KR20220050161A - Polymerizable liquid crystal composition, optically anisotropic layer, optical film, polarizing plate and image display device - Google Patents

Abstract

A¹은, 하기 식 (1-1)로 나타나는 기를 나타내고, A2는, 하기 식 (2-1) 또는 (2-2)로 나타나는 기를 나타낸다.

An object of the present invention is to provide a polymerizable liquid crystal composition excellent in storage stability, and an optically anisotropic layer, an optical film, a polarizing plate, and an image display device obtained using the same. 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 ¹ represents group represented by the following formula (1-1), and A2 represents group represented by the following formula (2-1) or (2-2).

Description

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

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.

DESCRIPTION OF RELATED ART Optical films, such as an optical compensation sheet and retardation film, are used in various image display apparatuses from viewpoints, such as image discoloration cancellation and a viewing angle expansion.

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

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

Patent Document 1: International Publication No. 2019/009255

As a result of the present inventors examining the optically anisotropic layer described in Patent Document 1, the problem that the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition decomposes over time, that is, the storage stability of the polymerizable liquid crystal composition is poor. revealed that there was a problem.

Then, this invention makes it a subject to provide the polymeric liquid crystal composition excellent in storage stability, and the optically anisotropic layer obtained using this, an optical film, a polarizing plate, and an image display device.

MEANS TO SOLVE THE PROBLEM As a result of the present inventors earnestly examining in order to achieve the said subject, the polymeric liquid crystal composition containing the copolymer which has a repeating unit represented by Formula (1) and (2) mentioned later with a polymeric liquid crystal compound is stored It found out that it was excellent in stability, and completed this invention.

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

[One]

A polymerizable liquid crystal composition comprising a 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).

[Formula 1]

Here, in the above formulas (1) and (2),

R ¹ and R ² each represent a hydrogen atom or a methyl group.

L ¹ and L ² represent a divalent linking group.

A ¹ represents group represented by the following formula (1-1), and A ² represents a group represented by the following formula (2-1) or (2-2).

[Formula 2]

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

* represents a bonding position with L ¹ .

n represents the integer of 1-6.

X represents a hydrogen atom or a fluorine atom.

[Formula 3]

Here, in the above formulas (2-1) and (2-2),

* represents a bonding position with L ² .

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

X represents a halogen atom.

[2]

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

[Formula 4]

Here, in the above formula (3),

R ³ represents a hydrogen atom or a methyl group.

L ³ represents a divalent linking group.

A ³ represents 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).

[Formula 5]

Here, in the above formula (4),

R ⁴ represents a hydrogen atom or a methyl group.

L ⁴ represents a divalent linking group.

A ⁴ represents the 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 with respect 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 according to [7] or the polarizing plate according to [8].

ADVANTAGE OF THE INVENTION According to this invention, the polymeric liquid crystal composition excellent in storage stability, and the optically anisotropic layer obtained using this, an optical film, a polarizing plate, and an image display device can be provided.

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

Hereinafter, the present invention will be described in detail.

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

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

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

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

In addition, in this specification, "(meth)acrylate" is a notation which shows acrylate or methacrylate, "(meth)acrylic acid" is a notation which shows acrylic acid or methacrylic acid, "(meth)acrylic acid" "Loyl" is a mark representing methacryloyl or acryloyl.

In addition, in this specification, the kind of substituent at the time of saying "you may have a substituent", the position of a substituent, and the number of substituents are not specifically limited. The number of substituents may be 1, 2, 3, or more, for example. As a substituent, a monovalent|monohydric nonmetallic atom group except a hydrogen atom is mentioned, for example, Specifically, it can select 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 a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; Acyloxy groups, such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; Acyl groups, such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; cycloalkyl group; aryl group; heteroaryl group; hydroxyl group; carboxyl group; form diary; sulfo group; cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; and combinations thereof.

[Polymerizable liquid crystal composition]

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

In this invention, as mentioned above, storage stability of a polymeric liquid crystal composition becomes favorable by mix|blending the copolymer which has a repeating unit represented by Formula (1) and (2) mentioned later with a polymeric liquid crystal compound as mentioned above.

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

First, the present inventors speculate that the basic substance unavoidably contained in a polymeric liquid crystal composition is the cause about the reason that the storage stability of a conventionally well-known polymeric liquid crystal composition is inferior.

Moreover, the present inventors have confirmed that the repeating unit represented by Formula (2) mentioned later which a copolymer has is decomposed|disassembled with time, and is releasing an acid (for example, HCl etc.).

Therefore, in this invention, it is thought that storage stability became favorable when the acid released|released from the repeating unit represented by Formula (2) mentioned later traps the basic substance contained inevitably in a polymeric liquid crystal composition.

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

[copolymer]

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

[Formula 6]

<Fluorine part>

The fluorine part which the copolymer of this invention has is a repeating unit represented by following formula (1).

[Formula 7]

In the formula (1), R ¹ represents a hydrogen atom or a methyl group.

Moreover, in said Formula (1), L< ¹ > represents a bivalent coupling group.

Moreover, in said Formula (1), A< ¹ > represents group represented by following formula (1-1).

[Formula 8]

In the formula (1-1), * represents a bonding position with L ¹ .

Moreover, in said Formula (1-1), n represents the integer of 1-6.

Moreover, in said Formula (1-1), X represents a hydrogen atom or a fluorine atom.

Examples of the divalent linking group represented by L ¹ in the formula (1) include -O-, -NR ^a11 - (provided that R ^a11 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aliphatic hydrocarbon group having 6 to carbon atoms. 20 aryl group), -S-, -CO-, -SO ₂ -, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a divalent group selected from a group formed by connecting two or more thereof A connector can be mentioned.

As a divalent linking group formed by connecting two or more, for example, -CO-O-, -O-CO-O-, -CO-NH-, -CO-O-(CH ₂ ) _ma O- (provided that , ma represents an integer of 1 to 20.) and the like.

Among these, as the divalent linking group, -O-, -CO-O-, -CO-NH-, or a group consisting of a combination of one or more of these and an alkylene group is preferable, and the following formulas (L-1) to ( The group represented by L-5) is more preferable.

[Formula 9]

In the formulas (L-1) to (L-5), *1 represents a bonding position with the carbon atom to which R ¹ in the formula (1) is bonded, and *2 represents a position in the formula (1). A binding position with A ¹ is shown.

