of-may be substituted by-O-, -S-or-NH-.

And, in the above formula (I), SP¹And SP²Each independently represents a single bond, -CH, or a linear or branched alkylene group having 1 to 12 carbon atoms, or-CH constituting a linear or branched alkylene group having 1 to 12 carbon atoms₂-one or more 2-valent linking groups substituted with-O-, -S-, -NH-, -N- (Q) -or-CO-, wherein Q represents a substituent.

And, in the above formula (I), L¹And L²Each independently represents an organic group having a valence of 1, L¹And L²At least one of them represents a polymerizable group. Wherein, when Ar is an aromatic ring represented by the following formula (Ar-3), L¹And L²And L in the following formula (Ar-3)³And L⁴At least one of them represents a polymerizable group.

In the above formula (I), it is preferable that all of a1, a2, g1 and g2 are 1, because the polymerizable liquid crystal composition of the present invention easily exhibits a smectic liquid crystal state.

In addition, from the viewpoint of the contrast of the image display device having the optically anisotropic layer being good, a1 and a2 are both 0, and g1 and g2 are both preferably 1.

In the above formula (I), q1 is preferably 1.

In the above formula (I), as D¹、D²、D³、D⁴、D⁵And D⁶Examples of the 2-valent linking group represented by (1) include-CO-, -O-, -CO-O-, -C (═ S) O-, -CR¹R²-、-CR¹R²-CR¹R²-、-O-CR¹R²-、-CR¹R²-O-CR¹R²-、-CO-O-CR¹R²-、-O-CO-CR¹R²-、-CR¹R²-O-CO-CR¹R²-、-CR¹R²-CO-O-CR¹R²-、-NR⁵-CR¹R²-, and, -CO-NR⁵-and the like. R¹、R²And R⁵Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 12 carbon atoms.

Among them, any of-CO-, -O-, and-CO-O-is preferable.

In the above formula (I), as G¹And G²The aromatic ring having 6 to 20 carbon atoms represented by one embodiment of (1) includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, phenanthroline ring, etc.; an aromatic heterocycle such as furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, or benzothiazole ring. Among them, preferred isBenzene rings (e.g., 1, 4-phenyl, etc.).

In the above formula (I), as G¹And G²The alicyclic hydrocarbon group having 2 valences and 5 to 20 carbon atoms represented by the above embodiment is preferably a 5-or 6-membered ring. The alicyclic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated alicyclic hydrocarbon group. As G¹And G²The alicyclic hydrocarbon group having a valence of 2 can be referred to, for example, in Japanese patent laid-open publication No. 2012-21068 [0078 ]]The contents of the paragraph are incorporated in the present specification.

In the present invention, G in the above formula (I) is considered to be good for the reason that the contrast of the image display device having the optically anisotropic layer becomes good¹And G²Preferred is a cycloalkane ring.

Specific examples of the cycloalkane ring include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclododecane ring.

Among these, a cyclohexane ring is preferable, 1, 4-cyclohexylene is more preferable, and trans-1, 4-cyclohexylene is even more preferable.

In the above formula (I), G represents¹And G²Examples of the substituent that may be contained in the aromatic ring having 6 to 20 carbon atoms or the 2-valent alicyclic hydrocarbon group having 5 to 20 carbon atoms include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamido group, an alkenyl group, an alkynyl group, a halogen atom, a cyano group, a nitro group, an alkylthiol group, and an N-alkylcarbamate group, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom are preferable.

The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl and the like), still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.), further preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom or a chlorine atom is preferable.

In the above formula (I), as A¹And A²The aromatic ring having 6 to 20 carbon atoms represented by one embodiment of (1) includes G in the formula (I)¹And G²The same aromatic ring as the aromatic ring described in (1).

In the above formula (I), A is¹And A²The alicyclic hydrocarbon group having 2 valence of 5 to 20 carbon atoms represented by one embodiment of (1) includes the group represented by the formula (I) above¹And G²The alicyclic hydrocarbon group described in (1) is the same as the alicyclic hydrocarbon group.

In addition, with respect to A¹And A²Examples of the substituent which may be contained in the aromatic ring having 6 to 20 carbon atoms or the alicyclic hydrocarbon group having 2-valent carbon atoms having 5 to 20 carbon atoms include G in the formula (I)¹And G²The same substituents as those that may be present.

In the above formula (I), as SP¹And SP²The linear or branched alkylene group having 1 to 12 carbon atoms represented by one embodiment of (1) includes, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, methylhexylene, hexyleneHeptyl, and the like.

In addition, as described above, SP¹And SP²May be a-CH constituting a linear or branched alkylene group having 1 to 12 carbon atoms₂One or more of-O-, -S-, -NH-, -N (Q) -or-CO-substituted 2-valent linking groups, and the substituent represented by Q is the same as that of G in the above formula (I)¹And G²The same substituents as those that may be present.

In the above formula (I), as L¹And L²Examples of the 1-valent organic group include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but is preferably linear. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but is preferably monocyclic. The number of carbon atoms of the aryl group is preferably 6 to 25, more preferably 6 to 10. Furthermore, the heteroaryl group may be monocyclic or polycyclic. The number of hetero atoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The number of carbon atoms of the heteroaryl group is preferably 6 to 18, more preferably 6 to 12. The alkyl group, the aryl group and the heteroaryl group may be unsubstituted or may have a substituent. The substituent includes G in the above formula (I)¹And G²The same substituents as those that may be present.

In the above formula (I), as L¹And L²The polymerizable group represented by at least one of the above-mentioned groups preferably includes the same polymerizable group as the polymerizable group capable of radical polymerization or cationic polymerization described in the polymerizable moiety of the above-mentioned copolymer, and among these, the polymerizable group represented by any of the above-mentioned formulas (P-1) to (P-20) is preferably included.

