CN118043707A

CN118043707A - Light absorbing anisotropic layer, optical film, viewing angle control system, and image display device

Info

Publication number: CN118043707A
Application number: CN202280066252.7A
Authority: CN
Inventors: 志贺溪伍; 西村直弥
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-09-29
Filing date: 2022-09-15
Publication date: 2024-05-14
Also published as: WO2023053995A1

Abstract

The invention provides a light absorption anisotropic layer with excellent plane uniformity and high contrast, and an optical film, a viewing angle control system and an image display device using the light absorption anisotropic layer. The light-absorbing anisotropic layer is formed from a liquid crystal composition containing a liquid crystalline compound, a dichroic material, and a surfactant, wherein the surfactant is a copolymer having a repeating unit A containing a fluorine atom and not containing a polymerizable group and a repeating unit B containing no fluorine atom and not containing a polymerizable group and satisfying a predetermined condition 1 or 2, and the angle [ theta ] between the central axis of transmittance of the light-absorbing anisotropic layer and the normal direction of the surface of the light-absorbing anisotropic layer is 0 DEG to 45 deg.

Description

Light absorbing anisotropic layer, optical film, viewing angle control system, and image display device

Technical Field

The invention relates to a light absorbing anisotropic layer, an optical film, a viewing angle control system and an image display device.

Background

When a vehicle-mounted display such as a car navigator is used, there is a problem in that light emitted upward from a display screen is reflected on a windshield or the like, and thus driving is hindered.

To solve such a problem, for example, patent document 1 describes the following: a viewing angle control system comprising a1 st polarizer and a 2 nd polarizer in a film form having a fixed orientation and containing an absorbing dichroic material, wherein the 1 st polarizer has an absorption axis in the film plane, and the 2 nd polarizer orients a dichroic compound in a liquid crystal polymer matrix and fixes the orientation thereof, and the absorption axis forms an angle of 0 DEG to 45 DEG with the normal line of the film plane. "([ claim 1 ]).

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent No. 4902516

Disclosure of Invention

Technical problem to be solved by the invention

The present inventors have studied the viewing angle (angle of view) control system described in patent document 1, and as a result, have found that when a liquid crystal composition containing a liquid crystal compound, a dichroic material, and a surfactant is used for forming the 2 nd polarizer (light absorbing anisotropic film), a uniform plane shape cannot be obtained, and that the difference between the transmittance from the front side direction of the light absorbing anisotropic layer and the transmittance from the oblique direction (hereinafter, simply referred to as "contrast") is poor.

Accordingly, an object of the present invention is to provide a light absorbing anisotropic layer having excellent planar uniformity and high contrast, and an optical film, a viewing angle control system, and an image display device using the light absorbing anisotropic layer.

Means for solving the technical problems

The present inventors have made intensive studies to achieve the above-mentioned problems, and as a result, have found that an optically anisotropic layer formed from a liquid crystal composition containing a liquid crystalline compound, a dichroic substance and a surfactant can be formed into a light absorbing anisotropic layer excellent in planar uniformity and high in contrast by using a copolymer having repeating units a and B satisfying predetermined conditions as a surfactant, and have completed the present invention.

That is, the present inventors have found that the above problems can be solved by the following configuration.

[1] A light absorbing anisotropic layer formed of a liquid crystal composition containing a liquid crystalline compound, a dichroic substance and a surfactant, wherein,

The surfactant is a copolymer having a repeating unit A containing a fluorine atom and not containing a polymerizable group and a repeating unit B containing no fluorine atom and a polymerizable group and satisfying the following condition 1 or 2,

The angle θ between the central axis of transmittance of the light-absorbing anisotropic layer and the normal direction of the surface of the light-absorbing anisotropic layer is 0 DEG to 45 deg.

Condition 1: the repeating unit A is represented by the following formula (A-1) and the repeating unit B has a polar group at the terminal of the side chain.

Condition 2: the repeating unit B is represented by the following formula (B-1) or (B-2).

[2] The light absorbing anisotropic layer according to [1], wherein,

The surfactant satisfies the condition 2, and the repeating unit B is a repeating unit represented by the formula (B-2).

[3] The light absorbing anisotropic layer according to [1] or [2], wherein,

The content of the repeating unit B is 5 to 50% by mass relative to the total mass of the surfactant.

[4] The light absorbing anisotropic layer according to any of [1] to [3], wherein,

The surfactant has a repeating unit C containing a polymerizable group.

[5] The light absorbing anisotropic layer according to any of [1] to [4], wherein,

The content of the surfactant is 0.001 to 5% by mass based on the total solid content mass of the liquid crystal composition.

[6] The light absorbing anisotropic layer according to any of [1] to [5], wherein,

The dichroic compound is contained in an amount of 5 to 30 mass% relative to the mass of the total solid component of the liquid crystal composition.

[7] The light absorbing anisotropic layer according to any one of [1] to [6], which exhibits a nematic liquid crystal phase.

[8] An optical film having a transparent film substrate and the light absorbing anisotropic layer of any one of [1] to [7] disposed on the transparent film substrate.

[9] The optical film according to [8], which has an orientation film between the transparent film base material and the light absorbing anisotropic layer.

[10] A viewing angle control system having a polarizer having an absorption axis in an in-plane direction and the light absorbing anisotropic layer of any one of [1] to [7] or the optical film of [8] or [9 ].

[11] An image display apparatus having a display element and the viewing angle control system of [10],

The viewing angle control system is disposed on at least one major surface of the display element.

[12] The image display device according to [11], wherein,

The light absorption anisotropic layer of the viewing angle control system is disposed on the viewing side of the polarizer of the viewing angle control system.

Effects of the invention

According to the present invention, it is possible to provide a light absorbing anisotropic layer excellent in planar uniformity and high in contrast, and an optical film, a viewing angle control system, and an image display device using the light absorbing anisotropic layer.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements is made in accordance with the representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present specification, the numerical range indicated by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the present specification, the term "parallel" and "perpendicular" refer to a range of ±5° parallel to a range of ±5° perpendicular to the axis, and are not strictly parallel to the axis.

In the present specification, the liquid crystal composition and the liquid crystal compound are both included as concepts of a substance that no longer exhibits liquid crystallinity by curing or the like.

In the present specification, 1 kind of substance corresponding to each component may be used alone, or 2 or more kinds may be used in combination. Here, when 2 or more kinds of the components are used together, the content of the components refers to the total content of the components used together unless otherwise specified.

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

[ Substituent W ]

The substituent W used in the present specification represents the following group.

As the substituent W, for example, examples thereof include a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C1-20 cycloalkyl group, a C1-10 alkylcarbonyl group, a C1-10 alkoxycarbonyl group, a C1-10 alkylcarbonyloxy group, a C1-10 alkylamino group, an alkylaminocarbonyl group, a C1-20 alkoxy group, a C1-20 alkenyl group, a C1-20 alkynyl group, a C1-20 aryl group, a heterocyclic group (also referred to as a heteroatom-containing group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an aryloxy group, a siloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a heterocyclic oxy group amino (including anilino), ammonio, amido, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamylamino, alkyl or arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclylthio, sulfamoyl, sulfo, alkyl or arylsulfinyl, alkyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heterocyclylazo, imido, phosphino, phosphinyloxy, phosphinylamino, phosphonyl, silyl, hydrazino, ureido, boric acid (-B (OH) ₂), phosphoric acid (-OPO (OH) ₂), sulfuric acid (-OSO ₃ H), other known substituents and the like.

Further, details of substituents are described in paragraph [0023] of Japanese patent application laid-open No. 2007-234651.

The substituent W may be a group represented by the following formula (W1).

[ Chemical formula 1]

*-LW-SPW-Q (W1)

In the formula (W1), LW represents a single bond or a divalent linking group, SPW represents a divalent spacer group, Q represents Q1 or Q2 in the formula (a-1) described later, and x represents a bonding position.

Examples of the divalent linking group represented by LW include an integer .)、-N(Z)-、-C(Z)＝C(Z')-、-C(Z)＝N-、-N＝C(Z)-、-C(Z)₂-C(Z')₂-、-C(O)-、-OC(O)-、-C(O)O-、-O-C(O)O-、-N(Z)C(O)-、-C(O)N(Z)-、-C(Z)＝C(Z')-C(O)O-、-O-C(O)-C(Z)＝C(Z')-、-C(Z)＝N-、-N＝C(Z)-、-C(Z)＝C(Z')-C(O)N(Z")-、-N(Z")-C(O)-C(Z)＝C(Z')-、-C(Z)＝C(Z')-C(O)-S-、-S-C(O)-C(Z)＝C(Z')-、-C(Z)＝N-N＝C(Z')-(Z、Z'、Z" having -O-、-(CH₂)_g-、-(CF₂)_g-、-Si(CH₃)₂-、-(Si(CH₃)₂O)_g-、-(OSi(CH₃)₂)_g-(g of 1 to 10, which independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom. ) -c≡c-, -n=n-, -S (O) -, - (O) S (O) O-, -O (O) S (O) O-, -SC (O) -and-C (O) S-, etc. LW may be a group (hereinafter also simply referred to as "L-C") composed of 2 or more of these groups.

Examples of the divalent spacer group represented by SPW include a linear, branched or cyclic alkylene group having 1 to 50 carbon atoms and a heterocyclic group having 1 to 20 carbon atoms.

The carbon atoms of the alkylene group and the heterocyclic group may be -O-、-Si(CH₃)₂-、-(Si(CH₃)₂O)_g-、-(OSi(CH₃)₂)_g-(g to an integer .)、-N(Z)-、-C(Z)＝C(Z')-、-C(Z)＝N-、-N＝C(Z)-、-C(Z)₂-C(Z')₂-、-C(O)-、-OC(O)-、-C(O)O-、-O-C(O)O-、-N(Z)C(O)-、-C(O)N(Z)-、-C(Z)＝C(Z')-C(O)O-、-O-C(O)-C(Z)＝C(Z')-、-C(Z)＝N-、-N＝C(Z)-、-C(Z)＝C(Z')-C(O)N(Z")-、-N(Z")-C(O)-C(Z)＝C(Z')-、-C(Z)＝C(Z')-C(O)-S-、-S-C(O)-C(Z)＝C(Z')-、-C(Z)＝N-N＝C(Z')-(Z、Z'、Z" of 1 to 10, and independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom. ) -c≡c-, -n=n-, -S-, -C (S) -, -S (O) -, -SO ₂ -, - (O) S (O) O-, -O (O) S (O) O-, -SC (O) -and-C (O) S-, substituted with a group consisting of 2 or more of these groups (hereinafter also referred to simply as "SP-C").

The hydrogen atom of the alkylene group and the hydrogen atom of the heterocyclic group may be substituted with a halogen atom or a cyano group 、-Z^H、-OH、-OZ^H、-COOH、-C(O)Z^H、-C(O)OZ^H、-OC(O)Z^H、-OC(O)OZ^H、-NZ^HZ^H'、-NZ^HC(O)Z^H'、-NZ^HC(O)OZ^H'、-C(O)NZ^HZ^H'、-OC(O)NZ^HZ^H'、-NZ^HC(O)NZ^H'OZ^H"、-SH、-SZ^H、-C(S)Z^H、-C(O)SZ^H、-SC(O)Z^H (hereinafter also referred to simply as "SP-H"). Here, Z ^H、Z^H' represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group, or a-L-CL (L represents a single bond or a divalent linking group): specific examples of the divalent linking group are the same as LW and SPW described above, and CL represents a crosslinkable group, and examples thereof include groups represented by Q1 or Q2 in the formula (A-1) described below, preferably polymerizable groups represented by the formulas (P1) to (P30) described below).

[ Light absorbing Anisotropic layer ]

The light-absorbing anisotropic layer of the present invention is a light-absorbing anisotropic layer formed from a liquid crystal composition containing a liquid crystalline compound, a dichroic material and a surfactant. That is, the light absorbing anisotropic layer is preferably formed by fixing the alignment state of the liquid crystal compound and the dichroic material contained in the liquid crystal composition containing the liquid crystal compound, the dichroic material, and the surfactant.

The surfactant (hereinafter, also simply referred to as "specific surfactant") contained in the liquid crystal composition is a copolymer having a repeating unit a containing a fluorine atom and containing no polymerizable group and a repeating unit B containing no fluorine atom and no polymerizable group, and satisfying the following conditions 1 or 2.

In the light-absorbing anisotropic layer of the present invention, an angle θ (hereinafter, also simply referred to as "transmittance central axis angle θ") between the transmittance central axis of the light-absorbing anisotropic layer and the normal direction of the surface of the light-absorbing anisotropic layer is 0 ° or more and 45 ° or less.

Here, the transmittance central axis means a direction showing the highest transmittance when the transmittance is measured by changing the inclination angle (polar angle) and the inclination direction (azimuth angle) with respect to the normal direction of the surface of the light absorbing anisotropic layer.

Specifically, a Mueller matrix at a wavelength of 550nm was actually measured using AxoScan OPMF-1 (manufactured by Opto Science, inc.). More specifically, in measurement, an azimuth angle at which the central axis of transmittance is inclined is first found, and then, in a plane including the normal direction of the light absorbing anisotropic layer along the azimuth angle (a plane including the central axis of transmittance and orthogonal to the layer surface), the angle with respect to the normal direction of the light absorbing anisotropic layer surface, that is, the polar angle is changed every 1 ° to-70 ° and the muller matrix at a wavelength of 550nm is actually measured, thereby deriving the transmittance of the light absorbing anisotropic layer. As a result, the direction in which the transmittance is highest is defined as the transmittance central axis.

The central transmittance axis represents the direction of the absorption axis (the long axis direction of the molecule) of the dichroic material contained in the light absorbing anisotropic layer.

In the present invention, a liquid crystal composition containing a liquid crystal compound, a dichroic material, and a specific surfactant is used to obtain a light absorbing anisotropic layer having excellent planar uniformity and high contrast.

The details thereof are not clear, but the present inventors speculate as follows.

In forming the light absorbing anisotropic layer using the liquid crystal composition, it is estimated that the surfactant is present on the surface of the light absorbing anisotropic layer. In this case, it is considered that the surfactant has a repeating unit a containing no fluorine atom and no polymerizable group and a repeating unit B containing no fluorine atom and no polymerizable group, and satisfies the following condition 1 or 2, whereby hydrophilicity and hydrophobicity between the surfactant and the liquid crystal composition can be appropriately set, vertical alignment of the liquid crystal composition can be improved, and a light absorbing anisotropic layer excellent in planar uniformity and high in contrast can be formed.

Further, it is considered that the specific surfactant satisfying the condition 1 or 2 has polar sites, and therefore, the compatibility with the hydrophobic liquid crystal composition can be reduced, and as a result, it is considered that the light absorbing anisotropic layer having excellent planar uniformity and high contrast can be formed.

In the present invention, the transmittance central axis angle θ is preferably 0 ° or more and less than 45 °, more preferably 0 ° or more and 35 ° or less, and still more preferably 0 ° or more and less than 35 °.

[ Liquid Crystal composition ]

The light absorbing anisotropic layer of the present invention is formed of a liquid crystal composition containing a liquid crystalline compound, a dichroic material and a specific surfactant.

The liquid crystal composition may contain a solvent, an aligning agent, a polymerization initiator, a polymerizable compound, and other additives.