Moreover, in said Formula (L-1) - (L-5), m represents the integer of 1-20, the integer of 2-16 is preferable, the integer of 2-12 is more preferable, 2-6 An integer of is more preferable.

Moreover, in said Formula (L-1) - (L-5), n represents the integer of 1-20, the integer of 2-16 is preferable, the integer of 2-12 is more preferable, 2-6 An integer of is more preferable.

As a repeating unit represented by said Formula (1), the repeating unit represented by following formula (F-1) - (F-12) is mentioned suitably, for example.

[Formula 10]

In the present invention, the reason why the coatability of the polymerizable liquid crystal composition of the present invention is improved, and the film thickness nonuniformity (hereinafter also abbreviated as “wind nonuniformity”) caused by the drying wind after application is alleviated. In, the content of the repeating unit represented by the formula (1) is preferably 20 to 90 mass%, more preferably 20 to 60 mass%, with respect to the total mass of all repeating units of the copolymer of the present invention, It is more preferable that it is 25-45 mass %.

<Halogen Part>

The halogen part which the copolymer of this invention has is a repeating unit represented by following formula (2).

[Formula 11]

In the formula (2), R ² represents a hydrogen atom or a methyl group.

Moreover, in said Formula (2), L< ² > represents a bivalent coupling group. Moreover, as a bivalent coupling group, the thing similar to L< ¹ > in said Formula (1) is mentioned, Among these, group represented by the said Formula (L-1) or (L-5) is preferable.

Moreover, in said Formula ( ² ), A2 represents group represented by following formula (2-1) or (2-2).

[Formula 12]

In the formulas (2-1) and (2-2), * represents a bonding position with L ² .

Moreover, in said formula (2-1) and (2-2), Y represents -O-, -NH-, or -NR ^Y- , and R ^Y represents a substituent. Moreover, as a substituent, what was described as the above-mentioned substituent T is mentioned.

Moreover, in said Formula (2-1) and (2-2), X represents a halogen atom.

It is preferable that it is -O- or -NH-, and, as for Y in said formula (2-1) and (2-2), it is more preferable that it is -O-.

Examples of the halogen atom represented by X in the formulas (2-1) and (2-2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, chlorine It is preferable that it is an atom or a bromine atom, and it is more preferable that it is a chlorine atom.

As a repeating unit represented by said formula (2), the repeating unit represented by following formula (X-1) - (X-17) is mentioned suitably, for example.

[Formula 13]

In the present invention, since the storage stability of the polymerizable liquid crystal composition of the present invention becomes better, the content of the repeating unit represented by the formula (2) is 0.001 with respect to the total mass of all the repeating units of the copolymer of the present invention. It is preferable that it is -60 mass %, It is more preferable that it is 0.005-30 mass %, It is more preferable that it is 0.01-20 mass %.

<Polymerizable parts>

In the present invention, since 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 good, the copolymer of the present invention has a repeating unit represented by the following formula (3) (Hereinafter, it is also abbreviated as "polymerizable part.") It is preferable to have further.

[Formula 14]

In the formula (3), R ³ represents a hydrogen atom or a methyl group.

Moreover, in said Formula (3), L< ³ > represents a bivalent coupling group. Moreover, as a bivalent coupling group, the thing similar to L< ¹ > in said Formula (1) is mentioned.

Moreover, in said Formula (3), A< ³ > represents a polymeric group.

As the polymerizable group represented by A ³ in the formula (3), a polymerizable group capable of radical polymerization or cationic polymerization is preferable.

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

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

As an example of a especially preferable polymeric group, the polymeric group represented by any one of following formula (P-1) - (P-20) is mentioned.

[Formula 15]

As a repeating unit represented by said formula (3), the repeating unit represented by following formula (J-1) - (J-10) is mentioned suitably, for example.

[Formula 16]

When it contains the repeating unit represented by the said Formula (3), content of the repeating unit represented by the said Formula (3) is adhesiveness with the layer provided in the upper layer of the optically anisotropic layer obtained by superposing|polymerizing the polymeric liquid crystal composition of this invention. For this reason, it is preferably 0.5 to 30 mass %, more preferably 1 to 20 mass %, more preferably 2 to 10 mass %, based on the total mass of all repeating units of the copolymer of the present invention. desirable.

<Aromatic ring part>

In this invention, since the orientation of the polymeric liquid crystal composition of this invention becomes favorable, the copolymer of this invention contains the repeating unit (henceforth abbreviated as "aromatic ring part") represented by following formula (4). It is better to have more.

[Formula 17]

In the formula (4), R ⁴ represents a hydrogen atom or a methyl group.

Moreover, in said Formula ( ⁴ ), L4 represents a bivalent coupling group. Moreover, as a bivalent coupling group, the thing similar to L< ¹ > in said Formula (1) is mentioned.

Moreover, in said Formula ( ⁴ ), A4 represents the aromatic ring group which may have a substituent. Moreover, as a substituent, what was described as the above-mentioned substituent T is mentioned.

Examples of the aromatic ring group represented by A ⁴ in the formula (4) include a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and specifically, a phenyl group, 2,6-diethylphenyl group, naphthyl group, A biphenyl group etc. are mentioned, Especially, it is preferable that they are a phenyl group, a naphthyl group, or a biphenyl group.

As a repeating unit represented by said formula (4), the repeating unit represented by following formula (H-1) - (H-6) is mentioned suitably, for example.

[Formula 18]

When the repeating unit represented by the formula (4) is contained, the content of the repeating unit represented by the formula (4) is, from the reason that the orientation of the polymerizable liquid crystal composition of the present invention becomes more favorable, the total amount of the copolymer of the present invention. It is preferable that it is 20-80 mass % with respect to the total mass of a repeating unit, It is more preferable that it is 40-80 mass %, It is more preferable that it is 50-70 mass %.

<Other parts>

The copolymer of this invention may have other repeating units other than the repeating unit represented by Formula (1)-(4) mentioned above as needed.

As a monomer forming another repeating unit, those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1 to 483 can be used.

For example, compounds having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. are mentioned. can

Specifically, the following monomers are mentioned.

(Acrylic acid esters)

Specific examples of the acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxy Benzyl acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc. are mentioned.