In the formula (I), L in the formula (I) is L in consideration of the reason that the durability of the optically anisotropic layer is improved¹And L²Both of them are preferably polymerizable groups, and more preferably acryloyloxy groups or methacryloyloxy groups.

On the other hand, in the above formula (I)Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7). When q1 is 2, Ar may be the same or different. In the following formulae (Ar-1) to (Ar-7), D is the same as D in the formula (I)¹Or D²The bonding position of (2).

[ chemical formula 19]

In the above formula (Ar-1), Q¹Represents N or CH, Q²represents-S-, -O-or-N (R)⁶)-，R⁶Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y¹Represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, an optionally substituted aromatic heterocyclic group having 3 to 12 carbon atoms, an optionally substituted alicyclic hydrocarbon group having 6 to 20 carbon atoms, -CH constituting the alicyclic hydrocarbon group₂More than 1 of-may be substituted by-O-, -S-or-NH-.

As R⁶Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

As Y¹The aromatic hydrocarbon group having 6 to 12 carbon atoms includes, for example, an aryl group such as a phenyl group, a2, 6-diethylphenyl group, or a naphthyl group.

As Y¹Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms include heteroaryl groups such as thienyl, thiazolyl, furyl and pyridyl.

As Y¹Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms include cyclohexylene, cyclopentylene, norbornylene, and adamantylene.

And as Y¹Examples of the substituent which may be contained include G in the above formula (I)¹And G²The same substituents as those that may be present.

And, in the above formulae (Ar-1) to (Ar-7), Z¹、Z²And Z³Independently represent a hydrogen atom, a C1-valent aliphatic hydrocarbon group, a C3-20 1-valent alicyclic hydrocarbon group, a C6-20 1-valent aromatic heterocyclic group, a halogen atom, a cyano group, a nitro group, -OR⁷、-NR⁸R⁹、-SR¹⁰、-COOR¹¹or-COR¹²，R⁷～R¹²Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z¹And Z²May be bonded to each other to form an aromatic ring.

The 1-valent 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, and specifically more preferably a methyl group, an ethyl group, an isopropyl group, a tert-amyl group (1, 1-dimethylpropyl group), a tert-butyl group, a1, 1-dimethyl-3, 3-dimethyl-butyl group, and particularly preferably a methyl group, an ethyl group, or a tert-butyl group.

Examples of the 1-valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, methylcyclohexyl, and ethylcyclohexyl; monocyclic unsaturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclooctenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl and cyclodecadiene; bicyclo [2.2.1]Heptyl, bicyclo [2.2.2]Octyl, tricyclo [5.2.1.0^2,6]Decyl, tricyclo [3.3.1.1^3,7]Decyl, tetracyclic [6.2.1.1^3,6.0^2,7]And polycyclic saturated hydrocarbon groups such as dodecyl and adamantyl.

Specific examples of the 1-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a2, 6-diethylphenyl group, a naphthyl group, and a biphenyl group, and preferably an aryl group having 6 to 12 carbon atoms (particularly a phenyl group).

Specific examples of the 1-valent aromatic heterocyclic group having 6 to 20 carbon atoms include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.

On the other hand, as R⁷～R¹⁰Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

As described above, Z¹And Z²May be bonded to each other to form an aromatic ring, for example, as Z in the above formula (Ar-1)¹And Z²Examples of the structure in which the aromatic rings are bonded to each other to form an aromatic ring include a group represented by the following formula (Ar-1 a). In the following formula (Ar-1a), one represents D in the formula (I)¹Or D²The bonding position of (2).

[ chemical formula 20]

Wherein, in the above formula (Ar-1a), Q¹、Q²And Y¹The same substances as those described in the above formula (Ar-1) can be mentioned.

And, in the above formulae (Ar-2) and (Ar-3), A³And A⁴Each independently represents a group selected from-O-, -N (R)¹³) A radical of the group consisting of-S-and-CO-, R¹³Represents a hydrogen atom or a substituent.

As R¹³Examples of the substituent include G in the above formula (I)¹And G²The same substituents as those that may be present.

In the formula (Ar-2), X represents a group 14 to 16 non-metal atom to which a hydrogen atom or a substituent may be bonded.

Examples of the non-metal atom of group 14 to 16 represented by X include an oxygen atom, a sulfur atom, a hydrogen atom, and a nitrogen atom to which a substituent is bondedAtom ═ N-R^N1，R^N1Represents a hydrogen atom or a substituent. C- (R), a hydrogen atom or a carbon atom (R) bonded with a substituent^C1)₂，R^C1Represents a hydrogen atom or a substituent. And (c) a temperature sensor.

Specific examples of the substituent include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (e.g., phenyl, naphthyl, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, and the like.

And, in the above formula (Ar-3), D⁷And D⁸Each independently represents a single bond, or a group consisting of-CO-, -O-, -S-, -C (. ═ S) -, -CR¹R²-、-CR³＝CR⁴-、-NR⁵-or a combination of 2 or more thereof, R¹～R⁵Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 12 carbon atoms.

Among them, the 2-valent linking group may be the one represented by the formula (I) above¹、D²、D³、D⁴、D⁵And D⁶The same linking groups as those described in (1).

And, in the above formula (Ar-3), SP³And SP⁴Each independently represents a single bond, -CH, a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms₂One or more of (A) and (B) are a 2-valent linking group substituted by-O-, -S-, -NH-, -N (Q) -or-CO-, and Q represents a substituent. As the substituent, there may be mentioned G in the above formula (I)¹And G²The same substituents as those that may be present.

Among them, the alkylene group includes SP in the above formula (I)¹And SP²The alkylene group in (1) is the same alkylene group as described in (1).

And, in the above formula (Ar-3), L³And L⁴Each independently represents an organic group having a valence of 1, L³And L⁴And L in the above formula (I)¹And L²At least one of them represents a polymerizable group.

As the 1-valent organic group, there may be mentioned L in the above formula (I)¹And L²The organic groups described in (1) are the same organic groups.