The components will be described below.

< Specific surfactant >

The specific surfactant contained in the liquid crystal composition is a copolymer (hereinafter, also referred to as "specific copolymer") having a repeating unit a containing no fluorine atom and containing no polymerizable group and a repeating unit B containing no fluorine atom and containing a polymerizable group and satisfying the following condition 1 or 2.

The repeating units a and B are each defined to contain no polymerizable group, but the definition is defined in consideration of distinction from any repeating unit C described later, and the description of the polymerizable group is the same as that described in the repeating unit C.

(Condition 1-repeating unit A)

The repeating unit A of the specific copolymer satisfying the condition 1 is a repeating unit represented by the following formula (A-1).

[ Chemical formula 2]

In the above formula (A-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

And LF ¹ represents a single bond or a divalent linking group.

And RF ¹ represents a group containing a fluorine atom. Wherein RF ¹ ends with-CF ₂ H.

In the above formula (A-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, as described above, but among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom or a methyl group is further preferable.

In the above formula (A-1), LF ¹ represents a single bond or a divalent linking group as described above, preferably selected from the group consisting of-O-; -COO-, -OCO-, divalent linking groups in the group consisting of divalent aliphatic groups and combinations thereof. In addition, -COO-means that the carbon to which R ¹ is bonded to c=o and RF ¹ is bonded to O, -OCO-means that the carbon to which R ¹ is bonded to O and RF ¹ is bonded to c=o.

Here, examples of the divalent aliphatic group include a divalent aliphatic chain group and an aliphatic cyclic group. The divalent aliphatic chain group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. The divalent aliphatic cyclic group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms.

Among these, as the LF ¹, preferably-COO-or-OCO-, more preferably-COO-.

In the formula (a-1), RF ¹ represents a group containing a fluorine atom, as described above, but among them, an alkyl group having 1 to 20 carbon atoms (hereinafter, also referred to as "fluoroalkyl group") in which at least 1 hydrogen atom is substituted with a fluorine atom is preferable, a fluoroalkyl group having 1 to 18 carbon atoms is more preferable, and a fluoroalkyl group having 2 to 15 carbon atoms is further preferable.

Also, it is preferable that the fluoroalkyl group contains at least 1-CF ₃ group.

The number of fluorine atoms is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.

In the present invention, the repeating unit represented by the above formula (A-1) is preferably a repeating unit represented by the following formula (A-1-1).

[ Chemical formula 3]

In the above formula (A-1-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms in the same manner as R ¹ in the above formula (A-1), and the preferable mode is the same.

In the formula (A-1-1), ma and na each independently represent an integer of 0 to 19. Among them, ma is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, from the viewpoint of raw material acquisition and the like. Na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, even more preferably an integer of 2 to 10, and most preferably an integer of 5 to 7. Wherein ma and na represent integers of 0 to 19 in total.

As the monomer forming the repeating unit represented by the above formula (A-1) or (A-1-1), specifically, for example, 2-trifluoroethyl (meth) acrylate, 2, 3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-hydroxypropyl (meth) acrylate, 3- (perfluoro-2-hydroxypropyl) acrylate, 3-perfluorohexyl (meth) 2-hydroxypropyl (meth) acrylate, and the like can be mentioned, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate, and the like.

(Condition 1-repeating unit B)

The repeating unit B of the specific copolymer satisfying the condition 1 is a repeating unit having a polar group at the terminal of the side chain.

Here, the polar group means a substituent having a hydrogen atom and having a charge bias between the hydrogen atom and a bond of an atom to which the hydrogen atom is bonded, or an ion pair composed of a deprotonated compound or a proton adduct of the substituent.

Examples of the substituent include an amino group, an amide group, an ureido group, a urethane group, a sulfonylamino group, a sulfo group, a phosphate group (phosphorus group), a hydroxyl group, a mercapto group, a carboxyl group, a methylene group substituted with an electron withdrawing group, and a methine group substituted with an electron withdrawing group.

Specific examples of the ion pair include carboxylate, onium salt, sulfonium salt, and phosphonium salt.

The repeating unit B of the specific copolymer satisfying the condition 1 is preferably a repeating unit represented by the following formula (K-1).

[ Chemical formula 4]

In the above formula (K-1), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom or a methyl group is further preferable.

Specific examples of the monomer forming the repeating unit represented by the above formula (K-1) include acrylic acid and methacrylic acid.

(Condition 2-repeating unit A)

The repeating unit a of the specific copolymer satisfying the condition 2 is not particularly limited as long as it is a repeating unit containing a fluorine atom and no polymerizable group, and is preferably a repeating unit represented by the above formula (a-1) similarly to the specific copolymer satisfying the condition 1. Wherein, in the specific copolymer satisfying the condition 2, the terminal of RF ¹ in the above formula (A-1) may be-CF ₂ H.

Specific examples of the monomer forming the repeating unit a included in the specific copolymer satisfying the condition 2 include 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 9H-hexadecylnonyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 3H-hexafluorobutyl (meth) acrylate, and the like, in addition to the monomers exemplified as the monomer forming the repeating unit represented by the above formula (a-1) or (a-1-1).

(Condition 2-repeating unit B)

The repeating unit B of the specific copolymer satisfying the condition 2 is a repeating unit represented by the following formula (B-1) or (B-2).

[ Chemical formula 5]

In the above formulae (B-1) and (B-2), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

In the formulae (B-1) and (B-2), L ¹ and L ³ represent a single bond or are selected from the group consisting of-O-, -S-, -COO-, -OCO-, -CONR ^L1-、-NR^L1COO-、-CRL¹ N-, a substituted or unsubstituted divalent aliphatic radical a divalent linking group of the group consisting of substituted or unsubstituted divalent aromatic groups and combinations thereof, R ^L1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

In the above formula (B-1), the ring A represents a ring structure having a cationized nitrogen atom.

In the formula (B-1), X represents an anion.

In the formula (B-1), L ² represents a hydrogen atom or a substituent.

In the above formula (B-2), R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R ⁴ and R ⁵ may be connected to each other via an alkylene linking group, an arylene linking group, or a linking group composed of a combination thereof.

In the above formulae (B-1) and (B-2), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, as described above, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom or a methyl group is further preferable.

In the formulae (B-1) and (B-2), as described above, L ¹ and L ³ represent a single bond or are selected from the group consisting of-O-, -S-, -COO-, -OCO-, -CONR ^L1-、-NR^L1COO-、-CR^L1 N-, a substituted or unsubstituted divalent aliphatic radical a divalent linking group of the group consisting of substituted or unsubstituted divalent aromatic groups and combinations thereof, R ^L1 represents a hydrogen atom or an alkyl group having 1to 20 carbon atoms.

Examples of the substituted or unsubstituted divalent aliphatic group represented by one embodiment of L ¹ and L ³ include an alkylene group having 1 to 20 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent (e.g., a cyclohexylene group), and the like, and among these, an alkylene group having 1 to 15 carbon atoms is preferable, an alkylene group having 1 to 8 carbon atoms is more preferable, and a methylene group, an ethylene group, a propylene group, and a butylene group are more preferable.

Examples of the substituted or unsubstituted divalent aromatic group represented by one embodiment of L ¹ and L ³ include a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include a group obtained by removing 1 hydrogen atom from 2 carbon atoms constituting the ring structure of an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, a Triphenylene (TRIPHENYLENE) ring, and a fluorene ring, and among these, a phenylene group or a naphthylene group obtained by removing 1 hydrogen atom from 2 carbon atoms constituting the ring structure of a benzene ring or a naphthalene ring is preferable. On the other hand, examples of the divalent aromatic heterocyclic group include groups obtained by removing 1 hydrogen atom from 2 carbon atoms constituting the ring structure of an aromatic heterocyclic ring such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, an oxadiazole ring, a thiazole ring, and a phenanthroline ring.

Examples of the substituent that may be included in the divalent aliphatic group or the divalent aromatic group include those described in the above substituent W.

The alkyl group having 1 to 20 carbon atoms represented by one embodiment of R ^L1 is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like are exemplified.

In the formula (B-1), the ring A represents a ring structure having a cationized nitrogen atom, as described above.

As the ring A, a ring structure represented by the following formula (B-1-1) is preferable. In the following formula (B-1-1), the bond position to L ¹ is shown.

[ Chemical formula 6]

Examples of the ring structure of the ring a include a pyridine ring, a picoline ring, a2, 2 '-bipyridine ring, a 4,4' -bipyridine ring, a1, 10-phenanthroline ring, a quinoline ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazine ring, a triazole ring, and a tetrazole ring.

Also, as the ring a, quaternary imidazolium ions and quaternary pyridinium ions are preferable.

In the formula (B-1), X represents an anion as described above.

Examples of x include halogen anions (e.g., fluoride ion, chloride ion, bromide ion, iodide ion, etc.), sulfonate ions (e.g., methanesulfonate ion, trifluoromethanesulfonate ion, methylsulfate ion, vinylsulfonate ion, allylsulfonate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, p-vinylbenzenesulfonate ion, 1, 3-benzenedisulfonate ion, 1, 5-naphthalenedisulfonate ion, 2, 6-naphthalenedisulfonate ion, etc.), sulfate ion, carbonate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, bittering ion, acetate ion, benzoate ion, p-vinylbenzoate ion, formate ion, trifluoroacetate ion, phosphate ion (e.g., hexafluorophosphate ion), hydroxide ion, etc. Preferably a halogen anion, a sulfonate ion, and a hydroxide ion. In addition, chloride ion, bromide ion, iodide ion, methanesulfonate ion, vinylsulfonate ion, p-toluenesulfonate ion, and p-vinylbenzenesulfonate ion are particularly preferable.

In the formula (B-1), L ² represents a hydrogen atom or a substituent as described above.

Examples of the substituent represented by one embodiment of L ² include those described in the above substituent W, and among them, alkylamino groups having 1 to 10 carbon atoms, aliphatic hydrocarbons (for example, alkyl groups having 1 to 20 carbon atoms, etc.), heterocyclic groups, and cyano groups are preferable.

In the above formula (B-2), as described above, R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R ⁴ and R ⁵ may be connected to each other via an alkylene linking group, an arylene linking group, or a linking group composed of a combination thereof.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by one embodiment of R ⁴ and R ⁵ include an alkyl group, an alkenyl group, or an alkynyl group which may have a substituent.

Specific examples of the alkyl group include straight-chain, branched or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-methylhexyl, cyclopentyl, cyclohexyl, 1-adamantyl, and 2-norbornyl groups.

Specific examples of the alkenyl group include a linear, branched or cyclic alkenyl group such as a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, a 1-cyclopentenyl group, a 1-cyclohexenyl group and the like.

Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a 1-octynyl group.

Examples of the substituted or unsubstituted aryl group represented by one embodiment of R ⁴ and R ⁵ include aryl groups in which 1 to 4 benzene rings form a condensed ring and aryl groups in which a benzene ring and an unsaturated five-membered ring form a condensed ring, and specifically include phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthylenyl, fluorenyl, pyrenyl, and the like.

Examples of the substituted or unsubstituted heteroaryl group represented by one embodiment of R ⁴ and R ⁵ include a group in which 1 hydrogen atom on a heteroaromatic ring containing 1 or more hetero atoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom is removed to use the heteroaryl group.

Specific examples of the heteroaromatic ring containing 1 or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thiazepine, dibenzothiophene, indazole benzimidazole, benzoylimine (anthranil), benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine, and the like.

Examples of the substituent that R ⁴ and R ⁵ may have include those described as substituent W above.

The monomer forming the repeating unit represented by the above formula (B-1) is specifically, for example, a monomer represented by the following formulas I-1 to I-11.

[ Chemical formula 7]

The monomer forming the repeating unit represented by the above formula (B-2) is specifically, for example, a monomer represented by the following formulas II-1 to II-12.

[ Chemical formula 8]

/>

In the present invention, it is more preferable that the repeating unit B of the specific copolymer satisfying the condition 2 is a repeating unit represented by the above formula (B-2) from the viewpoint of improving the uniformity of the surface and improving the contrast.

In the present invention, a specific copolymer satisfying the above condition 2 is preferable from the viewpoint of higher contrast.

The specific copolymer satisfying the condition 2 may have the repeating unit B of the specific copolymer satisfying the condition 1, that is, the repeating unit having a polar group at the terminal of the side chain, or may satisfy the condition 1.

In the present invention, the content of the repeating unit a in the specific copolymer is preferably 10 to 90 mass%, more preferably 30 to 80 mass%, relative to the total mass of the specific copolymer (specific surfactant).

In the present invention, the content of the repeating unit B in the specific copolymer is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass, based on the total mass of the specific surfactant (specific copolymer), from the viewpoint of higher contrast.

(Repeating unit C)

From the standpoint of improving the adhesion between the light-absorbing anisotropic layer and the adjacent layer, it is preferable that the specific copolymer further has a repeating unit C containing a polymerizable group.

The repeating unit C is preferably a repeating unit represented by the following formula (P-1).

[ Chemical formula 9]

In the above formula (P-1), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom or a methyl group is further preferable.

In the above formula (P-1), L ⁴ represents a single bond or is selected from the group consisting of-O-, -S-, -COO-, -OCO-, -CONR ¹²-、-NR^L2COO-、-CR^L2 N-, a substituted or unsubstituted divalent aliphatic radical a divalent linking group of the group consisting of substituted or unsubstituted divalent aromatic groups and combinations thereof, R ^L2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or-L ⁴-P¹. In addition, P ¹ when R ^L2 is-L ⁴-P¹ represents a polymerizable group in the same manner as in P ¹ in the above (P-1).

Here, examples of the divalent aliphatic group and the divalent aromatic group represented by L ⁴ include the same groups as those described in L ¹ in the above formula (B-1), and examples of the alkyl group having 1 to 20 carbon atoms represented by R ^L2 include the same groups as those described in R ^L1 in the above formula (B-1).

In the formula (P-1), P ¹ represents a polymerizable group.

In the present invention, the polymerizable group represented by P ¹ in the above formula (I) is preferably any polymerizable group selected from the group consisting of the groups represented by the following formulas (P-1) to (P-7), more preferably any polymerizable group selected from the group consisting of the groups represented by the following formulas (P-1) to (P-3), and still more preferably a polymerizable group represented by the following formulas (P-1) or (P-2).

[ Chemical formula 10]

In the above formulas (P-1) to (P-7), the bonding position with L ⁴ is represented. R ³⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and 2R ³⁰ may be the same or different, or may be connected to each other to form a ring structure.

Specific examples of the alkyl group having 1 to 5 carbon atoms represented by R ³⁰ include methyl, ethyl, propyl, isopropyl, and n-butyl.

In the present invention, from the viewpoints of ease of production, economy and radical polymerizability, preferably, the repeating unit represented by the formula (P-1) is one wherein R ¹¹ in the formula (P-1) is a hydrogen atom or a methyl group and L ⁴ in the formula (P-1) is one selected from the group consisting of-O-, -COO-, -OCO-a repeating unit of a divalent linking group of the group consisting of a combination of substituted or unsubstituted divalent aliphatic groups (preferably alkylene groups of 2 to 8 carbon atoms).

Specific examples of the repeating unit C include repeating units represented by the following formula.