(methacrylic acid esters)

Specifically as methacrylic acid esters, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylol propane Monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol monoacetate monomethacrylate, etc. can be heard

(acrylamides)

Specific examples of acrylamides include acrylamide, N-alkyl acrylamide (the alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group), N,N-dialkyl acrylamide (C1-C6 thing as an alkyl group), N-hydroxyethyl-N-methylacrylamide, N-2-acetamide ethyl-N-acetyl acrylamide, etc. are mentioned.

(Methacrylamides)

Specifically as methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (the alkyl group has 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group), N,N-di and alkyl methacrylamide (the alkyl group having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamide ethyl-N-acetyl methacrylamide, and the like.

(Allyl compound)

Specific examples of the allyl compound include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, acetoacetic acid) Allyl, allyl lactate, etc.), allyloxyethanol, etc. are mentioned.

(Vinyl ethers)

Specific examples of vinyl ethers include alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ether Toxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether , dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and the like.

(Vinyl esters)

Specific examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, and vinyl dichloro. acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, and the like.

(Dialkyl itaconic acid)

As dialkyl itaconic acid, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc. are mentioned.

(etc)

In addition, dialkyl esters or alkyl esters of fumaric acid; dibutyl fumarate; Crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene, styrene macromer (AS-6S manufactured by Toagosei Corporation), methyl methacrylate macromer (AA- manufactured by Toagosei Corporation) 6) and the like.

In the present invention, the content in the case of having other repeating units is preferably 1 to 50 mass%, more preferably 1 to 30 mass%, based on the total mass of all repeating units of the copolymer of the present invention, It is more preferable that it is 1-20 mass %.

10000-30000 are preferable, as for the weight average molecular weight (Mw) of the copolymer of this invention, it is preferable that it is 12000-100000, It is more preferable that it is 15000-50000.

Moreover, 3000-100000 are preferable, as for the number average molecular weight (Mn) of the copolymer of this invention, 5000-50000 are more preferable, 7000-30000 are still more preferable.

In addition, a weight average molecular weight and a number average molecular weight are the values measured on the following conditions by gel permeation chromatography (GPC).

<Measurement conditions>

Solvent: tetrahydrofuran

Flow rate (sample injection volume): 10 μL

Column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation

Column temperature: 40°C

Flow rate: 1.0 mL/min

Detector: polystyrene conversion value by differential refractive index detector (Refractive Index Detector)

Examples of the copolymer of the present invention include those obtained by selecting and combining each repeating unit exemplified as the above-described fluorine part and halogen part, and optional polymerizable part, aromatic ring part, and other parts. .

It is preferable that it is 0.01-0.20 mass part with respect to 100 mass parts of polymeric liquid crystal compounds mentioned later, and, as for content of the copolymer of this invention, it is more preferable that it is 0.05-10 mass parts.

[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 it is preferably a liquid crystal compound having two or more polymerizable groups.

As a polymeric group which a polymeric liquid crystal compound has, the thing similar to the polymeric group which can be radical polymerization or cationic polymerization demonstrated in the polymeric part of the above-mentioned copolymer is mentioned, Among these, Formula (P-1) - (P-) 20), the polymeric group represented by any one is mentioned suitably.

Here, in general, the liquid crystal compound can be classified into a rod-shaped type and a disk-shaped type from the shape thereof. There are also low molecular weight and high molecular weight types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (Physical/Phase Change Dynamics of Polymers, Masao Doi, p. 2, Iwanami Shoten, 1992).

Although any liquid crystal compound may be used in this invention, it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound). Two or more types of rod-shaped liquid crystal compounds, two or more types of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound may be used.

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

In the present invention, it is preferable that the polymerizable liquid crystal compound is a polymerizable liquid crystal compound having reverse wavelength dispersion (hereinafter also abbreviated as "reverse dispersion liquid crystal compound") from the reason that optical compensatory property is improved.

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

As an inverse dispersion liquid crystal compound, the compound represented by following formula (I) is mentioned, for example.

L ¹ -SP ¹ -D ⁵ -(A ¹ ) _a1 -D ³ -(G ¹ ) _g1 -D ¹ -[Ar-D ² ] _q1 -(G ² ) _g2 -D ⁴ -(A ² ) _a2 - D ⁶ -SP ² -L ² … (I)

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

Moreover, in said Formula (I), q1 represents 1 or 2.

In the formula (I), D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are each independently a single bond or -CO-, -O-, -S-, - C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group composed of a combination of two or more thereof, R ¹ to R ⁵ are each Independently, a hydrogen atom, a fluorine atom, or a C1-C12 alkyl group is represented. However, when q1 is ² , some D2 may be same or different, respectively.

Moreover, in said Formula ( ^I ), G1 and G2 are each independently a C6 ^- C20 aromatic ring which may have a substituent, or a C5-C20 divalent alicyclic carbonization which may have a substituent. It represents a hydrogen group and at least one of -CH ₂ - constituting the alicyclic hydrocarbon group may be substituted with -O-, -S-, or -NH-.

Moreover, in said Formula ( ^I ), A1 and A2 are each independently a C6 ^- C20 aromatic ring which may have a substituent, or a C5-C20 divalent alicyclic carbonization which may have a substituent. It represents a hydrogen group and at least one of -CH ₂ - constituting the alicyclic hydrocarbon group may be substituted with -O-, -S-, or -NH-.

Moreover, in said formula (I), SP ¹ and SP ² are each independently a single bond, a C1-C12 linear or branched alkylene group, or a C1-C12 linear or branched alkylene. One or more of -CH ₂ - constituting the group represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent .

Moreover, in said Formula (I), L< ¹ > and L< ² > respectively independently represent a monovalent organic group, and at least one ^of L< ¹ > and L2 represents a polymeric group. However, in the case where Ar is an aromatic ring represented by the following formula (Ar-3), at least one of L ¹ and L ² and L ³ and L ⁴ in the following formula (Ar-3) represents a polymerizable group.

In said formula (I), it is preferable that all of a1, a2, g1, and g2 are 1 from the reason that the polymeric liquid crystal composition of this invention becomes easy to show the liquid crystal state of a smectic phase.

Moreover, since the contrast of the image display apparatus which has an optically anisotropic layer becomes favorable, it is preferable that both a1 and a2 are 0, and that both g1 and g2 are 1.