The polymerizable group is preferably the same polymerizable group as the polymerizable group capable of radical polymerization or cationic polymerization described in the polymerizable moiety of the copolymer, and is preferably a polymerizable group represented by any one of the above formulae (P-1) to (P-20).

In the formulae (Ar-4) to (Ar-7), 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.

In the formulae (Ar-4) to (Ar-7), 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 heterocyclic ring.

Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring.

And, Q³Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

Ax and Ay are Ax and Ay described in paragraphs [0039] to [0095] of International publication No. 2014/010325.

And as Q³Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl groups, and examples of the substituent include the same as G in the above formula (I)¹And G²The same substituents as those that may be present.

Examples of the compound represented by the formula (I) include a compound represented by the general formula (1) described in Japanese patent application laid-open No. 2010-084032 (particularly, compounds described in paragraphs [0067] to [0073 ]), a compound represented by the general formula (II) described in Japanese patent application laid-open No. 2016-053709 (particularly, compounds described in paragraphs [0036] to [0043 ]), and a compound represented by the general formula (1) described in Japanese patent application laid-open No. 2016-081035 (particularly, compounds described in paragraphs [0043] to [0055 ]), and the like.

Further, as the compound represented by the formula (I), compounds represented by the following formulae (1) to (22) are preferably cited, and specifically, as K (side chain structure) in the formulae (1) to (22), compounds having side chain structures shown in the following tables 1 to 3 are cited.

In tables 1 to 3, each "+" indicated in the side chain structure of K indicates a bonding position to an aromatic ring.

In the side chain structures shown in 2-2 in table 2 and 3-2 in table 3, the groups adjacent to the acryloyloxy group and the methacryloyl group respectively represent propylene groups (groups in which the methyl group is substituted with ethylene) and represent a mixture of positional isomers in which the methyl group is in a different position.

[ chemical formula 21]

[ Table 1]

[ Table 2]

[ Table 3]

[ polymerization initiator ]

The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.

The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.

Examples of the photopolymerization initiator include α -carbonyl compounds (described in U.S. Pat. Nos. 2367661 and 2367670), ketol ethers (described in U.S. Pat. No. 2448828), α -hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Pat. No. 2722512), polyquinone compounds (described in U.S. Pat. Nos. 3046127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketones (described in U.S. Pat. No. 3549367), acridine and phenazine compounds (described in Japanese patent application laid-open No. Sho 60-105667 and U.S. Pat. No. 4239850), oxadiazole compounds (described in U.S. Pat. No. 4212970), and acylphosphine oxide compounds (described in Japanese patent application laid-open No. Sho 63-40799, Japanese patent publication No. Hei 5-29234, Japanese patent publication No. Sho 63-40799, Japanese patent application laid-open No. Hei 5-29234, and, Japanese patent laid-open Nos. H10-95788 and H10-29997).

In the present invention, the polymerization initiator is preferably an oxime-type polymerization initiator, and specific examples thereof include the initiators described in paragraphs [0049] to [0052] of International publication No. 2017/170443.

[ solvent ]

The polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability for forming the optically anisotropic layer of the present invention, and the like.

Specific examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, etc.), the number of the compounds may be 1 or more than 2.

[ orientation controlling agent ]

The polymerizable liquid crystal composition of the present invention may contain an alignment control agent as needed.

With the orientation controlling agent, various orientation states such as homeotropic orientation (homeotropic orientation), tilt orientation, hybrid orientation, cholesteric orientation, etc. can be formed in addition to the homogeneous orientation, and a specific orientation state can be controlled and realized more uniformly and more precisely.

As the orientation control agent for promoting uniform orientation, for example, a low molecular orientation control agent or a high molecular orientation control agent can be used.

As the low-molecular orientation controlling agent, for example, the contents of paragraphs [0009] to [0083] of Japanese patent laid-open No. 2002-.

Further, as the orientation controlling agent for the polymer, for example, the paragraphs [0021] to [0057] of Japanese patent laid-open No. 2004-198511 and the paragraphs [0121] to [0167] of Japanese patent laid-open No. 2006-106662 are incorporated herein by reference.

Examples of the orientation control agent for forming or promoting the vertical orientation include a boric acid compound and an onium salt compound, and specifically, compounds described in paragraphs [0023] to [0032] of Japanese patent laid-open No. 2008-225281, paragraphs [0052] to [0058] of Japanese patent laid-open No. 2012-208397, paragraphs [0024] to [0055] of Japanese patent laid-open No. 2008-026730, and paragraphs [0043] to [0055] of Japanese patent laid-open No. 2016-193869 are incorporated in the present specification.

On the other hand, the cholesteric alignment can be achieved by adding a chiral agent to the polymerizable liquid crystal composition of the present invention, and the rotation direction of the cholesteric alignment can be controlled by increasing the chirality.

In addition, the pitch of the cholesteric alignment can be controlled depending on the alignment restriction of the chiral agent.

The content of the orientation-controlling agent in the case of containing the orientation-controlling agent is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the composition. When the content is within this range, a desired alignment state can be achieved, and a uniform and highly transparent cured product can be obtained without precipitation, phase separation, alignment defects, and the like.

[ other Components ]

The polymerizable liquid crystal composition of the present invention may contain components other than the above components, for example, a surfactant, a tilt angle controller, an alignment aid, a plasticizer, a crosslinking agent, and the like.

[ optically Anisotropic layer ]

The optically anisotropic layer of the present invention is a cured product obtained by polymerizing the polymerizable liquid crystal composition of the present invention. The cured product can be formed on an arbitrary support on the optical film of the present invention described later, or on a polarizer on the polarizing plate of the present invention described later.

Examples of the method for forming the optically anisotropic film include a method in which the polymerizable liquid crystal composition of the present invention is used to set a desired alignment state, and then the composition is fixed by polymerization.