[ Chemical formula 11]

/>

When the specific copolymer contains the repeating unit C, the content of the repeating unit C is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, relative to the total mass of the specific surfactant (specific copolymer).

The content of the specific surface modifier (specific copolymer) is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, and even more preferably 0.01 to 2% by mass, based on the total solid content mass of the liquid crystal composition, from the viewpoint that the uniformity of the surface is improved and the contrast is also improved.

The weight average molecular weight (Mw) of the specific surface modifier (specific copolymer) is preferably 2000 to 500000, more preferably 3000 to 300000, and even more preferably 4000 to 100000, from the viewpoint of improving the uniformity of the surface and improving the contrast.

The weight average molecular weight and the number average molecular weight in the present invention are values measured by Gel Permeation Chromatography (GPC).

Solvent (eluent): tetrahydrofuran (THF)

Device name: TOSOH HLC-8220GPC

Tubular column: 3 TOSOH TSKgel Super HZM-H (4.6 mm. Times.15 cm) were used by ligating

Column temperature: 25 DEG C

Sample concentration: 0.1 mass%

Flow rate: 0.35 ml/min

Calibration curve: calibration curves for 7 samples were used up to TOSOH CORPORATION TSK standard polystyrene mw=2800000 to 1050 (Mw/mn=1.03 to 1.06)

< Liquid Crystal Compound >

The liquid crystal composition contains a liquid crystalline compound. By containing the liquid crystalline compound, the dichroic material can be aligned with a high degree of alignment while suppressing precipitation of the dichroic material.

The liquid crystal compound contained in the liquid crystal composition can be generally classified into a rod-like type and a disc-like type depending on the shape thereof.

The liquid crystal compound preferably does not exhibit dichroism in the visible region.

In the following description, "the degree of orientation of the formed light absorbing anisotropic layer becomes higher" is also referred to as "the effect of the present invention is more excellent".

As the liquid crystalline compound, either a low molecular liquid crystalline compound or a high molecular liquid crystalline compound can be used.

The "low-molecular liquid crystalline compound" herein refers to a liquid crystalline compound having no repeating unit in its chemical structure.

The term "polymer liquid crystalline compound" refers to a liquid crystalline compound having a repeating unit in its chemical structure.

Examples of the low-molecular liquid crystalline compound include liquid crystalline compounds described in JP-A2013-228706.

Examples of the polymer liquid crystalline compound include a thermotropic liquid crystalline polymer described in JP 2011-237513A. The polymer liquid crystalline compound may have a crosslinkable group (for example, an acryl group or a methacryl group) at the terminal.

For the reason that the effect of the present invention is easily exhibited, the liquid crystalline compound is preferably a rod-like liquid crystalline compound, and more preferably a polymer liquid crystalline compound.

The liquid crystal compound may be used alone or in combination of 2 or more.

From the viewpoint of further excellent effects of the present invention, the liquid crystalline compound preferably contains a high molecular liquid crystalline compound, and particularly preferably contains both a high molecular liquid crystalline compound and a low molecular liquid crystalline compound.

The liquid crystalline compound preferably contains a liquid crystalline compound represented by the formula (LC) or a polymer thereof. The liquid crystalline compound represented by the formula (LC) or a polymer thereof is a compound exhibiting liquid crystallinity. The liquid crystallinity may be a nematic phase or a smectic phase, or may be both of a nematic phase and a smectic phase, and preferably exhibits at least a nematic phase.

As the smectic phase, a higher order smectic phase may be used. The higher order smectic phase referred to herein is a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, a smectic L phase, and among these, a smectic B phase, a smectic F phase, a smectic I phase are preferable.

If the smectic liquid crystal phase exhibited by the liquid crystalline compound is these higher order smectic liquid crystal phases, a light absorbing anisotropic layer having a higher degree of orientation order can be produced. The light absorbing anisotropic layer formed of the high-order smectic liquid crystal phase having a high alignment order in this way is a layer that obtains bragg peaks derived from a high-order structure such as a hexagonal phase or a crystalline phase in X-ray diffraction measurement. The Bragg peak is a peak derived from a molecular oriented planar periodic structure, and the liquid crystal composition of the present invention can obtain a period interval of 3.0 to 5.0Is provided.

[ Chemical formula 12]

Q1-S1-MG-MG-S2-Q2 (LC)

In the formula (LC), Q1 and Q2 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heterocyclic group (also referred to as a heteroatom-containing ring group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an aryloxy group, a siloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyl oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including anilino group), an ammonium group, an amido group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, an oxyphosphino group, a P (-52) or a cross-linked by a cross-linking group represented by at least one of the formulae (OH, P (-52, P) of the following the formula (OH, P) and (OH) to P (-52) or P (-52) is preferably represented by the following the cross-linking groups (o group, P) by the formula (O).

[ Chemical formula 13]

In the formulae (P-1) to (P-30), R ^P represents a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkylene group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heterocyclic group (also referred to as a heteroatom-containing ring group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an aryloxy group, a siloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyl oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including anilino group), an ammonium group, an amido group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an azo group or an azo group, a phosphonyloxy group, an (OH) or a phosphonyl group (-82, an O (-OH, 3256, an O) or a phosphonyl group, the plurality of R ^P may be the same or different.

Preferable examples of the crosslinkable group include a radical polymerizable group and a cationic polymerizable group. As the radical polymerizable group, a vinyl group represented by the above formula (P-1), a butadienyl group represented by the above formula (P-2), a (meth) acrylic group represented by the above formula (P-4), a (meth) acrylamide group represented by the above formula (P-5), a vinyl acetate group represented by the above formula (P-6), a fumarate group represented by the above formula (P-7), a styryl group represented by the above formula (P-8), a vinylpyrrolidone group represented by the above formula (P-9), a maleic anhydride represented by the above formula (P-11) or a maleimide group represented by the above formula (P-12) is preferable. As the cationically polymerizable group, a vinyl ether group represented by the above formula (P-18), an epoxy group represented by the above formula (P-19), or an oxetanyl group represented by the above formula (P-20) is preferable.

In the formula (LC), S1 and S2 each independently represent a divalent spacer group, and a preferred embodiment of S1 and S2 includes the same structure as SPW in the formula (W1), and therefore, description thereof is omitted.

In the formula (LC), MG represents a mesogenic group described later. The mesogenic group denoted by MG means a group that represents a main skeleton of liquid crystal molecules contributing to formation of liquid crystal. The liquid crystal molecules exhibit liquid crystallinity in an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. The mesogenic group is not particularly limited, and for example, reference may be made to "Flussige KRISTALLE IN tabillen II" (VEB Deutsche Verlag fur Grundstoff Industrie, leipzig, 1984), particularly, the records on pages 7 to 16, the liquid crystal stool and stool editing committee, the liquid crystal stool and stool (wan, journal 2000), and particularly, the record on chapter 3.

The mesogenic group represented by MG preferably contains 2 to 10 cyclic structures, more preferably 3 to 7 cyclic structures.

Specific examples of the cyclic structure include an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group.

Ext> theext> mesogenicext> groupext> representedext> byext> MGext> isext> preferablyext> aext> groupext> representedext> byext> theext> followingext> formulaext> (ext> MGext> -ext> Aext>)ext> orext> (ext> MGext> -ext> Bext>)ext>,ext> moreext> preferablyext> aext> groupext> representedext> byext> theext> followingext> formulaext> (ext> MGext> -ext> Bext>)ext>,ext> fromext> theext> viewpointsext> ofext> theext> appearanceext> ofext> liquidext> crystalext> propertiesext>,ext> adjustmentext> ofext> theext> phaseext> transitionext> temperatureext> ofext> liquidext> crystalext>,ext> rawext> materialext> availabilityext> andext> synthesisext> suitabilityext>,ext> andext> theext> likeext>,ext> andext> theext> effectext> ofext> theext> presentext> inventionext> isext> moreext> excellentext>.ext>

[ Chemical formula 14]

Ext> inext> theext> formulaext> (ext> MGext> -ext> Aext>)ext>,ext> Aext> 1ext> isext> aext> divalentext> groupext> selectedext> fromext> theext> groupext> consistingext> ofext> anext> aromaticext> hydrocarbonext> groupext>,ext> aext> heterocyclicext> groupext> andext> anext> alicyclicext> groupext>.ext> These groups may be substituted with a substituent such as substituent W.

The divalent group represented by A1 is preferably a 4-15 membered ring. The divalent group represented by A1 may be a single ring or a condensed ring.

* The bonding position with S1 or S2 is indicated.

Examples of the divalent aromatic hydrocarbon group represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and naphthacene-diyl, and phenylene and naphthylene are preferable from the viewpoints of diversity in the design of the mesogenic skeleton, availability of the starting materials, and the like.

The divalent heterocyclic group represented by A1 may be any of aromatic and non-aromatic, but is preferably a divalent aromatic heterocyclic group from the viewpoint of further improving the degree of orientation.

Examples of the atom other than carbon constituting the divalent aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these atoms may be the same or different.

Specific examples of the divalent aromatic heterocyclic group include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene group (thiophene-diyl group), a quinolinylene group (quinoline-diyl group), an isoquinolylene group (isoquinoline-diyl group), an oxazol-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimide-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiofuran-diyl group, and a thienooxazole-diyl group, and the following structures (II-1) to (II-4).

[ Chemical formula 15]

In the formulae (II-1) to (II-4), D ₁ represents-S-, -O-or NR ¹¹-,R¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y ₁ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, Z ₁、Z₂ and Z ₃ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 monovalent carbon atoms, a halogen atom, a cyano group, a nitro group, -NR ¹²R¹³, or-SR ¹²,Z₁ and Z ₂ may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring, R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and J ₁ and J ₂ each independently represent a member selected from the group consisting of-O-, -NR ²¹-(R²¹ and a hydrogen atom or a substituent. ) -S-and C (O) -groups, E represents a hydrogen atom or a non-metal atom of groups 14 to 16 to which a substituent may be bonded, jx represents an organic group having 2 to 30 carbon atoms having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, jy represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, the aromatic rings of Jx and Jy may have a substituent, jx and Jy may be bonded to form a ring, D ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

In the formula (II-2), when Y ₁ is an aromatic hydrocarbon group having 6 to 12 carbon atoms, the aromatic hydrocarbon group may be a single ring or multiple rings. When Y ₁ is an aromatic heterocyclic group having 3 to 12 carbon atoms, the group may be a single ring or multiple rings.

In the formula (II-2), when J ₁ and J ₂ represent-NR ²¹ -, the substituent for R ²¹ can be described in paragraphs 0035 to 0045 of Japanese patent application laid-open No. 2008-107767, which is incorporated herein by reference.

In the formula (II-2), when E is a non-metal atom of groups 14 to 16 to which a substituent may be bonded, it is preferable that =o, =s, =nr ',=c (R ') R '. R' represents a substituent, and as a substituent, for example, reference can be made to the descriptions in paragraphs [0035] to [0045] of JP-A-2008-107767, and it is preferable that-NZ ^A1Z^A2(Z^A1 and Z ^A2 each independently represent a hydrogen atom, an alkyl group or an aryl group. ).

Specific examples of the divalent alicyclic group represented by A1 include cyclopentylene and cyclohexylene, the carbon atom may be represented by-O-, -Si (CH ₃)₂ -, -N (Z) - (Z represent hydrogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group, aryl group, cyano group or halogen atom.)) -C (O) -, -S-, -C (S) -, -S (O) -and-SO ₂ -, and a combination of more than 2 of these groups.

Ext> inext> theext> formulaext> (ext> MGext> -ext> Aext>)ext>,ext> aext> 1ext> representsext> anext> integerext> ofext> 2ext> toext> 10ext>.ext> The plurality of A1 may be the same or different.

In the formula (MG-B), A2 and A3 are each independently a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. Ext> specificext> examplesext> andext> preferredext> modesext> ofext> Aext> 2ext> andext> Aext> 3ext> areext> theext> sameext> asext> thoseext> ofext> Aext> 1ext> ofext> theext> formulaext> (ext> MGext> -ext> Aext>)ext>,ext> andext> thereforeext>,ext> theext> descriptionext> thereofext> willext> beext> omittedext>.ext>

In the formula (MG-B), A2 represents an integer of 1 to 10, and a plurality of A2's may be the same or different, and a plurality of LA 1's may be the same or different. For the reason that the effect of the present invention is more excellent, a2 is more preferably 2 or more.

In the formula (MG-B), LA1 is a single bond or a divalent linking group. Wherein when a2 is 1, LA1 is a divalent linking group, and when a2 is 2 or more, at least 1 of the plurality of LA1 is a divalent linking group.

In the formula (MG-B), the divalent linking group represented by LA1 is the same as LW, and therefore, the description thereof is omitted.

Specific examples of MG include structures in which hydrogen atoms on aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups may be substituted with the substituent W.

[ Chemical formula 16]

[ Chemical formula 17]

[ Chemical formula 18]

(Low molecular liquid Crystal Compound)

When the liquid crystalline compound represented by the formula (LC) is a low molecular liquid crystalline compound, preferable examples of the cyclic structure of the mesogenic group MG include cyclohexylene, cyclopentylene, phenylene, naphthylene, fluoren-diyl, pyridin-diyl, pyridazin-diyl, thiophen-diyl, oxazol-diyl, thiazol-diyl, thienothien-diyl, and the like, and the number of the cyclic structures is preferably 2 to 10, more preferably 3 to 7.

Preferred examples of the substituent W having a mesogenic structure include a halogen atom, a haloalkyl group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkylcarbonyloxy group having 1 to 10 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, an alkylaminocarbonyl group, LW of the above formula (W1) is a single bond, SPW is a divalent spacer group, and Q is a crosslinkable group represented by the above-mentioned (P1) to (P30), and the crosslinkable group is preferably a vinyl group, a butadienyl group, a (meth) acrylic group, a (meth) acrylamide group, a vinyl acetate group, a fumarate group, a styryl group, a vinylpyrrolidone group, maleic anhydride, a maleimide group, a vinyl ether group, an epoxy group, or an oxetanyl group.

The divalent spacer groups S1 and S2 are the same as the SPW described above, and therefore their description is omitted.

When a low-molecular liquid crystalline compound exhibiting near crystallinity is used, the number of carbon atoms of the spacer group (the number of atoms when the carbon is substituted with "SP-C") is preferably 6 or more, more preferably 8 or more.

When the liquid crystalline compound represented by the formula (LC) is a low molecular weight liquid crystalline compound, a plurality of low molecular weight liquid crystalline compounds may be used in combination, preferably 2 to 6 low molecular weight liquid crystalline compounds are used in combination, and more preferably 2 to 4 low molecular weight liquid crystalline compounds are used in combination. The use of a low-molecular liquid crystalline compound in combination can improve the solubility or adjust the phase transition temperature of the liquid crystal composition.

Specific examples of the low-molecular liquid crystalline compound include compounds represented by the following formulas (LC-1) to (LC-77), but the low-molecular liquid crystalline compound is not limited to these.

[ Chemical formula 19]

/>

[ Chemical formula 20]

/>

(Polymer liquid Crystal Compound)

The polymer liquid crystalline compound is preferably a homopolymer or copolymer containing a repeating unit described later, and may be any polymer such as a random polymer, a block polymer, a graft polymer, or a star polymer.