In said formula (I), it is preferable that q1 is 1.

In the formula (I), as a divalent linking group represented by one aspect of D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ , for example, -CO-, -O-, -CO-O -, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ¹ R ² -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ¹ R ² -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ¹ R ² -, -CR ¹ R ² -CO-O -CR ¹ R ² -, -NR ⁵ -CR ¹ R ² -, and -CO-NR ⁵ -, and the like. R ¹ , R ² and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms.

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

In said formula (I), as a C6-C20 aromatic ring which ^one aspect ^of G1 and G2 represents, For example, Aromatic hydrocarbon rings, such as a benzene ring, a naphthalene ring, anthracene ring, a phenanthroline ring; Aromatic heterocycles, such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring, are mentioned. Among them, a benzene ring (for example, a 1,4-phenyl group, etc.) is preferable.

In the formula (I), the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms in one aspect of G ¹ and G ² is preferably a 5-membered ring or a 6-membered ring. Moreover, although saturated or unsaturated may be sufficient as an alicyclic hydrocarbon group, a saturated alicyclic hydrocarbon group is preferable. As the divalent alicyclic hydrocarbon group represented by G ¹ and G ² , for example, reference can be made to the description of the paragraph [0078] of JP 2012-21068 A, the content of which is incorporated herein by reference.

In this invention, since the contrast of the image display apparatus which has an optically anisotropic layer becomes favorable, it is preferable that G< ¹ > and G< ² > in said Formula (I) are a cycloalkane ring.

Specific examples of the cycloalkane ring include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecaine ring, and a cyclodocosein ring.

Of these, a cyclohexane ring is preferable, a 1,4-cyclohexylene group is more preferable, and a trans-1,4-cyclohexylene group is still more preferable.

Moreover, as a substituent which the C6-C20 aromatic ring or a C5-C20 ^divalent alicyclic hydrocarbon group may have with respect to G1 and G2 in said formula ( ^I ), for example, an alkyl group, an alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, alkylamino group, dialkylamino group, alkylamide group, alkenyl group, alkynyl group, halogen atom, cyano group, nitro group, alkylthiol group, and , N-alkyl carbamate group and the like, and among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.

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

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

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

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

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

Examples of the aromatic ring having 6 to 20 or more carbon atoms in one aspect of A ¹ and A ² in the formula (I) include the same ones as those described for G ¹ and G ² in the formula (I).

In the formula (I), the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of A ¹ and A ² is the same as those described for G ¹ and G ² in the formula (I). can be heard

Moreover, as ^a substituent which the C6-C20 aromatic ring or a C5 ^- C20 ^divalent alicyclic hydrocarbon group may have with respect to A1 and A2, even if G1 and G2 in said Formula ( ^I ) have it, The same thing as the substituent used is mentioned.

In said formula (I), as a C1-C12 linear or branched alkylene group which one aspect of SP ¹ and SP ² represents, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, A hexylene group, a methylhexylene group, a heptylene group, etc. are mentioned suitably. In addition, SP ¹ and SP ² are, as described above, at least one of -CH ₂ - constituting a linear or branched alkylene group having 1 to 12 carbon atoms -O-, -S-, -NH-, - It may be a divalent linking group substituted with N(Q)- or -CO-, and examples of the substituent represented by Q include the same substituents as the substituents G ¹ and G ² in the formula (I) may have.

Examples of the monovalent organic group represented by L ¹ and L ² in the formula (I) include an alkyl group, an aryl group, and a heteroaryl group. Although linear, branched, or cyclic|annular form may be sufficient as an alkyl group, linear is preferable. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are still more preferable. Moreover, although monocyclic or polycyclic may be sufficient as an aryl group, monocyclic is preferable. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable. Moreover, the heteroaryl group may be monocyclic or polycyclic may be sufficient as it. The number of hetero atoms constituting the heteroaryl group is preferably 1-3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. 6-18 are preferable and, as for carbon number of a heteroaryl group, 6-12 are more preferable. Moreover, unsubstituted may be sufficient as an alkyl group, an aryl group, and a heteroaryl group may have a substituent. As a substituent, the thing similar to ^the substituent which G1 and G2 in said Formula ( ^I ) may have is mentioned.

Examples of the polymerizable group represented by at least one of L ¹ and L ² in the formula (I) include the same polymerizable group as capable of radical polymerization or cationic polymerization described in the polymerizable part of the above-mentioned copolymer, and among these, A polymerizable group represented by any one of formulas (P-1) to (P-20) is preferably exemplified.

In the above formula (I), since the durability of the optically anisotropic layer becomes good, it is preferable that both L ¹ and L ² in the above formula (I) are polymerizable groups, and are an acryloyloxy group or a methacryloyloxy group more preferably.

In addition, in said formula (I), Ar represents any one aromatic ring selected from the group which consists of groups represented by following formula (Ar-1) - (Ar-7). However, when q1 is 2, some Ar may be same or different, respectively. In addition, in the following formulas (Ar-1) to (Ar-7), * represents a bonding position with D ¹ or D ² in the formula (I).

[Formula 19]

In the formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N(R ⁶ )-, and R ⁶ is a hydrogen atom or represents a C1-C6 alkyl group, Y< ¹ > is a C6-C12 aromatic hydrocarbon group which may have a substituent, a C3-C12 aromatic heterocyclic group which may have a substituent, or carbon number which may have a substituent A 6-20 alicyclic hydrocarbon group is represented, and at least one of -CH ₂ - constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-.

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

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

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

As a C6-C20 alicyclic hydrocarbon group which Y< ¹ > represents, a cyclohexylene group, a cyclopentylene group, a norbornylene group, an adamantylene group, etc. are mentioned, for example.

Moreover, as a substituent which Y< ¹ > may have, the thing similar to the substituent which G< ¹ > and G< ² > in said Formula (I) may have is mentioned.

Further, in the formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. of monovalent alicyclic hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, -OR ⁷ , -NR ⁸ R ⁹ , or -SR ¹⁰ , -COOR ¹¹ , or -COOR ¹² , R ⁷ to R ¹² , each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z ¹ and Z ² may combine with each other to form an aromatic ring.

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

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

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

Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include 4-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. can be heard

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

On the other hand, specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁷ to R ¹⁰ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group etc. are mentioned.