The polymerization conditions are not particularly limited, and in polymerization by light irradiation, ultraviolet rays are preferably used. The irradiation dose is preferably 10mJ/cm²～50J/cm²More preferably 20mJ/cm²～5J/cm²More preferably 30mJ/cm²～3J/cm²Particularly preferably 50 to 1000mJ/cm². Further, the polymerization reaction may be carried out under heating to promote the polymerization reaction.

The optically anisotropic layer of the present invention is preferably an optically anisotropic layer satisfying the following formula (III).

0.50＜Re(450)/Re(550)＜1.00…(III)

In the formula (III), Re (450) represents an in-plane retardation of the optically anisotropic layer at a wavelength of 450nm, and Re (550) represents an in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm. In the present specification, the measurement wavelength is 550nm when the measurement wavelength of retardation is not clearly marked.

The values of the in-plane retardation and the retardation in the thickness direction are measured by using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Opto Science, inc.).

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

slow axis direction (°)

Re(λ)＝R0(λ)

Rth(λ)＝((nx+ny)/2-nz)×d。

R0(λ) is a numerical value calculated from Axoscan OPMF-1 and refers to Re (λ).

The optically anisotropic layer is preferably a positive a plate or a positive C plate, more preferably a positive a plate.

Wherein, the positive a plate (positive a plate) and the positive C plate (positive C plate) are defined as follows.

When the refractive index in the slow axis direction (direction in which the in-plane refractive index is maximized) in the film plane is nx, the refractive index in the direction orthogonal to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, the positive a plate satisfies the relationship of expression (a1), and the positive C plate satisfies the relationship of expression (C1). In addition, Rth of the positive a plate indicates a positive value, and Rth of the positive C plate indicates a negative value.

Formula (A1) nx > ny ≈ nz

Formula (C1) nz > nx ≈ ny

In addition, the above "≈" includes not only a case where both are completely the same but also a case where both are actually the same.

By "substantially the same", it is meant that, in the positive A plate, for example, the case where (ny-nz). times.d (where d is the thickness of the film) is-10 to 10nm, preferably-5 to 5nm is also included in "ny. apprxz", and the case where (nx-nz). times.d is-10 to 10nm, preferably-5 to 5nm is also included in "nx. apprxz". In addition, in the positive C plate, for example, (nx-ny) × d (wherein d is the thickness of the film) is 0 to 10nm, and preferably 0 to 5nm is also included in "nx ≈ ny".

When the optically anisotropic layer is a positive A plate, Re (550) is preferably 100 to 180nm, more preferably 120 to 160nm, further preferably 130 to 150nm, and particularly preferably 130 to 140nm, from the viewpoint of functioning as a lambda/4 plate.

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

[ optical film ]

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

Fig. 1A, 1B, and 1C (hereinafter, simply referred to as "fig. 1" without particularly distinguishing between these drawings) are schematic cross-sectional views each showing an example of the optical film of the present invention.

In addition, fig. 1 is a schematic view, and the relationship of the thickness, the positional relationship, and the like of each layer do not necessarily match the actual situation, and the support, the alignment film, and the hard coat layer shown in fig. 1 are all arbitrary structural members.

The optical film 10 shown in fig. 1 has, in order: a support 16, an alignment film 14, and an optically anisotropic layer 12 as a cured product.

Further, as shown in fig. 1B, the optical film 10 may have the hard coat layer 18 on the side opposite to the side on which the alignment film 14 of the support 16 is provided, or as shown in fig. 1C, may have the hard coat layer 18 on the side opposite to the side on which the alignment film 14 of the optically anisotropic layer 12 is provided.

Hereinafter, various members used in the optical film of the present invention will be described in detail.

[ optically anisotropic layer ]

The optical film of the present invention has the optically anisotropic layer of the present invention described above.

In the optical film of the present invention, the thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[ support body ]

As described above, the optical film of the present invention may have a support as a substrate for forming the optically anisotropic layer.

Such a support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.

Examples of such a support include a glass substrate and a polymer film, and examples of a material of the polymer film include a cellulose-based polymer; acrylic polymers having an acrylate polymer such as polymethyl methacrylate and polymers containing a lactone ring; a thermoplastic norbornene-based polymer; a polycarbonate-series polymer; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; a vinyl chloride polymer; amide polymers such as nylon and aromatic polyamide; an imide polymer; a sulfone-based polymer; a polyether sulfone-based polymer; a polyether ether ketone polymer; polyphenylene sulfide-based polymer; a vinylidene chloride polymer; a vinyl alcohol polymer; a vinyl butyral polymer; an aryl ester polymer; a polyoxymethylene polymer; an epoxy polymer; or a polymer obtained by mixing these polymers.

Further, a polarizer described later may also be provided with such a support.

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 30 μm.

[ alignment film ]

When the optical film of the present invention has any of the above-described supports, it is preferable to have an alignment film between the support and the optically anisotropic layer. In addition, the support may also be an embodiment having an alignment film as well.

The alignment film usually contains a polymer as a main component. As a polymer material for an alignment film, there are many documents describing it, and many commercial products are available.

The polymeric material utilized in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. Especially preferred are modified and unmodified polyvinyl alcohols.

Examples of the alignment film that can be used in the present invention include the alignment films described in international publication No. 01/88574, page 43, line 24 to page 49, line 8; modified polyvinyl alcohols described in paragraphs [0071] to [0095] of Japanese patent No. 3907735; and a liquid crystal alignment film formed from the liquid crystal alignment agent described in Japanese patent laid-open publication No. 2012-155308.

In the present invention, it is preferable to use a photo-alignment film as the alignment film, because the photo-alignment film does not contact the surface of the alignment film when the alignment film is formed, and thus planar degradation can be prevented.

The photo-alignment film is not particularly limited, and a polymer material such as a polyimide compound or a polyimide compound described in paragraphs [0024] to [0043] of international publication No. 2005/096041; a liquid crystal alignment film formed from a liquid crystal alignment agent having a photo-alignment group as described in Japanese patent laid-open publication No. 2012-155308; and a product name LPP-JP265CP manufactured by Rolic Technologies Ltd.