< Repeating unit (1) >

The polymer liquid crystalline compound preferably contains a repeating unit represented by formula (1) (hereinafter, also referred to as "repeating unit (1)").

[ Chemical formula 21]

In the formula (1), PC1 represents a main chain of a repeating unit, L1 represents a single bond or a divalent linking group, SP1 represents a spacer group, MG1 represents a mesogenic group MG in the above formula (LC), and T1 represents an end group.

Examples of the main chain of the repeating unit represented by PC1 include groups represented by the following formulas (P1-a) to (P1-D), and among them, the group represented by the following formula (P1-a) is preferable from the viewpoints of diversity of monomers to be used as a raw material and easiness of handling.

[ Chemical formula 22]

In the formulae (P1-a) to (P1-D), "×" indicates the bonding position to L1 in the formula (1). In the formulae (P1-A) to (P1-D), R ¹¹、R¹²、R¹³、R¹⁴ independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group may be a linear or branched alkyl group, or may be an alkyl group (cycloalkyl group) having a cyclic structure. The number of carbon atoms of the alkyl group is preferably 1 to 5.

The group represented by the formula (P1-A) is preferably one unit of the partial structure of a poly (meth) acrylate obtained by polymerization of a (meth) acrylate.

The group represented by the formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an epoxy group of a compound having an epoxy group.

The group represented by the formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetanyl group of a compound having an oxetanyl group.

The group represented by the formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one of an alkoxysilyl group and a silanol group. Here, as the compound having at least one group of an alkoxysilyl group and a silanol group, a compound having a group represented by the formula SiR ¹⁴(OR¹⁵)₂ -is exemplified. Wherein R ¹⁴ has the same meaning as R ¹⁴ in (P1-D), and each of R ¹⁵ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

The divalent linking group represented by L1 is the same divalent linking group as LW in the above formula (W1), and as a preferable mode, examples include-C (O) O-; -OC (O) -, -O-; -S-, -C (O) NR ¹⁶-、-NR¹⁶C(O)-、-S(O)₂ -and-NR ¹⁶R¹⁷ -, etc. Wherein R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent (for example, the substituent W). In the specific example of a divalent linking group, the left-hand linking bond is bonded to PC1 and the right-hand linking bond is bonded to SP 1.

When PC1 is a group represented by the formula (P1-A), L1 is preferably a group represented by-C (O) O-or-C (O) NR ¹⁶ -.

When PC1 is a group represented by the formulae (P1-B) to (P1-D), L1 is preferably a single bond.

The spacer group represented by SP1 represents the same group as S1 and S2 in the above formula (LC), and from the viewpoint of the degree of orientation, it is preferably a group containing at least 1 structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and a fluorinated alkylene structure, or a linear or branched alkylene group having 2 to 20 carbon atoms. Wherein, the alkylene group may contain-O-, -S-, -O-CO-, -CO-O-, -O-CO-O-, and-O-CNR- (R represents an alkyl group having 1 to 10 carbon atoms) or-S (O) ₂ -.

The spacer group represented by SP1 is more preferably a group containing at least 1 structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and a fluorinated alkylene structure, from the viewpoint of easy availability of liquid crystal properties, availability of raw materials, and the like.

The oxyethylene structure represented by SP1 is preferably a group represented by- (CH ₂-CH₂O)_n1 -) in the formula, n1 represents an integer of 1 to 20 and represents a bonding position with L1 or MG 1. N1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and most preferably 2 to 4, for the reason that the effect of the present invention is more excellent.

The oxypropylene structure represented by SP1 is preferably a group represented by- (CH (CH ₃)-CH₂O)_n2 -) in the formula, n2 represents an integer of 1 to 3, and represents a bonding position to L1 or MG 1.

The polysiloxane structure represented by SP1 is preferably a group represented by- (Si (CH ₃)₂-O)_n3 -) in the formula, n3 represents an integer of 6 to 10, and x represents a bonding position to L1 or MG 1.

The fluorinated alkylene structure represented by SP1 is preferably a group represented by- (CF ₂-CF₂)_n4 -) -. N4 represents an integer of 6 to 10, and represents a bonding position to L1 or MG 1.

Examples of the terminal group represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, -SH, a carboxyl group, a boric acid group, -SO ₃H、-PO₃H₂、-NR¹¹R¹²(R¹¹, and R ¹² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a ureido group having 1 to 10 carbon atoms, a crosslinkable group, and the like.

Examples of the crosslinkable group-containing group include the above-mentioned-L-CL. L represents a single bond or a linking group. Specific examples of the linking group are the same as those described above for LW and SPW. CL represents a crosslinkable group, and examples thereof include groups represented by Q1 or Q2, preferably groups represented by the formulas (P1) to (P30). T1 may be a group formed by combining 2 or more of these groups.

For the reason that the effect of the present invention is more excellent, T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and still more preferably a methoxy group. These terminal groups may be further substituted with these groups or with a polymerizable group described in JP-A2010-244038.

For the reason that the effect of the present invention is more excellent, the number of atoms of the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, particularly preferably 1 to 7. Since the number of atoms of the main chain of T1 is 20 or less, the degree of orientation of the light absorbing anisotropic layer is further improved. Here, the "main chain" in T1 means the longest molecular chain bonded to M1, and hydrogen atoms are not counted in the number of atoms of the main chain of T1. For example, when T1 is n-butyl, the number of atoms of the main chain is 4, and when T1 is sec-butyl, the number of atoms of the main chain is 3.

The content of the repeating unit (1) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, based on the total repeating unit (100% by mass) of the polymer liquid crystalline compound. When the content of the repeating unit (1) is 40 mass% or more, a more excellent light absorption anisotropic layer can be obtained due to good orientation. Further, when the content of the repeating unit (1) is 100 mass% or less, a more excellent light absorbing anisotropic layer can be obtained due to good orientation.

The polymer liquid crystalline compound may contain 1 kind of repeating unit (1) alone or 2 or more kinds of repeating units (1). When the repeating unit (1) is contained in an amount of 2 or more, the content of the repeating unit (1) means the total content of the repeating units (1).

In the formula (1), the difference (log p ₁-logP₂) between the log p values of PC1, L1 and SP1 (hereinafter, also referred to as "log p ₁") and the log p value of MG1 (hereinafter, also referred to as "log p ₂") is preferably 4 or more, more preferably 4.25 or more, and still more preferably 4.5 or more, from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

The upper limit of the difference is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less, from the viewpoint of adjusting the liquid crystal phase transition temperature and the synthesis suitability.

The log p value is an index indicating the hydrophilicity and hydrophobicity of the chemical structure, and is sometimes referred to as a hydrophilicity/hydrophobicity parameter. The log p value can be calculated using software such as ChemBioDraw Ultra or hsPIP (Ver.4.1.07). Further, the measurement can be experimentally obtained by a method of OECD Guidelines for THE TESTING of Chemicals, sectionsl, testNo.117, or the like. In the present invention, unless otherwise specified, a value calculated by inputting the structural formula of a compound into hsppi (ver.4.1.07) is employed as a log p value.

As described above, the log p ₁ refers to the log p values of PC1, L1, and SP 1. The "log p values of PC1, L1, and SP 1" refer to the log p values of the configuration in which PC1, L1, and SP1 are integrated, and are not obtained by adding up the respective log p values of PC1, L1, and SP1, specifically, log p ₁ is calculated by inputting a series of structural formulas of PC1 to SP1 in the formula (1) into the software.

Among these formulae, in calculating log P ₁, the moiety of the group represented by PC1 among the series of formulae PC1 to SP1 may be a structure of the group represented by PC1 itself (for example, formulae (P1-a) to (P1-D) described above), or a structure in which a monomer used to obtain the repeating unit represented by formula (1) is polymerized and then can be a group of PC 1.

The latter (group which can be PC 1) is specifically described below. When PC1 is obtained by polymerization of a (meth) acrylate, it is a group represented by CH ₂＝C(R¹) - (R ¹ represents a hydrogen atom or a methyl group. ). Also, when PCI is obtained by polymerization of ethylene glycol, it is ethylene glycol, and when PC1 is obtained by polymerization of propylene glycol, it is propylene glycol. And when PC1 is obtained by polycondensation of silanol, it is a compound represented by silanol (formula Si (R ²)₃ (OH): A plurality of R ² each independently represents a hydrogen atom or an alkyl group, wherein at least 1 of a plurality of R ² represents an alkyl group).

The log p ₁ may be lower than the log p ₂ or higher than the log p ₂ as long as the difference between the log p ₁ and the log p ₂ is 4 or more.

The typical mesogenic group tends to have a log P value (log P ₂ described above) in the range of 4 to 6. At this time, when logP ₁ is lower than logP ₂, the value of logP ₁ is preferably 1 or less, more preferably 0 or less. On the other hand, when log p ₁ is higher than log p ₂, the value of log p ₁ is preferably 8 or more, more preferably 9 or more.

When PCI in the above formula (1) is obtained by polymerization of (meth) acrylic acid ester and log p ₁ is lower than log p ₂, the log p value of SP1 in the above formula (1) is preferably 0.7 or less, more preferably 0.5 or less. On the other hand, when PC1 in the above formula (1) is obtained by polymerization of (meth) acrylic ester and log p ₁ is higher than log p ₂, the log p value of SP1 in the above formula (1) is preferably 3.7 or more, more preferably 4.2 or more.

Examples of the structure having a log p value of 1 or less include an oxyethylene structure and an oxypropylene structure. Examples of the structure having a log p value of 6 or more include a polysiloxane structure and a fluorinated alkylene structure.

< Repeating units (21) and (22) >

From the viewpoint of improving the degree of orientation, the polymer liquid crystalline compound preferably contains a repeating unit having electron donating property and/or electron withdrawing property at the terminal. More specifically, it more preferably contains: a repeating unit (21) having a mesogenic group and an electron withdrawing group having a sigma p value of greater than 0 present at the terminal; and a repeating unit (22) having a mesogenic group and a group having a sigma p value of 0 or less present at the terminal. In this way, when the polymer liquid crystalline compound contains the repeating unit (21) and the repeating unit (22), the degree of orientation of the light absorbing anisotropic layer formed using the same is improved as compared with the case where only either the repeating unit (21) or the repeating unit (22) is contained. The reason for this is not clear in detail, but is estimated as follows.

That is, it is assumed that the dipole moment in the opposite direction generated in the repeating unit (21) and the repeating unit (22) interacts with each other between molecules, and thus the interaction of the mesogenic group in the short axis direction becomes stronger, and the orientation of the liquid crystal becomes more uniform, and as a result, it is considered that the degree of order of the liquid crystal becomes higher. As a result, it is presumed that the alignment property of the dichroic material is also good, and therefore the degree of alignment of the formed light absorbing anisotropic layer is high.

The repeating units (21) and (22) may be repeating units represented by the formula (1).

The repeating unit (21) has a mesogenic group and an electron withdrawing group having a sigma p value of more than 0 present at the terminal of the mesogenic group.

The electron withdrawing group is a group having a σp value of more than 0 and located at the terminal of the mesogenic group. Examples of the electron-withdrawing group (group having a σp value of more than 0) include groups represented by EWG in the following formula (LCP-21), and specific examples thereof are also the same.

The σp value of the electron withdrawing group is preferably 0.3 or more, more preferably 0.4 or more, from the viewpoint that the degree of orientation of the light absorbing anisotropic layer becomes higher. The upper limit of the σp value of the electron withdrawing group is preferably 1.2 or less, more preferably 1.0 or less, from the viewpoint of excellent uniformity of orientation.

The σp value is a Hammett substituent constant σp value (also simply referred to as "σp value"), which is a value that numerically indicates the effect of substituting a substituent in the acid dissociation equilibrium constant of benzoic acid and is a parameter that indicates the intensity of electron withdrawing property and electron donating property of the substituent. The Hammett substituent constant σp value in the present specification means the substituent constant σ when the substituent is located at the para position of benzoic acid.

The Hammett substituent constant σp values of the various groups in this specification are values described in the literature "Hansch et al, CHEMICAL REVIEWS,1991,VOL,91,NO.2, 165-195". In addition, as for the group not showing the value of the hammett substituent constant σp in the above document, the hammett substituent constant σp value can be calculated from the difference between the pKa of benzoic acid and the pKa of the benzoic acid derivative having a substituent at the para position using software "ACD/ChemSketch (ACD/Labs 8.00Release Product Version:8.08)".

The repeating unit (21) is not particularly limited as long as it has a mesogenic group in a side chain and an electron withdrawing group having a σp value of more than 0 existing at the terminal of the mesogenic group, but is preferably a repeating unit represented by the following formula (LCP-21) from the viewpoint that the degree of orientation of the light absorbing anisotropic layer becomes higher.

[ Chemical formula 23]

In the formula (LCP-21), PC21 represents a main chain of a repeating unit, more specifically, represents the same structure as PC1 in the above formula (1), L21 represents a single bond or a divalent linking group, more specifically, represents the same structure as L1 in the above formula (1), SP21A and SP21B each independently represent a single bond or a spacer group, a specific example of a spacer group represents the same structure as SP1 in the above formula (1), MG21 represents a mesogenic structure, more specifically, represents a mesogenic group MG in the above formula (LC), and EWG represents an electron withdrawing group having a σp value of greater than 0.

The spacer group represented by SP21A and SP21B represents the same group as the above formulae S1 and S2, and preferably contains at least 1 structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and a fluorinated alkylene structure, or a linear or branched alkylene group having 2 to 20 carbon atoms. Wherein, the alkylene group may include-O-; -O-CO-, -CO-O-or-O-CO-O-.

The spacer group represented by SPl preferably contains at least 1 structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and a fluorinated alkylene structure, from the viewpoint of easy availability of liquid crystal properties, availability of raw materials, and the like.

SP21B is preferably a single bond or a straight-chain or branched alkylene group having 2 to 20 carbon atoms. Wherein, the alkylene group may include-O-; -O-CO-, -CO-O-or-O-CO-O-.

Among them, the spacer group represented by SP21B is preferably a single bond from the viewpoint that the degree of orientation of the light absorbing anisotropic layer becomes higher. In other words, the repeating unit 21 preferably has a structure in which the EWG as an electron-withdrawing group in the formula (LCP-21) is directly connected to the MG21 as a mesogenic group in the formula (LCP-21). As described above, it is assumed that when the electron withdrawing group is directly connected to the mesogenic group, intermolecular interaction by an appropriate dipole moment in the polymer liquid crystalline compound acts more effectively, and the orientation of the liquid crystal becomes more uniform, and as a result, it is considered that the degree of order of the liquid crystal becomes higher, and the degree of orientation becomes higher.

EWG represents an electron withdrawing group having a σp value greater than 0. Examples of the electron withdrawing group having a σp value of more than 0 include an ester group (specifically, a group represented by x-C (O) O-R ^E), (meth) acryl group, (meth) acryloyloxy group, carboxyl group, cyano group, nitro group, sulfo group, -S (O) -OR ^E、-S(O)(O)-R^F、-O-S(O)(O)-R^E, an acyl group (specifically, a group represented by x-C (O) R ^E), an acyloxy group (specifically, a group represented by x-OC (O) R ^E), an isocyanate group (-n=c (O)), -C (O) N (R ^F)₂, a halogen atom, and an alkyl group substituted with these groups (carbon number is preferably 1 to 20.) in the above groups, R ^E represents a bonding position with SP21B, and R ^F independently represents a hydrogen atom OR an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms).