As described above, Z ¹ and Z ² may be bonded to each other to form an aromatic ring, for example, when Z ¹ and Z ² in the formula (Ar-1) are bonded to each other to form an aromatic ring As a structure, group represented by a following formula (Ar-1a) is mentioned, for example. In addition, in the following formula (Ar-1a), * represents a bonding position with D ¹ or D ² in the formula (I).

[Formula 20]

Here, in the formula (Ar-1a), Q ¹ , Q ² , and Y ¹ are the same as those described in the formula (Ar-1).

In addition, in the formulas (Ar-2) and (Ar-3), A ³ and A ⁴ are each independently -O-, -N(R ¹³ )-, -S-, and -CO- A group selected from the group consisting of is represented, and R ¹³ represents a hydrogen atom or a substituent.

Examples of the substituent represented by R ¹³ include the same substituents as the substituents G ¹ and G ² in the formula (I) may have.

In addition, in the formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.

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

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

In addition, in the formula (Ar-3), D ⁷ and D ⁸ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, R ¹ to R ⁵ are each independently a hydrogen atom, a fluorine atom, or , an alkyl group having 1 to 12 carbon atoms.

Here, as a ^divalent coupling group, the thing similar to what ^was demonstrated ^for D1, D2, D3, ^D4 , ^D5 , and D6 ⁱⁿ said Formula (I) is mentioned.

In the formula (Ar-3), SP ³ and SP ⁴ are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched chain having 1 to 12 carbon atoms. At least one of -CH ₂ - constituting the alkylene group represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, Q is a substituent indicates As a substituent, the thing similar to ^the substituent which G1 and G2 in said Formula ( ^I ) may have is mentioned.

Here, as an alkylene group, the thing similar to what was demonstrated in ^SP1 and SP2 in said Formula ( ^I ) is mentioned.

In addition, in the formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in the formula (I) is a polymerizable group indicates

Examples of the monovalent organic group include the same as those described for L ¹ and L ² in the formula (I).

Moreover, as a polymeric group, the thing similar to the polymeric group which can be radical polymerization or cationic polymerization demonstrated in the polymeric part of the above-mentioned copolymer is mentioned, Among them, any of the above-mentioned formulas (P-1) - (P-20) A polymeric group which appears as one is mentioned suitably.

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

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

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

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

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

In addition, specific examples of the alkyl group having 1 to 20 carbon atoms represented by Q ³ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. A tyl group, n-pentyl group, and n-hexyl group are mentioned, As a substituent, the thing similar to the substituent which G< ¹ > and G< ² > in said Formula (I) may have is mentioned.

As a compound represented by said Formula (I), For example, the compound represented by General formula (1) described in Unexamined-Japanese-Patent No. 2010-084032 (particularly, the compound described in paragraph number [0067] - [0073]), Japan A compound represented by the general formula (II) described in Japanese Patent Application Laid-Open No. 2016-053709 (particularly, the compounds described in paragraphs [0036] to [0043]), and the general formula (1) described in Japanese Patent Application Laid-Open No. 2016-081035 The compound represented by (particularly, the compound described in paragraph number [0043] - [0055]) etc. are mentioned.

Moreover, as a compound represented by said Formula (I), the compound represented by following formula (1)-(22) is mentioned suitably, Specifically, K (side chain structure) in following formula (1)-(22) As such, compounds each having a side chain structure shown in Tables 1 to 3 below are exemplified.

In addition, in Tables 1-3 below, "*" shown in the side chain structure of K represents the bonding position with an aromatic ring.

In addition, in the side chain structure shown by 2-2 in Table 2 and 3-2 in Table 3 below, the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively, are propylene groups (groups in which a methyl group is substituted with an ethylene group) and represents a mixture of positional isomers having different positions of methyl groups.

[Formula 21]

[Table 1]

[Table 2]

[Table 3]

[Polymerization Initiator]

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

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

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

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

〔menstruum〕

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

Specific examples of the solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetra hydrofuran, etc.), aliphatic hydrocarbons (eg hexane, etc.), alicyclic hydrocarbons (eg cyclohexane etc.), aromatic hydrocarbons (eg toluene, xylene, tri methylbenzene, etc.), halogenated carbons (eg dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (eg methyl acetate, ethyl acetate, butyl acetate, etc.) , water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxide Sides (for example, dimethyl sulfoxide, etc.), amides (for example, dimethylformamide, dimethylacetamide, etc.) etc. are mentioned, These may be used individually by 1 type, or 2 or more types may be used together.

[Orientation controlling agent]

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

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

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

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

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

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

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

In addition, the pitch of the cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.

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

[Other ingredients]

The polymerizable liquid crystal composition of the present invention may contain components other than those described above, and examples thereof include surfactants, tilt angle control agents, orientation aids, plasticizers, and crosslinking agents.

[Optical Anisotropic Layer]

The optically anisotropic layer of this invention is hardened|cured material obtained by superposing|polymerizing the polymeric liquid crystal composition of this invention mentioned above. In addition, hardened|cured material can be formed on the arbitrary support body in the optical film of this invention mentioned later, or on the polarizer in the polarizing plate of this invention mentioned later.

As a formation method of hardened|cured material, after setting it as a desired orientation state using the polymeric liquid crystal composition of this invention mentioned above, the method of fixing by superposition|polymerization, etc. are mentioned, for example.

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

It is preferable that the optically anisotropic layer of this invention is an optically anisotropic layer which satisfy|fills following formula (III).

0.50<Re(450)/Re(550)<1.00 … (III)

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

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

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

Slow axis direction (°)

Re(λ)=R0(λ)

Rth(λ)=((nx+ny)/2-nz)×d

is calculated

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

Moreover, it is preferable that it is a positive A plate or a positive C plate, and, as for such an optically anisotropic layer, it is more preferable that it is a positive A plate.

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

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

Formula (A1) nx>ny≒nz

Formula (C1) nz>nx≒ny

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

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

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

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

[optical film]

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

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

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

The optical film 10 shown in FIG. 1 has the support body 16, the orientation film 14, and the optically anisotropic layer 12 as hardened|cured material in this order.