In the present invention, the thickness of the alignment film is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm, and still more preferably 0.01 to 0.5 μm, from the viewpoint of forming an optically anisotropic layer having a uniform thickness by neutralizing surface irregularities that may exist in the support.

[ hard coating ]

The optical film of the present invention preferably has a hard coat layer in order to impart physical strength to the film. Specifically, the substrate may have a hard coat layer on the side opposite to the side on which the alignment film of the support is provided (see fig. 1B), or may have a hard coat layer on the side opposite to the side on which the alignment film of the optically anisotropic layer is provided (see fig. 1C).

As the hard coat layer, the hard coat layers described in paragraphs [0190] to [0196] of Japanese patent laid-open No. 2009-98658 can be used.

[ ultraviolet light absorber ]

The optical film of the present invention preferably contains an Ultraviolet (UV) absorber in consideration of the influence of external light (particularly, ultraviolet rays).

The ultraviolet absorber may be contained in the optically anisotropic layer of the present invention, or may be contained in a member other than the optically anisotropic layer constituting the optical film of the present invention. As the member other than the optically anisotropic layer, for example, a support is preferable.

As the ultraviolet absorber, any conventionally known ultraviolet absorber that can achieve ultraviolet absorbability can be used. Among such ultraviolet absorbers, benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbers can be preferably used from the viewpoint of high ultraviolet absorptivity and obtaining ultraviolet absorbing ability (ultraviolet cut-off ability) used in image display devices.

In addition, in order to expand the ultraviolet absorption range, more than 2 kinds of ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.

Specific examples of the ultraviolet absorber include compounds described in paragraphs [0258] to [0259] of Japanese patent laid-open No. 2012 and 18395, and compounds described in paragraphs [0055] to [0105] of Japanese patent laid-open No. 2007 and 72163.

Examples of commercially available products include Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, and Tinuvin1577 (both manufactured by BASF corporation).

[ polarizing plate ]

The polarizing plate of the present invention includes the optical film of the present invention and a polarizer.

In the case where the optically anisotropic layer of the present invention is a λ/4 plate (positive a plate), the polarizing plate of the present invention can be used as a circular polarizing plate.

In the polarizing plate of the present invention, when the optically anisotropic layer of the present invention is a λ/4 plate (positive a plate), the angle formed by the slow axis of the λ/4 plate and the absorption axis of the polarizer described later is preferably 30 to 60 °, more preferably 40 to 50 °, still more preferably 42 to 48 °, and particularly preferably 45 °.

The "slow axis" of the λ/4 plate means a direction in which the refractive index becomes maximum in the plane of the λ/4 plate, and the "absorption axis" of the polarizer means a direction in which the absorbance is highest.

[ polarizer ]

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

As the absorption polarizer, an iodine polarizer, a dye polarizer using a dichroic dye, a polyene polarizer, and the like can be used. As the iodine-based polarizer and the dye-based polarizer, both a coating-type polarizer and an extension-type polarizer can be applied, but a polarizer prepared by absorbing iodine or a dichroic dye with polyvinyl alcohol and extending the absorbed iodine or dichroic dye is preferable.

Further, as a method for obtaining a polarizer by stretching and dyeing a laminated film of a polyvinyl alcohol layer formed on a substrate, there can be mentioned japanese patent No. 5048120, japanese patent No. 5143918, japanese patent No. 4691205, japanese patent No. 4751481, and japanese patent No. 4751486, and known techniques relating to these polarizers can also be preferably used.

As the reflective polarizer, a polarizer in which films having different birefringence are stacked, a wire grid polarizer, a polarizer in which cholesteric liquid crystal having a selective reflection region and an 1/4 wavelength plate are combined, or the like can be used.

Among them, from the viewpoint of more excellent adhesion, it is preferable to contain a polyvinyl alcohol resin (containing-CH as a repeating unit)₂-CHOH-, in particular, at least 1 selected from the group comprising polyvinyl alcohol and ethylene-vinyl alcohol copolymers) of a polarizer.

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, and still more preferably 5 μm to 15 μm.

[ adhesive layer ]

The polarizing plate of the present invention may have an adhesive layer disposed between the optically anisotropic layer of the optical film of the present invention and the polarizer.

The pressure-sensitive adhesive layer for laminating a cured product and a polarizer includes, for example, a material having a ratio (tan δ ═ G "/G ') of storage modulus G' to loss modulus G ″ measured by a dynamic viscoelasticity measuring apparatus of 0.001 to 1.5, and includes a so-called pressure-sensitive adhesive, a material that is easily subject to creep, and the like. Examples of the binder that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based binder.

[ image display apparatus ]

The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.

The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as "EL") display panel, and a plasma display panel.

Among these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element, and more preferably a liquid crystal display device.

[ liquid Crystal display device ]

A liquid crystal display device as an example of the image display device of the present invention is a liquid crystal display device having the polarizing plate and the liquid crystal cell of the present invention.

In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, the polarizing plate of the present invention is preferably used as the front polarizing plate, and more preferably used as the front and rear polarizing plates.

Hereinafter, a liquid crystal cell constituting the liquid crystal display device will be described in detail.

< liquid crystal cell >

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

In the TN-mode liquid crystal cell, when no voltage is applied, rod-like liquid crystalline molecules are substantially horizontally aligned, and further are twisted and aligned at 60 to 120 °. TN mode liquid crystal cells are most widely used as color TFT liquid crystal display devices and are described in many documents.