Among the above groups, from the viewpoint of further exhibiting the effects of the present invention, EWG is preferably a group represented by x-C (O) O-R ^E, (meth) acryloyloxy, cyano, or nitro.

The content of the repeating unit (21) is preferably 60 mass% or less, more preferably 50 mass% or less, particularly preferably 45 mass% or less, relative to the total repeating unit (100 mass%) of the polymeric liquid crystalline compound, from the viewpoint of maintaining the high degree of alignment of the light absorbing anisotropic layer and enabling uniform alignment of the polymeric liquid crystalline compound and the dichroic substance.

From the viewpoint of further exhibiting the effects of the present invention, the lower limit of the content of the repeating unit (21) is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total repeating unit (100% by mass) of the polymer liquid crystalline compound.

In the present invention, the content of each repeating unit contained in the polymer liquid crystalline compound is calculated from the amount (mass) of each monomer to be added to obtain each repeating unit.

The polymer liquid crystalline compound may contain 1 kind of repeating unit (21) alone or 2 or more kinds of repeating units (21). When the polymer liquid crystalline compound contains at least 2 kinds of repeating units (21), there are advantages such as improved solubility of the polymer liquid crystalline compound in a solvent and easy adjustment of the liquid crystal phase transition temperature. When the repeating unit (21) is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.

When the repeating unit (21) contains 2 or more kinds, the repeating unit (21) containing no crosslinkable group in the EWG and the repeating unit (21) containing a polymerizable group in the EWG may be used in combination. Thereby, the curability of the light absorbing anisotropic layer is further improved. Further, as the crosslinkable group, vinyl group, butadienyl group, (meth) acrylic group, (meth) acrylamide group, vinyl acetate group, fumarate group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, vinyl ether group, epoxy group, and oxetanyl group are preferable.

In this case, the content of the repeating unit (21) containing a polymerizable group in the EWG is preferably 1 to 30 mass% relative to the total repeating unit (100 mass%) of the polymer liquid crystalline compound from the viewpoint of balance between the curability and the degree of alignment of the light absorbing anisotropic layer.

Hereinafter, an example of the repeating unit (21) is shown, but the repeating unit (21) is not limited to the following repeating unit.

[ Chemical formula 24]

As a result of intensive studies on the composition (content ratio) and the electron-withdrawing property and electron-withdrawing property of the terminal groups of the repeating units (21) and the repeating units (22), the inventors have found that, when the electron-withdrawing property of the electron-withdrawing group of the repeating units (21) is strong (i.e., when the σp value is large), the degree of orientation of the light-absorbing anisotropic layer becomes higher if the content ratio of the repeating units (21) is low, and when the electron-withdrawing property of the electron-withdrawing group of the repeating units (21) is weak (i.e., when the σp value is close to 0), the degree of orientation of the light-absorbing anisotropic layer becomes higher if the content ratio of the repeating units (21) is high.

The reason for this is not clear in detail, but is estimated as follows. That is, it is assumed that the intermolecular interaction due to the moderate dipole moment acts in the polymer liquid crystalline compound, and the orientation of the liquid crystal is more uniform, and as a result, it is considered that the degree of order of the liquid crystal is higher, and the degree of orientation of the light absorbing anisotropic layer is higher.

Specifically, the product of the σp value of the electron withdrawing group (EWG in the formula (LCP-21)) in the repeating unit (21) and the content ratio (mass basis) of the repeating unit (21) in the polymer liquid crystalline compound is preferably 0.020 to 0.150, more preferably 0.050 to 0.130, and particularly preferably 0.055 to 0.125. If the product is within the above range, the degree of orientation of the light absorbing anisotropic layer becomes higher.

The repeating unit (22) has a mesogenic group and a group having a sigma p value of 0 or less existing at the terminal of the mesogenic group. The polymer liquid crystalline compound has a repeating unit (22), so that the polymer liquid crystalline compound and the dichroic material can be uniformly aligned.

The mesogenic group is a group that represents a main skeleton of a liquid crystal molecule that contributes to the formation of liquid crystal, and specific examples thereof are the same as described in detail below in MG of formula (LCP-22).

The above group is a group located at the terminal of a mesogenic group and having a σp value of 0 or less. Examples of the group (group having a σp value of 0 or less) include a hydrogen atom having a σp value of 0 and a group represented by T22 (electron donating group) in the following formula (LCP-22) having a σp value of less than 0. Of the above groups, a specific example of a group having a σp value of less than 0 (electron donating group) is the same as T22 in the following formula (LCP-22).

The σp value of the above group is 0 or less, preferably less than 0, more preferably-0.1 or less, and particularly preferably-0.2 or less, from the viewpoint of more excellent uniformity of orientation. The lower limit of the σp value of the above group is preferably-0.9 or more, more preferably-0.7 or more.

The repeating unit (22) is not particularly limited as long as it has a mesogenic group in a side chain and a group having a σp value of 0 or less existing at the terminal of the mesogenic group, but is preferably a repeating unit represented by the following formula (PCP-22) which does not correspond to the repeating unit represented by the formula (LCP-21) from the viewpoint of higher uniformity of liquid crystal alignment.

[ Chemical formula 25]

In the formula (LCP-22), PC22 represents the main chain of the repeating unit, more specifically, the same structure as PC1 in the above formula (1), L22 represents a single bond or a divalent linking group, more specifically, the same structure as L1 in the above formula (1), SP22 represents a spacer group, more specifically, the same structure as SP1 in the above formula (1), MG22 represents a mesogenic structure, more specifically, the same structure as the mesogenic group MG in the above formula (LC), and T22 represents an electron donating group having a hamite substituent constant σp of less than 0.

T22 represents an electron donating group having a σp value of less than 0. Examples of the electron donating group having a σp value of less than 0 include a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylamino group having 1 to 10 carbon atoms.

The degree of orientation of the light absorbing anisotropic layer is further improved by the number of atoms of the main chain of T22 being 20 or less. Here, the "main chain" in T22 means the longest molecular chain bonded to M622, and hydrogen atoms are not counted in the number of atoms of the main chain of T22. For example, when T22 is n-butyl, the number of atoms of the main chain is 4, and when T22 is sec-butyl, the number of atoms of the main chain is 3.

Hereinafter, an example of the repeating unit (22) is shown, but the repeating unit (22) is not limited to the following repeating unit.

[ Chemical formula 26]

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The repeating unit (21) and the repeating unit (22) are preferably partially identical in structure. It is presumed that the more similar the repeating units are to each other, the more uniform the liquid crystal alignment is. Thereby, the degree of orientation of the light absorbing anisotropic layer becomes higher.

Specifically, from the viewpoint of the degree of orientation of the light absorbing anisotropic layer becoming higher, SP21A satisfying the formula (LCP-21) and SP22 satisfying the formula (LCP-22) are preferably the same structure, MG21 of the formula (LCP-21) and MG22 of the formula (LCP-22) are the same structure, and L21 of the formula (LCP-21) and L22 of the formula (LCP-22) are at least 1 of the same structure, more preferably 2 or more, particularly preferably all.

From the viewpoint of excellent uniformity of alignment, the content of the repeating unit (22) is preferably 50 mass% or more, more preferably 55 mass% or more, particularly preferably 60 mass% or more, relative to the total repeating unit (100 mass%) of the polymer liquid crystalline compound.

From the viewpoint of improving the degree of alignment, the upper limit of the content of the repeating unit (22) is preferably 99 mass% or less, more preferably 97 mass% or less, relative to the total repeating unit (100 mass%) of the polymer liquid crystalline compound.

The polymer liquid crystalline compound may contain 1 kind of repeating unit (22) alone or 2 or more kinds of repeating units (22). When the polymer liquid crystalline compound contains at least 2 kinds of repeating units (22), there are advantages such as improved solubility of the polymer liquid crystalline compound in a solvent and easy adjustment of the liquid crystal phase transition temperature. When the repeating unit (22) is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.

< Repeating unit (3) >

From the viewpoint of improving the solubility in a general-purpose solvent, the polymer liquid crystalline compound may contain a repeating unit (3) containing no mesogen. In particular, in order to suppress the decrease in the degree of orientation and to improve the solubility, the repeating unit (3) containing no mesogen is preferably a repeating unit having a molecular weight of 280 or less. As a reason why the solubility is improved by suppressing the decrease in the degree of orientation by containing a repeating unit having a molecular weight of 280 or less without mesogen, it is estimated as follows.

That is, it is considered that the solubility is improved because the polymer liquid crystalline compound contains the repeating unit (3) having no mesogen in the molecular chain thereof, and the solvent easily enters the polymer liquid crystalline compound, but the non-mesogenic repeating unit (3) lowers the degree of alignment. However, it is estimated that the alignment of the repeating unit (1), the repeating unit (21), or the repeating unit (22) containing the mesogenic group is not easily disturbed because the molecular weight of the repeating unit is small, and thus the decrease in the degree of alignment can be suppressed.

The repeating unit (3) is preferably a repeating unit having a molecular weight of 280 or less.

The molecular weight of the repeating unit (3) does not refer to the molecular weight of the monomer used to obtain the repeating unit (3), but refers to the molecular weight of the repeating unit (3) in a state of being incorporated into the polymer liquid crystalline compound by polymerization of the monomer.

The molecular weight of the repeating unit (3) is 280 or less, preferably 180 or less, more preferably 100 or less. The lower limit of the molecular weight of the repeating unit (3) is usually 40 or more, more preferably 50 or more. When the molecular weight of the repeating unit (3) is 280 or less, a light-absorbing anisotropic layer having excellent solubility of the polymer liquid crystalline compound and a high degree of orientation can be obtained.

On the other hand, if the molecular weight of the repeating unit (3) exceeds 280, the alignment of the liquid crystal in the repeating unit (1), repeating unit (21) or repeating unit (22) may be disturbed, and the degree of alignment may be reduced. In addition, the solvent is less likely to enter the polymer liquid crystalline compound, and therefore the solubility of the polymer liquid crystalline compound may be lowered.

Specific examples of the repeating unit (3) include a repeating unit (hereinafter, also referred to as "repeating unit (3-1)") containing no crosslinkable group (e.g., an ethylenically unsaturated group) and a repeating unit (hereinafter, also referred to as "repeating unit (3-2)") containing a crosslinkable group.

Repeating units (3-1)

Specific examples of the monomer used in the polymerization of the repeating unit (3-1) include acrylic acid [72.1], alpha-alkylacrylic acids (e.g., methacrylic acid [86.1], itaconic acid [130.1 ]), esters and amides derived from these (e.g., N-isopropylacrylamide [113.2], N-N-butylacrylamide [127.2], N-t-butylacrylamide [127.2], N, N-dimethylacrylamide [99.1], N-methylacrylamide [99.1], acrylamide [71.1], methacrylamide [85.1], diacetone acrylamide [169.2], acryloylmorpholine [141.2], N-methylolacrylamide [101.1], N-methylolmethacrylamide [115.1], methyl acrylate [86.0], ethyl acrylate [100.1], hydroxyethyl acrylate [116.1], N-propyl acrylate [114.1], isopropyl acrylate [114.2], 2-hydroxypropyl acrylate [130.1], 2-methyl-2-nitropropyl acrylate [173.2], N-butyl acrylate [128.2], isobutyl acrylate [128.2], t-butyl acrylate [128.2], t-amyl acrylate [142.2], 2-methoxyethyl acrylate [130.1], 2-ethoxyethyl acrylate [144.2], 2-ethoxyethyl acrylate [188.2], 2-trifluoroethyl acrylate [130.1, 2-trifluoro-N-propyl acrylate [114.1], 2-nitro propyl acrylate [173.2, 2-butyl acrylate ], N-butyl acrylate [ 156.2.2 ] 2-butyl acrylate, 2-butyl acrylate ] and 2.158 Cyclohexyl acrylate [154.2], cyclopentyl acrylate [140.2], N-octyl acrylate [162.2], 2-ethylhexyl acrylate [184.3], 4-methyl-2-propylpentyl acrylate [198.3], methyl methacrylate [100.1], 2-trifluoroethyl methacrylate [168.1], hydroxyethyl methacrylate [130.1], 2-hydroxypropyl methacrylate [144.2], N-butyl methacrylate [142.2], N-octyl methacrylate [142.2], sec-butyl methacrylate [198.3], 2-methoxyethyl methacrylate [144.2], 2-ethoxyethyl methacrylate [158.2], 5-norbornyl methacrylate [194.3], 5-norbornyl methacrylate [53 ] such as ethyl styrene [144.1], maleic anhydride [1, 6- (vinyl) or (e.g. 1, 66, 53) of the maleic acid, such as vinyl-bis [ 1] maleate [142.2], styrene-vinyl-bis [ 1] or (e.g. 1,6, vinyl-bis [ 1] maleate ] Tert-butylstyrene [160.3], alpha-methylstyrene [118.2 ]), N-vinylpyrrolidone [111.1], N-vinyloxazolidinone [113.1], N-vinylsuccinimide [125.1], N-vinylformamide [71.1], N-vinyl-N-methylformamide [85.1], N-vinylacetamide [85.1], N-vinyl-N-methylacetamide [99.1], 1-vinylimidazole [94.1], 4-vinylpyridine [105.2], vinylsulfonic acid [108.1], sodium vinylsulfonate [130.2], sodium allylsulfonate [144.1], sodium methallylsulfonate [158.2], vinylidene chloride [96.9], vinyl alkyl ethers (e.g., methyl vinyl ether [58.1 ]), ethylene [28.0], propylene [42.1], 1-butene [56.1], and isobutylene [56.1]. In addition, the values in [ (C ] refer to the molecular weight of the monomers).

The above monomers may be used alone or in combination of at least 2.

Among the above monomers, acrylic acid, α -alkylacrylic acid, esters and amides derived therefrom, acrylonitrile, methacrylonitrile, and aromatic vinyl compounds are preferable.

As the monomer other than the above, for example, a compound described in Research Disclosure No.1955 (1980, 7 month) can be used.

Specific examples of the repeating unit (3-1) and the molecular weight thereof are shown below, but the present invention is not limited to these specific examples.

[ Chemical formula 27]

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Repeating units (3-2)

Specific examples of the crosslinkable group in the repeating unit (3-2) include groups represented by the above-mentioned P1 to P30, more preferably a vinyl group, a butadienyl group, a (meth) acrylic group, a (meth) acrylamide group, a vinyl acetate group, a fumarate group, a styryl group, a vinylpyrrolidone group, maleic anhydride, a maleimide group, a vinyl ether group, an epoxy group, and an oxetanyl group.

From the viewpoint of easy polymerization, the repeating unit (3-2) is preferably a repeating unit represented by the following formula (3).

[ Chemical formula 28]

In the above formula (3), PC32 represents a main chain of a repeating unit, more specifically, a structure similar to that of PC1 in the above formula (1), L32 represents a single bond or a divalent linking group, more specifically, a structure similar to that of L1 in the above formula (1), and P32 represents crosslinkable groups represented by the above formulas (P1) to (P30).

Specific examples of the repeating unit (3-2) and the weight average molecular weight (Mw) thereof are shown below, but the present invention is not limited to these specific examples.