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

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

[Optical Anisotropic Layer]

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

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

[Support]

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

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

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

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

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

[Orientation film]

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

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

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

Regarding the alignment film usable in the present invention, for example, the alignment film described in International Publication No. 01/88574, page 43, line 24 to page 49, line 8; Modified polyvinyl alcohol described in paragraphs [0071] to [0095] of Japanese Patent Publication No. 3907735; A liquid crystal aligning film formed by the liquid crystal aligning agent of Unexamined-Japanese-Patent No. 2012-155308; and the like.

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

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

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

[hard coat layer]

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

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

[Ultraviolet absorber]

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

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

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

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

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

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

[Polarizer]

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

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

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

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

[Polarizer]

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

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

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

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

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

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

[Adhesive layer]

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

As an adhesive layer used for lamination|stacking of a hardened|cured material and a polarizer, the ratio (tanδ=G"/G') of storage elastic modulus G' and loss elastic modulus G" measured with a dynamic viscoelasticity measuring apparatus (tanδ=G"/G') is, for example, 0.001 to 1.5 Substances are shown, and so-called adhesives and substances which are easy to creep are included. As an adhesive which can be used for this invention, although polyvinyl alcohol-type adhesive is mentioned, for example, it is not limited to this.

[Image display device]

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

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

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

[Liquid crystal display device]

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

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

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

<Liquid crystal cell>

The liquid crystal cell used in the liquid crystal display device is preferably a VA (Virtual Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but limited to these it is not going to be

In the liquid crystal cell of the TN mode, rod-shaped liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are again twisted at 60 to 120*. The liquid crystal cell of TN mode is most used as a color TFT liquid crystal display device, and there exists description in many documents.

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

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

[Organic EL display device]

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

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

Example

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

[Synthesis Examples 1-4]

In a flask equipped with a cooling tube, a thermometer, and a stirrer, 7.5 parts by mass of cyclohexanone was put as a solvent, and nitrogen was flowed into the flask at 50 mL/min while heating to 80° C. by water bath heating.

Here, the compounding amount (part by mass) shown in Table 4 below of the monomers 1 to 3 shown in Table 4, 0.25 parts by mass of 2,2'-azobis(isobutyronitrile) as a polymerization initiator, and cyclo as a solvent The solution mixed with 22.5 mass parts of hexanone was dripped over 3 hours, and it stirred in the state which maintained the heating state for 30 minutes.

Then, after adding 0.1 mass part of 2,2'- azobis (isobutyronitrile), the temperature was raised to 90 degreeC, and heating was continued for 3 hours.

It stood to cool to room temperature after completion|finish of reaction, and the polymer solution containing about 50 mass % of copolymers P-1 to P-4 represented by the following formula was obtained. In addition, in the following formula, the numerical value described in each repeating unit of a copolymer shows content (mass %) of each repeating unit with respect to all repeating units.

[Table 4]

copolymer P-1

[Formula 22]

copolymer P-2

[Formula 23]

copolymer P-3

[Formula 24]

copolymer P-4

[Formula 25]

[Synthesis Example 5]

100 parts by mass of a polymer solution containing copolymer P-1 synthesized in Synthesis Example 1 in a flask equipped with a cooling tube, a thermometer, and a stirrer, 0.025 parts by mass of p-methoxyphenol, and 1 part by mass of triethylamine In addition, it heated at 60 degreeC by water bath heating for 4 hours.

After heating, it is allowed to cool to room temperature, 150 parts by mass of ethyl acetate is added, and liquid separation washing is performed in the order of 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and water, and the obtained organic layer is dried over anhydrous magnesium sulfate, and the air expressed by the following formula A polymer solution containing about 20% by mass of coalescing P-5 was obtained. In addition, content of the halogen part computed by combustion ion chromatography was 1 mass %.

copolymer P-5

[Formula 26]

[Synthesis Examples 6 to 8]

Instead of using the polymer solution containing the copolymer P-1 synthesized in Synthesis Example 1, each polymer solution containing the copolymer P-2 to the copolymer P-4 synthesized in Synthesis Examples 2 to 4 was used. , The polymer solution containing about 20 mass % of copolymer P-6 - copolymer P-8 respectively represented by a following formula by the method similar to Synthesis Example 5 was obtained.

copolymer P-6

[Formula 27]

copolymer P-7

[Formula 28]

copolymer P-8

[Formula 29]

[Synthesis Example 9]

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 butyl acrylate, and the blending amount of each monomer was changed, the copolymer P-9 represented by the following formula was reduced to about 20 A polymer solution containing mass % was obtained.

copolymer P-9

[Formula 30]

[Synthesis Example 10]

Copolymer FA-1 represented by the following formula was synthesize|combined.

In the following formula, a to c are a:b:c=40:54:6, and represent the content (mass %) of each repeating unit with respect to all repeating units.

In addition, when the content of each repeating unit is expressed as "mol%" in the following formula, a:b:c=60:30:10 as in Patent Document 1 (International Publication No. 2019/009255).

Copolymer FA-1

[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.

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

polymerizable liquid crystal composition

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

・The following polymerizable liquid crystal compound L-3 42.00 parts by mass

・The following polymerizable liquid crystal compound L-4 42.00 parts by mass

・The following polymerizable liquid crystal compound A-1 16.00 parts by mass

· The following polymerization initiator S-1 (oxime esters) 0.50 parts by mass

· Copolymers in Table 5 below 0.15 parts by mass

・Hisolv MTEM (manufactured by Toho Chemical High School) 2.00 parts by mass

・NK Ester A-200 (made by Shin-Nakamura Chemical High School) 1.00 parts by mass

・Methyl ethyl ketone 424.8 parts by mass

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

In addition, the group adjacent to the acryloyloxy group of the following polymerizable liquid crystal compounds L-3 and L-4 represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and the following polymerizable liquid crystal compounds L-3 and L-4 represents a mixture of positional isomers having different positions of methyl groups.

Polymerizable Liquid Crystal Compound L-3

[Formula 32]

Polymerizable liquid crystal compound L-4

[Formula 33]

Polymerizable liquid crystal compound A-1

[Formula 34]

polymerization initiator S-1

[Formula 35]

[Preparation of a composition for forming a photo-alignment film]

The photo-alignment film forming material described in Example 1 of WO2016/002722 was prepared, and this was used for manufacture of the liquid crystal film of this invention.

[Production of Cellulose Acylate Film 1]

<Preparation of core layer cellulose acylate dope>

The following composition was thrown into the mixing tank, stirred, each component was melt|dissolved, and the cellulose acetate solution used as core layer cellulose acylate dope was prepared.