In the VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. In addition to (1) a liquid crystal cell of VA mode in a narrow sense in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied and aligned substantially horizontally when a voltage is applied (described in japanese patent application laid-open No. 2-176625), a liquid crystal cell of VA mode includes: (2) liquid crystal cells of a VA mode (MVA mode) (SID97, Digest of tech. papers (proceedings) 28 (1997)) 845, which are multizoned to enlarge a viewing angle, (3) liquid crystal cells of a n-ASM mode (n-ASM mode) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and are twisted and oriented in multiple domains when a voltage is applied (proceedings 58 to 59(1998) of japan liquid crystal research institute), and (4) liquid crystal cells of a surveyal mode (published in LCD international 98). Further, any of a PVA (Patterned Vertical Alignment) type, a photo-Alignment type (Optical Alignment) and a PSA (Polymer-Sustained Alignment) type may be used. The details of these modes are described in detail in Japanese patent laid-open No. 2006-215326 and Japanese Table 2008-538819.

In the IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in plane by applying a parallel electric field to the substrate surface. The IPS mode displays black in a state where no electric field is applied, and absorption axes of a pair of upper and lower polarizing plates are orthogonal to each other. Methods for improving the viewing angle by reducing light leakage during black display, which is improved in the oblique direction, using an optical compensation sheet are disclosed in japanese patent application laid-open nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[ organic EL display device ]

As an example of the image display device of the present invention, an organic EL display device may be preferably exemplified by a λ/4 plate (positive a plate) having a polarizer, an optically anisotropic layer of the present invention, and an organic EL display panel in this order from the viewing side.

The organic EL display panel is a display panel including organic EL elements in which an organic light-emitting layer (organic electroluminescent layer) is interposed between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure can be employed.

Examples

The present invention will be described in further detail with reference to the following examples. The materials, the amounts used, the ratios, the contents of the processes, the processing steps, and the like shown in the following examples can be appropriately modified within the scope not departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed restrictively based on the examples shown below.

[ Synthesis examples 1 to 4]

7.5 parts by mass of cyclohexanone as a solvent was added to a flask equipped with a cooling tube, a thermometer and a stirrer, and the flask was heated at 80 ℃ by water bath heating while adding 50mL/min of nitrogen gas.

Here, a solution obtained by mixing the blending amounts (parts by mass) shown in table 4 below of monomers 1 to 3 shown in table 4 below, 0.25 part by mass of 2, 2' -azobis (isobutyronitrile) as a polymerization initiator, and 22.5 parts by mass of cyclohexanone as a solvent was added dropwise over 3 hours, and stirred while maintaining a heated state for 30 minutes.

Then, 0.1 part by mass of 2, 2' -azobis (isobutyronitrile) was added, and the temperature was raised to 90 ℃ to continue heating for 3 hours.

After the reaction, the reaction mixture was naturally cooled to room temperature to obtain a polymer solution containing about 50 mass% of copolymers P-1 to P-4 represented by the following formulae. In the following formula, the numerical value described in each repeating unit of the copolymer represents the content (mass%) of each repeating unit with respect to all repeating units.

[ Table 4]

Copolymer P-1

[ chemical formula 22]

Copolymer P-2

[ chemical formula 23]

Copolymer P-3

[ chemical formula 24]

Copolymer P-4

[ chemical formula 25]

[ Synthesis example 5]

Into a flask equipped with a cooling tube, a thermometer and a stirrer, 100 parts by mass of a polymer solution containing the copolymer P-1 synthesized in Synthesis example 1, 0.025 parts by mass of P-methoxyphenol, and 1 part by mass of triethylamine were added, and the mixture was heated in a water bath at 60 ℃ for 4 hours.

After the heating, the mixture was naturally cooled to room temperature, 150 parts by mass of ethyl acetate was added, liquid-separation washing was performed in the order of fixed hydrochloric acid, a saturated aqueous sodium bicarbonate solution and water, and the obtained organic layer was dried over anhydrous magnesium sulfate to obtain a polymer solution containing about 20 mass% of copolymer P-5 represented by the following formula. The content of the halogen moiety calculated by combustion ion chromatography was 1 mass%.

Copolymer P-5

[ chemical formula 26]

[ Synthesis examples 6 to 8]

Polymer solutions containing about 20 mass% of each of copolymers P-6 to P-8 represented by the following formulae were obtained in the same manner as in Synthesis example 5 except that each of the polymer solutions containing copolymer P-2 to copolymer P-4 synthesized in Synthesis examples 2 to 4 was used instead of the polymer solution containing copolymer P-1 synthesized in Synthesis example 1.

Copolymer P-6

[ chemical formula 27]

Copolymer P-7

[ chemical formula 28]

Copolymer P-8

[ chemical formula 29]

[ Synthesis example 9]

A polymer solution containing about 20 mass% of a copolymer P-9 represented by the following formula was obtained in the same manner as in Synthesis example 1, except that the monomer 3 used for the synthesis of the copolymer P-1 was changed to an acrylic butyl group and the blending amount of each monomer was changed.

Copolymer P-9

[ chemical formula 30]

[ Synthesis example 10]

A copolymer FA-1 represented by the following formula was synthesized.

In the following formulae, a to c are a: b: c: 40:54:6, and the content (mass%) of each repeating unit relative to all repeating units is represented.

In the following formulae, when the content of each repeating unit is expressed in "mol%", a: b: c is 60:30:10 as in patent document 1 (international publication No. 2019/009255).

Copolymer FA-1

[ chemical formula 31]

Examples 1 to 9 and comparative example 1

[ preparation of polymerizable liquid Crystal composition ]

A polymerizable liquid crystal composition having the following composition was prepared.

In addition, the groups adjacent to the acryloyloxy groups of the following polymerizable liquid crystal compounds L-3 and L-4 represent propylene groups (groups in which methyl groups are substituted with ethylene groups), and the following polymerizable liquid crystal compounds L-3 and L-4 represent mixtures of positional isomers in which the positions of the methyl groups are different.

Polymerizable liquid Crystal Compound L-3

[ chemical formula 32]

Polymerizable liquid Crystal Compound L-4

[ chemical formula 33]

Polymerizable liquid Crystal Compound A-1

[ chemical formula 34]

Polymerization initiator S-1

[ chemical formula 35]

[ preparation of composition for Forming photo-alignment film ]

The photo-alignment layer forming material described in example 1 of WO2016/002722 was prepared and used to produce the liquid crystal film of the present invention.