[ Chemical formula 29]

The content of the repeating unit (3) is less than 14 mass%, preferably 7 mass% or less, and more preferably 5 mass% or less, based on the total repeating unit (100 mass%) of the polymer liquid crystalline compound. The lower limit of the content of the repeating unit (3) is preferably 2% by mass or more, more preferably 3% by mass or more, relative to the total repeating unit (100% by mass) of the polymer liquid crystalline compound. If the content of the repeating unit (3) is less than 14 mass%, the degree of orientation of the light absorbing anisotropic layer is further improved. When the content of the repeating unit (3) is 2 mass% or more, the solubility of the polymer liquid crystalline compound is further improved.

The polymer liquid crystalline compound may contain 1 kind of repeating unit (3) alone or 2 or more kinds of repeating units (3). When the repeating unit (3) is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.

< Repeating unit (4) >

From the viewpoint of improving adhesion or planar uniformity, the polymer liquid crystalline compound may contain a repeating unit (4) having a soft structure with a molecular chain length (SP 4 of formula (4) described below). The reason for this is estimated as follows.

That is, by the soft structure containing such a molecular chain length, entanglement is likely to occur between the molecular chains constituting the polymer liquid crystalline compound, and thus the cohesive failure of the light absorbing anisotropic layer (specifically, the light absorbing anisotropic layer itself is broken) is suppressed. As a result, it is presumed that the adhesion between the light absorbing anisotropic layer and the underlayer (for example, the substrate or the alignment film) is improved. Further, it is considered that the decrease in planar uniformity is caused by low compatibility of the dichroic material with the polymer liquid crystalline compound. That is, if the compatibility of the dichroic material with the polymer liquid crystalline compound is insufficient, a planar defect (alignment defect) having the precipitated dichroic material as a core is considered to occur. On the other hand, it is estimated that the polymer liquid crystalline compound contains a soft structure having a molecular chain length, and suppresses precipitation of the dichroic material, whereby a light absorbing anisotropic layer having excellent planar uniformity can be obtained. The excellent planar uniformity means that the liquid crystal composition containing the polymer liquid crystalline compound is repelled from the underlayer (for example, the substrate or the alignment film) and causes few alignment defects.

The repeating unit (4) is a repeating unit represented by the following formula (4).

[ Chemical formula 30]

In the above formula (4), PC4 represents a main chain of a repeating unit, more specifically, a structure similar to that of PC1 in the above formula (1), L4 represents a single bond or a divalent linking group, more specifically, a structure similar to that of L1 in the above formula (1) (preferably a single bond), SP4 represents an alkylene group having 10 or more atoms in the main chain, and T4 represents a terminal group, more specifically, a structure similar to that of T1 in the above formula (1).

Specific examples and preferred modes of the PC4 are the same as those of the PC1 of the formula (1), and therefore, the description thereof is omitted.

From the viewpoint of further exhibiting the effects of the present invention, L4 is preferably a single bond.

In the formula (4), SP4 represents an alkylene group having 10 or more atoms in the main chain. Wherein at least 1-CH ₂ -constituting the alkylene group represented by SP4 may be substituted by the above-mentioned "SP-C", particularly preferably selected from the group consisting of-O-, -S-, -N (R ²¹)-、-C(＝O)-、-C(＝S)-、-C(R²²)＝C(R²³) -, alkynylene group-Si (R ²⁴)(R²⁵)-、-N＝N-、-C(R²⁶)＝N-N＝C(R²⁷)-、-C(R²⁸) =n-and-S (=o) ₂ -, and at least 1 group substitution. Wherein R ²¹～R²⁸ independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms. The hydrogen atom contained in-CH ₂ -constituting 1 or more of the alkylene groups represented by SP4 may be replaced with "SP-H" described above.

The number of atoms of the main chain of SP4 is 10 or more, preferably 15 or more, more preferably 19 or more, from the viewpoint that a light absorbing anisotropic layer excellent in at least one of adhesion and planar uniformity can be obtained. Further, from the viewpoint that a light absorbing anisotropic layer having a more excellent degree of orientation can be obtained, the upper limit of the number of atoms of the main chain of SP2 is preferably 70 or less, more preferably 60 or less, and particularly preferably 50 or less.

Here, the "main chain" in SP4 refers to a partial structure required for directly connecting L4 and T4, and the "number of atoms of the main chain" refers to the number of atoms constituting the above partial structure. In other words, the "main chain" in SP4 is a partial structure in which the number of atoms connecting L4 and T4 is the shortest. For example, the number of atoms of the main chain is 10 when SP4 is 3, 7-dimethyldecyl and 12 when SP4 is 4, 6-dimethyldodecyl. In the following formula (4-1), the number of atoms in the main chain (corresponding to the total number of atoms surrounded by a circle of a broken line) corresponding to SP4 and SP4 in the frame indicated by the broken line quadrangle is 11.

[ Chemical formula 31]

The alkylene group represented by SP4 may be linear or branched.

The number of carbon atoms of the alkylene group represented by SP4 is preferably 8 to 80, more preferably 15 to 80, still more preferably 25 to 70, particularly preferably 25 to 60, from the viewpoint that a light absorbing anisotropic layer having a more excellent degree of orientation can be obtained.

From the viewpoint of obtaining a light-absorbing anisotropic layer having more excellent adhesion and planar uniformity, 1 or more of-CH ₂ -constituting the alkylene group represented by SP4 is preferably substituted with the above-mentioned "SP-C".

In the case of-CH ₂ -having a plurality of alkylene groups constituting the group represented by SP4, it is more preferable that only a part of the plurality of-CH ₂ -is substituted with the above-mentioned "SP-C" from the viewpoint that a light absorbing anisotropic layer having more excellent adhesion and plane uniformity can be obtained.

In "SP-C", at least 1 group selected from the group consisting of-O-, -S-, -N (R ²¹)-、-C(＝0)-、-C(＝S)-、-C(R²²)＝C(R²³) -, alkynylene, -Si (R ²⁴)(R²⁵)-、-N＝N-、-C(R²⁶)＝N-N＝C(R²⁷)-、-C(R²⁸) =n-and-S (=o) ₂ -, and from the viewpoint that a light absorbing anisotropic layer more excellent in adhesion and plane uniformity can be obtained, at least 1 group selected from the group consisting of-O-, -N (R ²¹) -, -C (=o) -and-S (=o) ₂ -, and particularly at least 1 group selected from the group consisting of-O-, -N (R ²¹) -and C (=0) -are more preferable.

In particular, SP4 preferably contains at least 1 group selected from the group consisting of an alkylene oxide structure of 1 or more-CH ₂ -substituted with-O-, an ester structure of 1 or more-CH ₂-CH₂ -substituted with-O-and-C (=0) -and an urethane bond of 1 or more-CH ₂-CH₂-CH₂ -substituted with-O-, -C (=0) -and-NH-and constituting an alkylene group.

The hydrogen atom contained in at least 1-CH ₂ -constituting the alkylene group represented by SP4 may be replaced with "SP-H" as described above. In this case, 1 or more hydrogen atoms contained in-CH ₂ -may be replaced by "SP-H". That is, only 1 hydrogen atom contained in-CH ₂ -may be replaced with "SP-H", or all (2) hydrogen atoms contained in-CH ₂ -may be replaced with "SP-H".

In "SP-H", at least 1 group selected from the group consisting of a halogen atom, a cyano group, a nitro group, a hydroxyl group, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, and a haloalkyl group having 1 to 10 carbon atoms is preferable, and at least 1 group selected from the group consisting of a hydroxyl group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 1 to 10 carbon atoms is more preferable.

As described above, T4 represents the same terminal group as T1, and is preferably a hydrogen atom, a methyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boric acid group, an amino group, a cyano group, a nitro group, or a phenyl group which may have a substituent, -L-CL (L represents a single bond or a divalent linking group; specific examples of the divalent linking group are the same as LW and SPW described above; CL represents a crosslinkable group, and examples thereof include groups represented by the above Q1 or Q2, and are preferably crosslinkable groups represented by the formulae (P1) to (P30)), and as the CL, vinyl, butadienyl, (meth) acrylic acid group, (meth) acrylamide group, vinyl acetate group, fumarate group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, vinyl ether group, epoxy group, or oxetanyl group are preferable.

The epoxy group may be an epoxycycloalkyl group, and the number of carbon atoms of the cycloalkyl moiety in the epoxycycloalkyl group is preferably 3 to 15, more preferably 5 to 12, and particularly preferably 6 (i.e., when the epoxycycloalkyl group is epoxycyclohexyl), from the viewpoint of more excellent effects of the present invention.

Examples of the substituent of the oxetanyl group include an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable from the viewpoint of further excellent effects of the present invention. The alkyl group as a substituent of the oxetanyl group may be linear or branched, and is preferably linear from the viewpoint of further excellent effect of the present invention.

Examples of the substituent for the phenyl group include a boric acid group, a sulfonic acid group, a vinyl group and an amino group, and a boric acid group is preferable from the viewpoint of further excellent effects of the present invention.

Specific examples of the repeating unit (4) include the following structures, but the present invention is not limited to these. In the following specific examples, n1 represents an integer of 2 or more, and n2 represents an integer of 1 or more.

[ Chemical formula 32]

The content of the repeating unit (4) is preferably 2 to 20 mass%, more preferably 3 to 18 mass%, based on the total repeating unit (100 mass%) of the polymer liquid crystalline compound. When the content of the repeating unit (4) is 2 mass% or more, a light absorbing anisotropic layer having more excellent adhesion can be obtained. Further, when the content of the repeating unit (4) is 20 mass% or less, a light absorbing anisotropic layer having more excellent planar uniformity can be obtained.

The polymer liquid crystalline compound may contain 1 kind of repeating unit (4) alone or 2 or more kinds of repeating units (4). When the repeating unit (4) is contained in an amount of 2 or more, the content of the repeating unit (4) means the total content of the repeating units (4).

< Repeating unit (5) >

From the viewpoint of planar uniformity, the polymer liquid crystalline compound may contain a repeating unit (5) introduced by polymerizing a polyfunctional monomer. In particular, in order to suppress the decrease in the degree of orientation and to improve the planar uniformity, it is preferable that the repeating unit (5) introduced by polymerizing the polyfunctional monomer is contained in an amount of 10 mass% or less. As a reason why the reduction of the degree of orientation and the improvement of the planar uniformity are suppressed by containing 10 mass% or less of the repeating unit (5), the following is estimated.

The repeating unit (5) is a unit obtained by introducing a polyfunctional monomer into a polymer liquid crystalline compound by polymerizing the polyfunctional monomer. Therefore, it is considered that the polymer liquid crystalline compound contains a high molecular weight body having a three-dimensional crosslinked structure formed by the repeating unit (5). Here, it is considered that the content of the repeating unit (5) is small, and therefore the content of the high molecular weight body containing the repeating unit (5) is small.

In this way, it is presumed that the light absorbing anisotropic layer having excellent planar uniformity can be obtained by suppressing the repulsion of the liquid crystal composition by the presence of a small amount of the high molecular weight body having the three-dimensional crosslinked structure formed therein.

Further, it is presumed that the effect of suppressing the decrease in the degree of orientation can be maintained because the content of the high molecular weight body is small.

The repeating unit (5) introduced by polymerizing the polyfunctional monomer is preferably a repeating unit represented by the following formula (5).

[ Chemical formula 33]

In the formula (5), PC5A and PC5B represent the main chain of the repeating unit, more specifically, the same structure as PC1 in the formula (1), L5A and L5B represent a single bond or a divalent linking group, more specifically, the same structure as L1 in the formula (1), SP5A and SP5B represent a spacer group, more specifically, the same structure as SP1 in the formula (1), MG5A and MG5B represent a mesogenic structure, more specifically, the same structure as the mesogenic group MG in the formula (LC), and a and B represent integers of 0 or 1.

The PC5A and the PC5B may be the same group or may be different groups, but are preferably the same group from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

Both L5A and L5B may be single bonds, may be the same groups, or may be different groups, but are preferably single bonds or the same groups, and more preferably the same groups, from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

The SP5A and the SP5B may each be a single bond, the same group, or different groups, but are preferably both single bonds or the same group, and more preferably the same group, from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

Here, the same group in formula (5) means that the chemical structures are the same regardless of the orientation to which each group is bonded, for example, when SP5A is CH ₂-CH₂ -O-material (where SP5A represents a bonding position to L5A and SP5B is CH ₂-CH₂ — (where SP represents a bonding position to MG5B and L5B).

A and b are each independently an integer of 0 or 1, and are preferably 1 from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

A and b may be the same or different, but are preferably each 1 from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

From the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer, the total of a and b is preferably 1 or 2 (i.e., the repeating unit represented by formula (5) has a mesogenic group), more preferably 2.

From the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer, the partial structure represented by- (MG 5A) _a-(MG5B)_b -preferably has a ring structure. In this case, the number of ring structures in the partial structure represented by- (MG 5A 2) _a-(MG5B)_b -is preferably 2 or more, more preferably 2 to 8, still more preferably 2 to 6, particularly preferably 2 to 4, from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

From the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer, the mesogenic groups represented by MG5A and MG5B each independently preferably contain 1 or more cyclic structures, preferably contain 2 to 4 cyclic structures, more preferably contain 2 to 3 cyclic structures, and particularly preferably contain 2 cyclic structures.

Specific examples of the cyclic structure include an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group, and among them, an aromatic hydrocarbon group and an alicyclic group are preferable.

MG5A and MG5B may be the same group or may be different groups, but are preferably the same group from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer.

The mesogenic groups represented by MG5A and MG5B are preferably mesogenic groups MG in the above formula (LC) from the viewpoints of appearance of liquid crystal properties, adjustment of liquid crystal phase transition temperature, raw material availability and synthesis suitability, and further from the viewpoint of more excellent effects of the present invention.

In particular, regarding the repeating unit (5), it is preferable that PC5A and PC5B are the same group, L5A and L5B are both single bonds or the same group, and SP5A and SP5B are both single bonds or the same group, and MG5A and MG5B are the same group. This further improves the degree of orientation of the light absorbing anisotropic layer.

The content of the repeating unit (5) is preferably 10 mass% or less, more preferably 0.001 to 5 mass%, and even more preferably 0.05 to 3 mass%, based on the total content (100 mass%) of the repeating units of the polymer liquid crystalline compound.

The polymer liquid crystalline compound may contain 1 kind of repeating unit (5) alone or 2 or more kinds of repeating units (5). When the repeating unit (5) is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.

The polymer liquid crystalline compound may be a star polymer. The star polymer in the present invention is a polymer having 3 or more polymer chains extending from a core, and specifically, is represented by the following formula (6).

The star polymer represented by the formula (6) as a high molecular liquid crystalline compound has high solubility (excellent solubility in a solvent) and can form a light absorbing anisotropic layer having a high degree of orientation.

[ Chemical formula 34]

In formula (6), n _A represents an integer of 3 or more, preferably an integer of 4 or more. The upper limit of n _A is not limited thereto, but is usually 12 or less, preferably 6 or less.

Each of the plurality of P1's independently represents a polymer chain containing any one of the repeating units represented by the above formulas (1), (21), (22), (3), (4), (5). Wherein at least one of the PIs represents a polymer chain containing a repeating unit represented by the above formula (1).