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

Core layer cellulose acylate dope

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

Cellulose acetate with acetyl substitution degree of 2.88 100 parts by mass

・In the example of Japanese Patent Application Laid-Open No. 2015-227955

Described polyester compound B 12 parts by mass

The following compound G 2 parts by mass

Methylene chloride (first solvent) 430 parts by mass

・Methanol (2nd solvent) 64 parts by mass

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

compound G

[Formula 36]

<Preparation of outer layer cellulose acylate dope>

10 mass parts of the following mat agent solutions were added to 90 mass parts of said core layer cellulose acylate dope, and the cellulose acetate solution used as outer layer cellulose acylate dope was prepared.

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

mat solution

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

· Silica particles with an average particle size of 20 nm

(AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass

Methylene chloride (first solvent) 76 parts by mass

・Methanol (2nd solvent) 11 parts by mass

The above-mentioned core layer cellulose acylate dope 1 part by mass

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

<Production of Cellulose Acylate Film 1>

After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope with filter paper having an average pore diameter of 34 μm and a sintered metal filter having an average pore diameter of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate on both sides thereof Dope was cast|flow_spreaded on the drum of 20 degreeC from the casting tool at the same time as 3 layers (band casting machine). In the state of the solvent content of the film on the drum of about 20% by mass, the film was peeled from the drum, both ends of the obtained film in the width direction were fixed with tenter clips, and the film was dried while stretching in the transverse direction at a stretching ratio of 1.1 times. Then, the obtained film was further dried by conveying between the rolls of a heat processing apparatus, the 40-micrometer-thick optical film was produced, and this was made into 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, respectively. The in-plane retardation in wavelength 550nm of the obtained cellulose acylate film 1 was 0 nm.

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

[Production of optical film]

The composition for photo-alignment film formation prepared previously was apply|coated to the surface of one side of the produced cellulose acylate film 1 with a bar coater.

After applying the composition for photo-alignment film formation, the obtained film was dried on a hot plate at 120°C for 1 minute to remove the solvent to form a 0.3 µm-thick composition layer for photo-alignment film formation.

The photo-alignment layer was formed by irradiating the obtained composition layer for photo-alignment film formation with polarization|polarized-light ultraviolet-ray (10 mJ/cm< ² >, using an ultra-high pressure mercury lamp).

Next, on the photo-alignment layer, the polymerizable liquid crystal compositions of Examples 1 to 9 and Comparative Example 1 prepared previously were respectively applied with a bar coater to form a polymerizable liquid crystal composition layer.

The formed polymerizable liquid crystal composition layer was once heated to 110°C on a hot plate, and then cooled to 60°C to stabilize the orientation.

After that, the orientation is fixed by UV irradiation (500 mJ/cm ² , using an ultra-high pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration of 100 ppm), maintained at 60 ° C., and an optically anisotropic layer with a thickness of 2.3 μm is formed, made the film. The in-plane retardation in wavelength 550nm of the obtained optical film was 140 nm.

[Example 10]

Except having changed the polymerizable liquid crystal composition to what is shown below, it carried out similarly to Examples 1-9 and the comparative example 1, and produced the optical film.

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

polymerizable liquid crystal composition

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

・The following polymerizable liquid crystal compound L-1 62.00 parts by mass

・The following polymerizable liquid crystal compound L-2 22.00 parts by mass

- The said polymerizable liquid crystal compound A-1 16.00 parts by mass

The polymerization initiator S-1 (oxime esters) 0.50 parts by mass

・The copolymer P-5 0.15 parts by mass

・Hisolv MTEM (manufactured by Toho Chemical High School) 2.00 parts by mass

・NK Ester A-200 (made by Shin-Nakamura Chemical High School) 1.00 parts by mass

・Methyl ethyl ketone 424.8 parts by mass

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

Polymerizable liquid crystal compound L-1

[Formula 37]

Polymerizable liquid crystal compound L-2

[Formula 38]

[Evaluation of storage stability]

[Preparation of polymerizable liquid crystal composition with aging]

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

Next, by heating the obtained polymerizable liquid-crystal composition at 60 degreeC for 7 days, the polymeric liquid-crystal composition with time-lapsed heating was prepared.

〔evaluation〕

In place of the polymerizable liquid crystal composition of Examples 1 to 10 and Comparative Example 1, an optical film was produced in the same manner as above, except that a heat-aged polymerizable liquid crystal composition was used, and the in-plane retardation at a wavelength of 550 nm was measured. did.

The measured in-plane retardation and the in-plane retardation of the optical films produced using the polymerizable liquid crystal compositions of Examples 1 to 10 and Comparative Example 1 that are not aging with heating (hereinafter, abbreviated as "reference value" in this paragraph). ) was calculated and evaluated on the basis of the following criteria.

<Standard>

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

B: The ratio of the measured 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 the reference value is 5% or more

[Evaluation of orientation]

About the produced optical film, it observed in the state shifted|deviated by 2 degrees from the extinction position using the polarizing microscope. When observed, the state in which the partial light-dark difference does not exist was evaluated as being orientating the liquid crystal director uniformly (it is excellent in orientation).

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

AAA: The liquid crystal director is finely arranged and aligned, so the display performance is very good

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

A: There is no disorder of the liquid crystal director, and the surface shape is stable

B: Disorder of the liquid crystal director is very slight, and the surface shape is stable

C: Disorder of the liquid crystal director is partial, and the surface shape is stable

D: The liquid crystal director is greatly disturbed, the surface shape is not stable, and the display performance is very poor.

[Production of antireflection plate (circularly polarizing plate) for organic EL]

<Production of positive C plate film 1>

As the branch support, a commercially available triacetyl cellulose film "Z-TAC" (manufactured by Fujifilm) was used. Hereinafter, this is abbreviated as cellulose acylate film 2.

Cellulose acylate film 2 was passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature was raised to 40 ° C. m ² , heated to 110° C., and conveyed for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. Then, with respect to the obtained film, 3 ml/m< ² > of pure water was apply|coated similarly using the bar coater. Subsequently, after repeating water washing with a fountain coater and dehydration with an air knife 3 times, the obtained film was conveyed to a 70 degreeC drying zone for 10 seconds and dried, and the alkali saponification process cellulose acylate film 2 was produced.