[ production of cellulose acylate film 1]

< preparation of concentrated cellulose acylate solution for core layer >

The following composition was put into a mixing tank, and the components were dissolved by stirring to prepare a cellulose acetate solution used as a concentrated cellulose acylate solution for the core layer.

Compound G

[ chemical formula 36]

< preparation of concentrated cellulose acylate solution in outer layer >

To 90 parts by mass of the above-mentioned core layer cellulose acylate dope was added 10 parts by mass of the following matting agent solution to prepare a cellulose acetate solution to be used as an outer layer cellulose acylate dope.

< production of cellulose acylate film 1 >

The cellulose acylate dope of the core layer and the cellulose acylate dope of the outer layer were filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, and then the cellulose acylate dope of the core layer and the cellulose acylate dopes of the outer layers on both sides thereof were cast from a casting port onto a roll at 20 ℃ in 3 layers (a belt casting machine). The film was peeled from the roll in a state where the solvent content of the film on the roll was approximately 20 mass%, and both ends in the width direction of the obtained film were fixed with tenter clips, and dried while being stretched in the transverse direction at a stretch ratio of 1.1 times. Then, the obtained film was transported between rollers of a heat treatment apparatus and further dried to produce an optical film having a thickness of 40 μm, which was used as the cellulose acylate film 1.

The core layer of the cellulose acylate film 1 had a thickness of 36 μm, and the outer layers disposed on both sides of the core layer had a thickness of 2 μm. The in-plane retardation of the resulting cellulose acylate film 1 at a wavelength of 550nm was 0 nm.

The cellulose acylate film 1 thus obtained was used as a support.

[ production of optical film ]

The prepared cellulose acylate film 1 was coated on one side with a previously prepared composition for forming a photo-alignment film by a bar coater.

After coating the composition for forming a photo-alignment film, the obtained film was dried on a hot plate at 120 ℃ for 1 minute to remove the solvent, thereby forming a composition layer for forming a photo-alignment film having a thickness of 0.3 μm.

The obtained composition layer for forming a photo-alignment film was irradiated with polarized ultraviolet light (10 mJ/cm)²An ultra-high pressure mercury lamp is used) to form the photo-alignment layer.

Then, the polymerizable liquid crystal compositions of examples 1 to 9 and comparative example 1 prepared in advance were applied to the photo-alignment layer by a bar coater to form a polymerizable liquid crystal composition layer.

The resultant polymerizable liquid crystal composition layer was heated on a hot plate temporarily to 110 ℃ and then cooled to 60 ℃ to stabilize the alignment.

Then, the mixture was maintained at 60 ℃ and irradiated with ultraviolet rays (500 mJ/cm) under a nitrogen atmosphere (oxygen concentration: 100ppm)²Using an ultra-high pressure mercury lamp) to fix the orientation and form an optically anisotropic layer having a thickness of 2.3 μm, thereby producing an optical film. The in-plane retardation of the resulting optical film at a wavelength of 550nm was 140 nm.

[ example 10]

Optical films were produced in the same manner as in examples 1 to 9 and comparative example 1 except that the polymerizable liquid crystal composition was changed as shown below.

Polymerizable liquid Crystal Compound L-1

[ chemical formula 37]

Polymerizable liquid Crystal Compound L-2

[ chemical formula 38]

[ evaluation of storage stability ]

[ preparation of a polymerizable liquid Crystal composition by heating ]

A polymerizable liquid crystal composition was obtained in the same manner as in examples 1 to 10 and comparative example 1, except that 1000ppm of triethylamine was added.

Subsequently, the resultant polymerizable liquid crystal composition was heated at 60 ℃ for 7 days to prepare a heated polymerizable liquid crystal composition.

[ evaluation ]

An optical film was produced in the same manner as described above except that a heated polymerizable liquid crystal composition was used instead of the polymerizable liquid crystal compositions of examples 1 to 10 and comparative example 1, and the in-plane retardation at a wavelength of 550nm was measured.

The ratio of the measured in-plane retardation to the in-plane retardation of the optical film produced using the polymerizable liquid crystal compositions of examples 1 to 10 and comparative example 1 which were not heated (hereinafter, abbreviated as "reference value" in this paragraph) was calculated, and the evaluation was performed according to the following criteria.

< Standard >

A: the ratio of the measured in-plane retardation to the reference value was less than 2%

B: the ratio of the in-plane retardation to the reference value is 2% or more and less than 5%

C: the ratio of the measured in-plane retardation to a reference value is 5% or more

[ evaluation of orientation ]

The optical film thus produced was observed in a state of being shifted from the extinction position by 2 degrees using a polarizing microscope. The state where there was no local difference in brightness at the time of observation was evaluated as the liquid crystal director being uniformly aligned (excellent alignment property).

The results of the observation were distinguished according to the following criteria. The results are shown in table 5 below.

AAA: the liquid crystal has fine and oriented directional texture and excellent display performance

AA: the liquid crystal director is uniformly aligned, and the display performance is excellent

A: no blurring of liquid crystal orientation and planar stability

B: slight blurring and planar stabilization of liquid crystal director

C: the liquid crystal director is locally blurred and is stable in a planar manner

D: the liquid crystal director is blurred in a wide range and is not planar-stable, and the display properties are very poor

[ production of reflection preventing plate (circular polarizing plate) for organic EL ]

< production of Positive C plate film 1 >

As the dummy support, commercially available triacetyl cellulose film "Z-TAC" (manufactured by FUJIFILM Corporation) was used. Hereinafter, this is omitted as the cellulose acylate film 2.