A represents an atomic group serving as a core of the star polymer. Specific examples of A include structures obtained by removing hydrogen atoms from thiol groups of polyfunctional thiol compounds described in paragraphs [0052] to [0058] of JP 2011-074280, paragraphs [0017] to [0021] of JP 2012-189847, paragraphs [0012] to [0024] of JP 2013-031986, and paragraphs [0118] to [0142] of JP 2014-104631. At this time, a is bonded to PI through a thioether bond.

The number of thiol groups of the polyfunctional thiol compound which becomes a source of a is preferably 3, more preferably 4. The upper limit of the number of thiol groups of the polyfunctional thiol compound is usually 12 or less, preferably 6 or less.

Specific examples of the polyfunctional thiol compound are shown below.

[ Chemical formula 35]

From the viewpoint of improving the degree of orientation, the polymer liquid crystalline compound may be a thermotropic liquid crystal, and may be a crystalline polymer.

The thermotropic liquid crystal is a liquid crystal that exhibits a transition to a liquid crystal phase by a temperature change.

The specific compound is a thermotropic liquid crystal, and may exhibit either a nematic phase or a smectic phase, but it is preferable to exhibit at least a nematic phase from the viewpoint that the degree of orientation of the light absorbing anisotropic layer becomes higher and the haze becomes more difficult to observe (the haze becomes better).

Since the degree of orientation of the light absorbing anisotropic layer becomes higher and the haze becomes more difficult to observe, the temperature range showing the nematic phase is preferably (23 ℃) to 450 ℃, more preferably 40 ℃ to 400 ℃ from the viewpoint of handling or manufacturing applicability.

The crystalline polymer is a polymer that shows transition to the crystalline layer according to a temperature change. In addition to the transition to the crystalline layer, the crystalline polymer may be a polymer exhibiting glass transition.

Since the degree of orientation of the light absorbing anisotropic layer becomes higher and the haze becomes more difficult to observe, the crystalline polymer is preferably a polymer liquid crystalline compound having a transition from a crystal phase to a liquid crystal phase (may have a glass transition in the middle) when heated or a polymer liquid crystalline compound having a transition to a crystal phase (may have a glass transition in the middle) when the temperature is lowered after being brought into a liquid crystal state by heating.

The presence or absence of crystallinity of the polymer liquid crystalline compound was evaluated as follows.

Two light-absorbing anisotropic layers of an optical microscope (NIKON co., ltd. ECLIPSE E600 POL) were arranged in a mutually orthogonal manner, and a sample stage was provided between the two light-absorbing anisotropic layers. Then, a small amount of a polymer liquid crystalline compound was placed on the slide glass, and the slide glass was set on a hot stage placed on the sample stage. While observing the state of the sample, the temperature of the heat stage is raised to a temperature at which the polymer liquid crystalline compound exhibits liquid crystallinity, thereby bringing the polymer liquid crystalline compound into liquid crystalline state. After the polymer liquid crystalline compound is brought into a liquid crystal state, the state of liquid crystal phase transition is observed while gradually lowering the temperature of the heat stage, and the temperature of liquid crystal phase transition is recorded. In addition, if the polymer liquid crystalline compound exhibits a plurality of liquid crystal phases (for example, a nematic phase and a smectic phase), the transition temperatures thereof are also all recorded.

Next, about 5mg of the polymer liquid crystalline compound sample was placed in an aluminum pan, covered with a lid, and set in a Differential Scanning Calorimeter (DSC) (an empty aluminum pan was used as a reference). The polymer liquid crystalline compound measured in the above was heated to a temperature showing a liquid crystal phase, and then the temperature was maintained for 1 minute. Then, while the temperature was lowered at a rate of 10 ℃ per minute, the heat was measured. The heating peak was confirmed from the obtained heat spectrum.

As a result, when a heat generation peak is observed at a temperature other than the temperature at which the liquid crystal changes phase, the heat generation peak is a peak generated by crystallization, and it can be said that the polymer liquid crystalline compound has crystallinity.

On the other hand, when no heat generation peak is observed at a temperature other than the temperature at which the liquid crystal phase changes, it can be said that the polymer liquid crystalline compound does not have crystallinity.

The method for obtaining the crystalline polymer is not particularly limited, and a method using a polymer liquid crystalline compound containing the repeating unit (1) is preferable as a specific example, and among them, a method using a preferable mode among polymer liquid crystalline compounds containing the repeating unit (1) is more preferable.

Crystallization temperature

Since the degree of orientation of the light absorbing anisotropic layer becomes higher and the haze becomes more difficult to observe, the crystallization temperature of the polymer liquid crystalline compound is preferably-50 ℃ or higher and less than 150 ℃, more preferably 120 ℃ or lower, further preferably-20 ℃ or higher and less than 120 ℃, and particularly preferably 95 ℃ or lower. From the viewpoint of reducing haze, the crystallization temperature of the polymer liquid crystalline compound is preferably less than 150 ℃.

The crystallization temperature is a temperature of a heat generation peak generated by crystallization in the DSC described above.

From the viewpoint of further excellent effects of the present invention, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 1000 to 500000, more preferably 2000 to 300000. When the Mw of the polymer liquid crystalline compound is within the above range, the polymer liquid crystalline compound can be handled easily.

In particular, from the viewpoint of suppressing cracks at the time of coating, the weight average molecular weight (Me) of the polymer liquid crystalline compound is preferably 10000 or more, more preferably 10000 to 300000.

From the viewpoint of the temperature range (temperature latitude) of the degree of orientation, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably less than 10000, preferably 2000 or more and less than 10000.

Solvent (eluent): n-methylpyrrolidone

Device name: TOSOH HLC-8220GPC

Tubular column: 3 TOSOH TSKgelSuperAWM-H (6 mm. Times.15 cm) were used in conjunction with each other

Column temperature: 25 DEG C

Sample concentration: 0.1 mass%

Flow rate: 0.35 ml/min

The liquid crystallinity of the polymer liquid crystalline compound may exhibit any of nematic and smectic properties, but preferably exhibits at least nematic properties.

The temperature range showing the nematic phase is preferably 0 to 450 ℃, and from the viewpoint of handling or manufacturing applicability, it is preferably 30 to 400 ℃.

From the viewpoint of further excellent effects of the present invention, the content of the liquid crystalline compound is preferably 10 to 97% by mass, more preferably 40 to 95% by mass, and even more preferably 60 to 95% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition.

When the liquid crystalline compound contains a polymer liquid crystalline compound, the content of the polymer liquid crystalline compound is preferably 10 to 99 mass%, more preferably 30 to 95 mass%, and even more preferably 40 to 90 mass% based on the total mass (100 parts by mass) of the liquid crystalline compound.

When the liquid crystalline compound contains a low molecular weight liquid crystalline compound, the content of the low molecular weight liquid crystalline compound is preferably 1 to 90 mass%, more preferably 5 to 70 mass%, and even more preferably 10 to 60 mass% relative to the total mass (100 parts by mass) of the liquid crystalline compound.

When the liquid crystalline compound contains both the high molecular liquid crystalline compound and the low molecular liquid crystalline compound, the mass ratio of the content of the low molecular liquid crystalline compound to the content of the high molecular liquid crystalline compound (low molecular liquid crystalline compound/high molecular liquid crystalline compound) is preferably 5/95 to 70/30, more preferably 10/90 to 50/50, from the viewpoint of further excellent effects of the present invention.

The "solid component in the liquid crystal composition" refers to a component other than a solvent, and specific examples of the solid component include the liquid crystalline compound, a dichroic material described later, a polymerization initiator, a surface modifier, and the like.

< Dichroic substance >

The liquid crystal composition further contains a dichroic substance.

In the present invention, the dichroic material means a dye having absorbance different depending on the direction. The dichroic material may or may not exhibit liquid crystallinity.

The dichroic material is not particularly limited, and examples thereof include a visible light absorbing material (dichroic dye), a light emitting material (fluorescent material, phosphorescent material), an ultraviolet absorbing material, an infrared absorbing material, a nonlinear optical material, carbon nanotubes, an inorganic material (e.g., quantum rod), and the like, and a conventionally known dichroic material (dichroic dye) can be used.

In the present invention, the dichroic substance is preferably a dichroic azo dye compound.

The dichroic azo dye compound is not particularly limited, and conventionally known dichroic azo dyes can be used.

Further, when the dichroic azo dye compound exhibits liquid crystallinity, either nematic property or smectic property may be exhibited. The temperature range showing the liquid crystal phase is preferably room temperature (about 20 ℃ to 28 ℃) and 300 ℃, and more preferably 50 to 200 ℃ from the viewpoints of handleability and manufacturing applicability.

As the dichroic substance, specifically, for example, examples thereof include paragraphs [0067] to [0071] of Japanese patent application laid-open No. 2013-228706, paragraphs [0008] to [0026] of Japanese patent application laid-open No. 2013-227532, paragraphs [0008] to [0015] of Japanese patent application laid-open No. 2013-209367, paragraphs [0045] to [0058] of Japanese patent application laid-open No. 2013-109090, paragraphs [0012] to [0029] of Japanese patent application laid-open No. 2013-109090, paragraphs [0009] to [0017] of Japanese patent application laid-open No. 2013-101328, paragraphs [0051] to [0065] of Japanese patent application laid-open No. 2012-63387 ] to [ 00473 ], paragraphs [0016] to [0018] of Japanese patent application laid-open No. 20111-305036, paragraphs [0009] to [ 003630 ], and paragraphs [0009] to [0011] of Japanese patent application laid-open No. 2013-101328, and [ 2011 ] to [ 2159 ] of Japanese patent application laid-open No. 2012. Paragraph [0021] to [0075] of Japanese patent application laid-open No. 2010-106242, paragraph [0011] to [0025] of Japanese patent application laid-open No. 2010-215846, paragraph [0017] to [0069] of Japanese patent application laid-open No. 2011-048311, paragraph [0013] to [0133] of Japanese patent application laid-open No. 2011-213610, paragraph [0074] to [0246] of Japanese patent application laid-open No. 2011-237513, paragraph [0005] to [00051] of Japanese patent application laid-open No. 2016-006502, paragraph [0014] to [0032] of Japanese patent application laid-open No. 2018-053167, paragraph [0014] to [0014] of Japanese patent application laid-open No. 2020-11716, paragraph [ 2016/060173 ], paragraph [0005] to [0008] of International patent application laid-open No. 2017/154835, paragraph [ 20114 ] to [0034] of International patent application laid-open No. 2015/0033, and paragraph [ 0035 ] of International patent application laid-open No. 2017/003835 Paragraphs [00013] to [0037] of International publication No. 2017/195833, paragraphs [00014] to [0034] of International publication No. 2018/164252, paragraphs [0021] to [0030] of International publication No. 2018/186503, paragraphs [0043] to [0063] of International publication No. 2019/189345, paragraphs [0043] to [0085] of International publication No. 2019/225468, paragraphs [0050] to [0074] of International publication No. 2020/004106, and paragraphs [0015] to [0038] of International publication No. 2021/044843, and the like.

As a technique for aligning a dichroic material in a desired direction, a technique for producing a polarizer using a dichroic material, a technique for producing a guest-host liquid crystal cell, or the like can be referred to.

For example, a method of producing a dichroic polarizing element described in japanese patent application laid-open No. 11-305036 or japanese patent application laid-open No. 2002-90526 can be used; a method for manufacturing a guest-host liquid crystal display device described in Japanese patent application laid-open No. 2002-99388 or 2016-27387; the technique used in the present invention is used for the production of the light absorbing anisotropic layer.

Specifically, in the case of a technique using a guest-host liquid crystal cell, a dichroic material serving as a guest and a rod-like liquid crystalline compound serving as a host liquid crystal are mixed, the host liquid crystal is aligned, and the molecules of the dichroic material are aligned along the alignment of the liquid crystal molecules, whereby the alignment state is fixed, whereby the light absorbing anisotropic layer of the present invention can be produced.

In order to prevent the light absorption characteristics of the light absorption anisotropic layer of the present invention from being changed by the influence of the use environment, it is preferable to fix the orientation of the dichroic substance by the formation of chemical bonds. For example, the alignment can be fixed by polymerizing the host liquid crystal, the dichroic material, and the polymerizable component added as needed.

In the present invention, 2 or more dichroic materials, preferably 3 or more dichroic materials, may be used in combination.

When 2 or more dichroic materials are used in combination, for example, from the viewpoint that the contrast ratio becomes higher and the change in hue with respect to the original image can be further suppressed for the reflected image to the surroundings when used in a viewing angle control system, it is preferable to use at least 1 dichroic material having a maximum absorption wavelength in the range of 370 to 550nm and at least 1 dichroic material having a maximum absorption wavelength in the range of 500 to 700nm in combination.

When 3 or more dichroic materials are used in combination, it is more preferable to use at least 1 dichroic material having a maximum absorption wavelength in a range of from 560 to 700nm, at least 1 dichroic material having a maximum absorption wavelength in a range of from 455 to less than 560nm, and at least 1 dichroic material having a maximum absorption wavelength in a range of from 370 to less than 455nm for the same reason as described above.

Among them, examples of at least 1 dichroic material having a maximum absorption wavelength in a wavelength range of 560 to 700nm include a compound represented by formula (1) described in paragraph [0043] of the international publication No. 2019/189345, and examples of at least 1 dichroic material having a maximum absorption wavelength in a wavelength range of 455 to less than 560nm include a compound represented by formula (2) described in paragraph [0054] of the international publication No. 2019/189345.

The content of the dichroic substance is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and even more preferably 15 to 20% by mass, based on the total solid content mass of the liquid crystal composition.

When the content of the dichroic material is 5 mass% or more, the contrast ratio becomes higher, and when the content of the dichroic material is 30 mass% or less, the planar uniformity becomes better.

< Solvent >

From the viewpoint of handleability, the liquid crystal composition preferably contains a solvent.

Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetylacetone, etc.), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, cyclopentylmethyl ether, dibutyl ether, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, tetrahydronaphthalene, trimethylbenzene, etc.), halocarbons (e.g., methylene chloride, chloroform, dichloroethane, dichlorobenzene, 1, 2-tetrachloroethane, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, diethyl carbonate, ethyl acetoacetate, N-pentyl acetate, ethyl benzoate, benzyl benzoate, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, isoamyl acetate, and the like), alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, furfuryl alcohol, 2-ethylhexanol, octanol, benzyl alcohol, ethanolamine, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like), phenols (e.g., phenol, cresol, and the like), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, and 1, 2-dimethoxyethane, and the like), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, and the like), amides (e.g., dimethylformamide and dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1, 3-dimethyl-2-imidazolidone, etc.) and heterocyclic compounds (e.g., pyridine, 2, 6-lutidine, etc.) and water.

These solvents may be used alone or in combination of 2 or more.

When the liquid crystal composition contains a solvent, the content of the solvent is preferably 60 to 99.5% by mass, more preferably 70 to 99% by mass, particularly preferably 75 to 98% by mass, relative to the total mass (100% by mass) of the liquid crystal composition.

< Alignment agent >

The liquid crystal composition preferably contains an aligning agent.