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

alkaline solution

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

・Potassium hydroxide 4.7 parts by mass

·water 15.8 parts by mass

·Isopropanol 63.7 parts by mass

・Surfactant SF-1

(C ₁₄ H ₂₉ O(CH ₂ CH ₂ O) ₂₀ H) 1.0 parts by mass

·Propylene glycol 14.8 parts by mass

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

To the cellulose acylate film 2 subjected to the alkali saponification treatment, a coating liquid for forming an alignment film having the following composition was continuously applied to a #8 wire bar. The applied coating liquid for forming an alignment film was dried with warm air at 60° C. for 60 seconds and further with warm air at 100° C. for 120 seconds to form an alignment film.

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

Composition of coating liquid for forming alignment film

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

・Polyvinyl alcohol (Kurare, PVA103) 2.4 parts by mass

・Isopropyl alcohol 1.6 parts by mass

・Methanol 36 parts by mass

·water 60 parts by mass

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

On the cellulose acylate film 2 which has the orientation film formed above, the following coating liquid N for optically anisotropic films was apply|coated. After aging the applied coating liquid N for an optically anisotropic film at 60° C. for 60 seconds, an air-cooled metal halide lamp of 70 mW/cm ² under air (manufactured by Eye Graphics Co., Ltd.) was used to irradiate an ultraviolet ray of 1000 mJ/cm ² . . Thereby, the state in which the rod-shaped polymerizable liquid crystal compound was vertically aligned was fixed, and the positive C plate film 1 was produced. The positive C plate film 1 had a retardation of -60 nm in the thickness direction at a wavelength of 550 nm.

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

Composition of coating liquid N for optically anisotropic film

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

The following polymerizable liquid crystal compound L-1 80 parts by mass

The following polymerizable liquid crystal compound L-2 20 parts by mass

The following vertical alignment agent S01 1 part by mass

The following vertical alignment agent S02 0.5 parts by mass

Ethylene oxide modified trimethylol propane triacrylate

(V#360, made by Osaka Yuki Chemical Co., Ltd.) 8 parts by mass

Irgacure 907 (made by BASF) 3 parts by mass

Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass

compound B03 0.4 parts by mass

methyl ethyl ketone 170 parts by mass

cyclohexanone 30 parts by mass

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

Polymerizable liquid crystal compound L-1

[Formula 39]

Polymerizable liquid crystal compound L-2

[Formula 40]

vertical alignment agent S01

[Formula 41]

vertical alignment agent S02

[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.]

[Formula 43]

<Production of circular polarizer>

Corona treatment was performed on the surface of the optically anisotropic layer of the produced optical film, and also the epoxy-type ultraviolet (UV) adhesive was coated. The positive C plate film 1 prepared above was transferred thereto and the UV adhesive was UV cured, and then the cellulose acylate film 2 was removed. Moreover, the PVA (polyvinyl alcohol) polarizing plate with a protective film was bonded together through the pressure-sensitive adhesive to the cellulose acylate film 1 side of the optical laminated body, and the circularly-polarizing plate was obtained.

[Evaluation of adhesion]

Between the optical laminate of the produced circularly polarizing plate and the positive C plate film 1, a part (uncoated part) to which UV adhesive is not applied is made, and this uncoated part is used as a grip part, 180° peeling according to JIS6854-2 The force was measured (unit: N/25mm).

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

<Standard>

A: Peel force is 1.6N/25mm or more

B: Peel force is less than 1.6N/25mm

[Table 5]

From the results shown in Table 5, it was found that when the copolymer blended with both the polymerizable liquid crystal compound did not have the repeating unit (halogen part) represented by the formula (2), the storage stability was inferior ( Comparative Example 1).

On the other hand, when the copolymer mix|blended with both a polymeric liquid crystal compound had the repeating unit (halogen part) represented by said Formula (2), it turned out that storage stability becomes favorable (Examples 1-10).

In particular, when Examples 1-4 and Examples 5-8 were compared, when the copolymer had the repeating unit (polymerizable part) represented by the said Formula (3), it turned out that adhesiveness with an upper layer becomes favorable. .

Moreover, when Examples 1-4 and Example 9 were contrasted, when a copolymer had the repeating unit (aromatic ring part) represented by said Formula (4), it turned out that the orientation with an upper layer becomes favorable.

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

Claims (9)

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).
[Formula 1]

Here, in the above formulas (1) and (2),
R ¹ and R ² each represent a hydrogen atom or a methyl group.
L ¹ and L ² represent a divalent linking group.
A ¹ represents group represented by the following formula (1-1), and A ² represents a group represented by the following formula (2-1) or (2-2).
[Formula 2]

Here, in the above formula (1-1),
* represents a bonding position with L ¹ .
n represents the integer of 1-6.
X represents a hydrogen atom or a fluorine atom.
[Formula 3]

Here, in the above formulas (2-1) and (2-2),
* represents a bonding position with L ² .
Y represents -O-, -NH-, or -NR ^Y -, and R ^Y represents a substituent.
X represents a halogen atom. The method according to claim 1,
The polymerizable liquid crystal composition wherein the copolymer is a copolymer further having a repeating unit represented by the following formula (3).
[Formula 4]

Here, in the above formula (3),
R ³ represents a hydrogen atom or a methyl group.
L ³ represents a divalent linking group.
A ³ represents a polymerizable group. The method according to claim 1 or 2,
The polymerizable liquid crystal composition wherein the copolymer is a copolymer further having a repeating unit represented by the following formula (4).
[Formula 5]

Here, in the above formula (4),
R ⁴ represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent linking group.
A ⁴ represents the aromatic ring group which may have a substituent. 4. The method according to any one of claims 1 to 3,
Polymeric liquid crystal composition whose content of the repeating unit represented by said Formula (2) is 0.001-60 mass % with respect to the total mass of all the repeating units of the said copolymer. 5. The method according to any one of claims 1 to 4,
The polymerizable liquid crystal composition, wherein the content of the copolymer is 0.01 to 0.20 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. An optically anisotropic layer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 5. An optical film having the optically anisotropic layer according to claim 6. The polarizing plate which has the optical film of Claim 7, and a polarizer. The image display device which has the optical film of Claim 7, or the polarizing plate of Claim 8.

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