After the surface temperature of the cellulose acylate film 2 was raised to 40 ℃ by passing it through a heating roller of a dielectric type having a temperature of 60 ℃, the film was coated on one surface thereof by a bar coater in an amount of 14ml/m²An alkaline solution of the composition shown below was applied and heated to 110 ℃, and the resulting film was conveyed for 10 seconds under a steam-type far-infrared heater manufactured by Noritake co. Then, the obtained film was coated with 3ml/m of pure water by the same bar coater². Subsequently, washing with water by a jet coater and dehydration by an air knife were repeated 3 times, and the obtained film was conveyed to a drying zone at 70 ℃ for 10 seconds and dried to produce a cellulose acylate film 2 subjected to an alkali saponification treatment.

The alkali-saponified cellulose acylate film 2 was continuously coated with an alignment film-forming coating liquid having the following composition using a #8 wire bar. The coated alignment film-forming coating liquid was dried with 60 ℃ warm air for 60 seconds and further with 100 ℃ warm air for 120 seconds to form an alignment film.

The following coating liquid N for an optically anisotropic film was applied on the cellulose acylate film 2 having the alignment film formed as described above. After coating liquid N for the coated optically anisotropic film was aged at 60 ℃ for 60, 70mW/cm was used under air²The gas-cooled metal halide lamp (EYE GRAPHICS Co., Ltd.) was irradiated with 1000mJ/cm²Ultraviolet rays of (1). Thus, the rod-like polymerizable liquid crystal compound was immobilized in a vertically aligned state, and a positive C-plate film 1 was produced. The positive C plate film 1 had a retardation in the thickness direction at a wavelength of 550nm of-60 nm.

Polymerizable liquid Crystal Compound L-1

[ chemical formula 39]

Polymerizable liquid Crystal Compound L-2

[ chemical formula 40]

Vertical alignment agent S01

[ chemical formula 41]

Vertical alignment agent S02

[ chemical formula 42]

Compound B03 [ weight average molecular weight: 15000. the numerical value in the following formula represents the content (mass%) of each repeating unit with respect to all repeating units. Angle (c)

[ chemical formula 43]

< manufacture of circular polarizing plate >

The surface of the optically anisotropic layer of the optical film thus produced was subjected to corona treatment, and an epoxy-based Ultraviolet (UV) adhesive was further applied. The positive C plate film 1 produced in the above was transferred thereon, and after UV curing of the UV adhesive, the cellulose acylate film 2 was removed. A PVA (polyvinyl alcohol) polarizing plate with a protective film was bonded to the cellulose acylate film 1 side of the optical laminate via a pressure-sensitive adhesive, to obtain a circularly polarizing plate.

[ evaluation of adhesion ]

A part (non-coating part) not coated with the UV adhesive was prepared in advance between the optical laminate of the prepared circularly polarizing plate and the front C plate film 1, and the 180 DEG peel force (unit: N/25mm) was measured in accordance with JIS6854-2 with the non-coating part as a nip.

The measured values were evaluated according to the following criteria. The results are shown in table 5 below.

< Standard >

A: a peeling force of 1.6N/25mm or more

B: peeling force less than 1.6N/25mm

[ Table 5]

From the results shown in Table 5, it is understood that when the copolymer blended with the polymerizable liquid crystal compound does not have the repeating unit (halogen moiety) represented by the above formula (2), the storage stability is poor (comparative example 1).

On the other hand, it is found that when the copolymer blended with the polymerizable liquid crystal compound has a repeating unit (halogen moiety) represented by the above formula (2), the storage stability is improved (examples 1 to 10).

In particular, it is seen from comparison of examples 1 to 4 and examples 5 to 8 that when the copolymer has the repeating unit (polymerizable moiety) represented by the above formula (3), the adhesion to the upper layer is good.

Further, it is understood by comparing examples 1 to 4 and example 9 that the copolymer having the repeating unit (aromatic ring moiety) represented by the above formula (4) has good orientation with the upper layer.

Description of the symbols

10-optical film, 12-optically anisotropic layer, 14-oriented film, 16-support, 18-hard coat layer.

Claims

1. A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound and a copolymer having at least a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2),

wherein, in the formulas (1) and (2),

R¹and R²Represents a hydrogen atom or a methyl group,

L¹and L²Represents a linking group having a valence of 2,

A¹represents a group represented by the following formula (1-1), A²Represents a group represented by the following formula (2-1) or (2-2),

*-C_nF_2nCF₂X (1-1)

wherein, in the formula (1-1),

is represented by¹The bonding position of (a) to (b),

n represents an integer of 1 to 6,

x represents a hydrogen atom or a fluorine atom,

wherein in the formulas (2-1) and (2-2),

is represented by²The bonding position of (a) to (b),

y represents-O-, -NH-or-NR^Y-，R^YRepresents a substituent group, and a pharmaceutically acceptable salt thereof,

x represents a halogen atom.

2. The polymerizable liquid crystal composition according to claim 1,

the copolymer is a copolymer further having a repeating unit represented by the following formula (3),

wherein, in the formula (3),

R³represents a hydrogen atom or a methyl group,

L³represents a linking group having a valence of 2,

A³represents a polymerizable group.

3. The polymerizable liquid crystal composition according to claim 1 or 2,

the copolymer is a copolymer further having a repeating unit represented by the following formula (4),

wherein, in the formula (4),

R⁴represents a hydrogen atom or a methyl group,

L⁴represents a linking group having a valence of 2,

A⁴represents an aromatic ring group which may have a substituent.

4. The polymerizable liquid crystal composition according to any one of claims 1 to 3,

the content of the repeating unit represented by the formula (2) is 0.001 to 60% by mass relative to the total mass of all repeating units of the copolymer.

5. The polymerizable liquid crystal composition according to any one of claims 1 to 4,

the content of the copolymer is 0.01-0.20 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

6. An optically anisotropic layer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 5.

7. An optical film having the optically anisotropic layer of claim 6.

8. A polarizing plate having the optical film according to claim 7 and a polarizer.

9. An image display device having the optical film of claim 7 or the polarizing plate of claim 8.