Examples of the alignment agent include those described in paragraphs [0042] to [0076] of JP-A2013-543526, paragraphs [0089] to [0097] of JP-A2016-523997, and paragraphs [0153] to [0170] of JP-A2020-076920, and these may be used singly or in combination of 1 or 2 or more.

In the present invention, the alignment agent is preferably an onium compound represented by the following formula (B1) for the reason that the contrast ratio is higher.

[ Chemical formula 36]

In the above formula (B1), the ring a represents a ring structure having a cationized nitrogen atom.

And X represents an anion.

And, L ¹ represents a divalent linking group.

And L ² represents a single bond or a divalent linking group.

And Y ¹ represents a divalent linking group having a 5-membered ring or a 6-membered ring as a partial structure.

Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure.

P ¹ and P ² each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated bond.

Ring a represents a ring structure having a cationized nitrogen atom.

X represents an anion. Examples of X include halogen anions (e.g., fluoride ion, chloride ion, bromide ion, iodide ion, etc.), sulfonate ions (e.g., methanesulfonate ion, trifluoromethanesulfonate ion, methylsulfate ion, vinylsulfonate ion, allylsulfonate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, p-vinylbenzenesulfonate ion, 1, 3-benzenedisulfonate ion, 1, 5-naphthalenedisulfonate ion, 2, 6-naphthalenedisulfonate ion, etc.), sulfate ion, carbonate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, bittering ion, acetate ion, benzoate ion, p-vinylbenzoate ion, formate ion, trifluoroacetate ion, phosphate ion (e.g., hexafluorophosphate ion), hydroxide ion, etc. Preferably a halogen anion, a sulfonate ion, and a hydroxide ion. In addition, chloride ion, bromide ion, iodide ion, methanesulfonate ion, vinylsulfonate ion, p-toluenesulfonate ion, and p-vinylbenzenesulfonate ion are particularly preferable.

L ¹ represents a divalent linking group. Examples of L ¹ include divalent linking groups having 1 to 20 carbon atoms, each of which is composed of a combination of an alkylene group, -O-, -S-, -CO-, -SO ₂ -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, an alkynylene group, or an arylene group. L ¹ is preferably-AL-having 1 to 10 carbon atoms-O-AL-, -CO-O-AL-, -O-CO-AL-, -and/or-O-CO-AL-, further, it is preferable that the carbon number is-AL-, -O-AL-, most preferred are-AL-, -O-AL-having 1 to 5 carbon atoms. In addition, AL represents an alkylene group.

L2 represents a single bond or a divalent linking group. Examples of L ² include a divalent linking group having 1 to 10 carbon atoms, which is a combination of an alkylene group, -O-, -S-, -CO-, -SO ₂ -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, an alkynylene group, or an arylene group, a single bond 、-O-、-O-CO-、-CO-O-、-O-AL-O-、-O-AL-O-CO-、-O-AL-CO-O-、-CO-O-AL-O-、-CO-O-AL-O-CO-、-CO-O-AL-CO-O-、-O-CO-AL-O-、-O-CO-AL-O-CO-、-O-CO-AL-CO-O-, and the like. In addition, AL represents an alkylene group. L2 is preferably a single bond, an-AL-having 1 to 10 carbon atoms-O-AL-, -NRa-AL-O-, -and more preferably a single bond, an-AL-having 1 to 5 carbon atoms-O-AL-, -NRa-AL-O-, -and-O-AL-, -NRa-AL-O-.

Y ¹ represents a divalent linking group having a 5-membered ring or a 6-membered ring as a partial structure. Examples of Y ¹ include a cyclohexyl ring, an aromatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring, and a benzene ring, a biphenyl ring, and a naphthalene ring are particularly preferable. The hetero atom constituting the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and examples thereof include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, a pyrazoline ring, a pyrazolidine ring, a triazole ring, a furazan ring, a tetrazole ring, a pyran ring, a dioxane ring, a dithiane ring, a thiopyran ring, a pyridine ring, a piperidine ring, an oxazine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, a triazine ring or the like. The heterocycle is preferably a 6 membered ring. The divalent linking group having a 5-membered ring or 6-membered ring represented by Y ¹ as a partial structure may also have a substituent (for example, the substituent W described above).

The divalent linking group represented by Y ¹ is preferably a divalent linking group having 2 or more 5-membered or 6-membered rings, more preferably a structure in which 2 or more rings are linked through a linking group. Examples of the linking group include linking groups represented by L1 and L2, and examples of the linking groups include-c≡c-, -ch=ch-, -ch=n-, -n=ch-, -n=n-, and the like.

Z represents an alkylene group having 2 to 20 carbon atoms as a partial structure and is represented by-O-; a divalent linking group consisting of a combination of S-, -CO-, -SO2-, the alkylene group may have a substituent. Examples of the divalent linking group include an alkyleneoxy group and a polyalkyleneoxy group. The number of carbon atoms of the alkylene group represented by Z is more preferably 2 to 16, still more preferably 2 to 12, particularly preferably 2 to 8.

P1 and P2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated group. Examples of the monovalent substituent having a polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-8). That is, the monovalent substituent having a polymerizable ethylenically unsaturated group may be a substituent composed of only a vinyl group as in (M-8).

[ Chemical formula 37]

In the formulae (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. In the above formulae (M-1) to (M-8), the formulae (M-1), (M-2) and (M-8) are preferable, and the formulae (M-1) and (M-8) are more preferable. In particular, as P1, (M-1) is preferable. Further, as P2, (M-1) or (M-8) is preferable, P2 is preferably (M-8) or (M-1) in the compound in which ring A is a quaternary imidazolium ion, and P2 is preferably (M-1) in the compound in which ring A is a quaternary pyridinium ion.

Examples of the onium compound represented by the above formula (B1) include onium salts described in paragraphs 0052 to 0058 of japanese unexamined patent application publication No. 2012-208397, onium salts described in paragraphs 0024 to 0055 of japanese unexamined patent application publication No. 2008-026730, and onium salts described in japanese unexamined patent application publication No. 2002-37777.

In the present invention, the alignment agent is preferably a boric acid compound represented by the following formula (B2) for the reason that the contrast ratio is higher.

[ Chemical formula 38]

In the above (B2), R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.

And, R ³ represents a substituent.

Examples of the aliphatic hydrocarbon group represented by one embodiment of R ¹ and R ² include a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group, etc.), a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms (for example, cyclohexyl group, etc.), and an alkenyl group having 2 to 20 carbon atoms (for example, vinyl group, etc.).

Examples of the aryl group represented by one embodiment of R ¹ and R ² include a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms (for example, phenyl group, tolyl group, etc.), a substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms, etc.

Examples of the heterocyclic group represented by one embodiment of R ¹ and R ² include a substituted or unsubstituted 5-or 6-membered ring group containing at least one heteroatom (for example, nitrogen atom, oxygen atom, sulfur atom, etc.), and specifically include pyridyl, imidazolyl, furyl, piperidyl, morpholinyl, etc.

R ¹ and R ² may be linked to each other to form a ring, for example, the isopropyl groups of R ¹ and R ² may be linked to form 4, 5-tetramethyl-1, 3, 2-dioxaborolan.

R ¹ and R ² are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a ring formed by connecting them, and more preferably a hydrogen atom.

The substituent represented by R ³ is preferably a substituent containing a functional group capable of bonding to a (meth) acrylic group.

Examples of the functional group capable of bonding to the (meth) acrylic group include a vinyl group, an acrylate group, a methacrylate group, an acrylamide group, a styryl group, a ketene group, a butadienyl group, a vinyl ether group, an ethylene oxide group, an aziridine group, and an oxetanyl group, and among them, a vinyl group, an acrylate group, a methacrylate group, a styrene group, an ethylene oxide group, and an oxetanyl group are preferable, and a vinyl group, an acrylate group, an acrylamide group, and a styryl group are more preferable.

As R ³, a substituted or unsubstituted aliphatic hydrocarbon group, aryl group, or heterocyclic group having a functional group capable of bonding to a (meth) acrylic group is preferable.

Examples of the aliphatic hydrocarbon group include a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-methylhexyl and the like), a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms (for example, cyclopentyl, cyclohexyl, 1-adamantyl, 2-norbornyl and the like), and an alkenyl group having 2 to 20 carbon atoms (for example, vinyl, 1-propenyl, 1-butenyl, 1-methyl-1-propenyl and the like).

Examples of the aryl group include a substituted or unsubstituted phenyl group having 6 to 50 carbon atoms (for example, phenyl group, tolyl group, styryl group, 4-benzoyloxyphenyl group, 4-phenoxycarbonylphenyl group, 4-biphenyl group, 4- (4-octyloxybenzoyloxy) phenoxycarbonylphenyl group and the like), a substituted or unsubstituted naphthyl group having 10 to 50 carbon atoms (for example, unsubstituted naphthyl group and the like).

Examples of the heterocyclic group include a substituted or unsubstituted 5-or 6-membered ring group containing at least one hetero atom (for example, nitrogen atom, oxygen atom, sulfur atom, etc.), and examples thereof include groups such as pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thiaindene, dibenzothiophene, indazole benzimidazole, benzoylimine, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine, morpholine, piperidine, and the like.

Examples of the boric acid compound represented by the above formula (B2) include boric acid compounds represented by the general formula (I) described in paragraphs 0023 to 0032 of jp 2008-225281 a.

As the compound represented by the above formula (B2), the following compounds are preferable.

[ Chemical formula 39]

The aligning agent may be at least 1 compound selected from the group consisting of nonionic silane compounds and ionic compounds, in addition to the compounds represented by the formula (B1) or (B2).

Here, the ionic compound is not contained in the compound represented by the formula (B1).

Examples of the nonionic silane compound include nonionic silane compounds described in paragraphs [0035] to [0039] of JP-A2020-181150.

The ionic compound described in paragraphs [0017] to [0029] of JP 2020-181150 may be mentioned.

When the liquid crystal composition contains an aligning agent, the content of the aligning agent is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, relative to 100 parts by mass of the total of the liquid crystal compound and the dichroic material contained in the liquid crystal composition.

< Polymerization initiator >

The liquid crystal composition may contain a polymerization initiator.

The polymerization initiator is not particularly limited, but is preferably a photopolymerization initiator which is a compound having photosensitivity.

As the photopolymerization initiator, various compounds can be used without particular limitation. Examples of the photopolymerization initiator include an α -carbonyl compound (U.S. Pat. No. 2367661 and U.S. Pat. No. 2367670), an acyloin ether (U.S. Pat. No. 2448828), a d-hydrocarbon substituted aromatic acyloin compound (U.S. Pat. No. 2722512), a polynuclear quinone compound (U.S. Pat. No. 3046127 and U.S. Pat. No. 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (U.S. Pat. No. 3549367), an acridine and phenazine compound (Japanese patent application laid-open No. 60-105667 and U.S. Pat. No. 4239850), an oxadiazole compound (Japanese patent application laid-open No. 4212970), an orthoacyloxime compound (Japanese patent application laid-open No. 2016-27384 [0065 ]), and an acylphosphine oxide compound (Japanese patent application laid-open No. 63-40799, japanese patent application laid-open No. 5-29234, japanese patent application laid-open No. 10-95788 and Japanese patent application laid-open No. 10-29997).

As such photopolymerization initiators, commercially available ones can be used, and examples thereof include IRGACURE-184, IRGACURE-907, IRGACURE-369, IRGACURE-651, IRGACURE-819, IRGACURE-OXE-01, IRGACURE-OXE-02, etc. manufactured by BASF corporation.

When the liquid crystal composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content mass of the liquid crystal composition.

< Polymerizable Compound >

The liquid crystal composition may contain a polymerizable compound.

Examples of the polymerizable compound include compounds containing an acrylic acid ester (for example, (meth) acrylic acid ester monomers, and the like).

When the liquid crystal composition contains a polymerizable compound, the content of the polymerizable compound is preferably 0.5 to 50% by mass, more preferably 1.0 to 40% by mass, relative to the total solid content mass of the liquid crystal composition.

[ Method for Forming light absorbing Anisotropic layer ]

The method for forming the light absorbing anisotropic layer of the present invention is not particularly limited, and examples thereof include the following steps in order: a step of forming a coating film by applying the liquid crystal composition (hereinafter, also referred to as a "composition for forming a light-absorbing anisotropic layer"); and a step of aligning the liquid crystalline component or the dichroic material contained in the coating film (hereinafter, also referred to as an "alignment step").

The liquid crystalline component is a component that contains not only the liquid crystalline compound but also a dichroic substance having liquid crystallinity when the dichroic substance has liquid crystallinity.

< Coating film Forming Process >

The coating film forming step is a step of forming a coating film by applying the composition for forming a light absorbing anisotropic layer.

The composition for forming a light-absorbing anisotropic layer can be easily applied by using the composition for forming a light-absorbing anisotropic layer containing the above-mentioned solvent or using a substance in which the composition for forming a light-absorbing anisotropic layer is formed into a liquid material such as a melt by heating or the like.

Specific examples of the method for applying the composition for forming the light-absorbing anisotropic layer include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

< Alignment procedure >

The alignment step is a step of aligning the liquid crystal component contained in the coating film. Thus, a light absorbing anisotropic layer can be obtained.

The orientation process may include a drying process. The drying treatment can remove components such as a solvent from the coating film. The drying treatment may be performed by a method (for example, natural drying) of leaving the coating film at room temperature for a predetermined time, or may be performed by a method of heating and/or air blowing.

Here, the liquid crystalline component contained in the composition for forming a light absorbing anisotropic layer may be oriented by the coating film forming step or the drying treatment. For example, in a mode of preparing the composition for forming a light absorbing anisotropic layer as a coating liquid containing a solvent, a coating film having light absorbing anisotropy (i.e., a light absorbing anisotropic layer) is obtained by drying the coating film to remove the solvent from the coating film.

When the drying treatment is performed at a temperature equal to or higher than the transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase, the heating treatment described later may not be performed.

The transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase is preferably 10 to 250 ℃, more preferably 25 to 190 ℃, from the viewpoint of manufacturing applicability and the like. If the transition temperature is 10 ℃ or higher, it is not necessary to perform a cooling treatment or the like for reducing the temperature to a temperature range in which the liquid crystal phase is present, and thus it is preferable. Further, when the above-mentioned transition temperature is 250 ℃ or lower, even when the liquid crystalline component is brought into an isotropic liquid state at a temperature higher than the temperature range in which the liquid crystalline phase is temporarily present, a high temperature is not required, and therefore waste of heat energy, deformation and deterioration of the substrate, and the like can be reduced, which is preferable.

The orientation process preferably includes a heat treatment. In this way, the liquid crystalline component contained in the coating film can be oriented, and therefore, the coating film after the heat treatment can be preferably used as the light absorbing anisotropic layer.

The heat treatment is preferably 10 to 250℃and more preferably 25 to 190℃in view of the production suitability and the like. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

The orientation process may include a cooling process performed after the heating process. The cooling treatment is a treatment of cooling the heated coating film to about room temperature (20 to 25 ℃). This fixes the orientation of the liquid crystal component contained in the coating film. The cooling method is not particularly limited, and can be performed by a known method.

Through the above steps, a light absorbing anisotropic layer can be obtained.

In the present embodiment, the method of aligning the liquid crystalline component contained in the coating film includes a drying process, a heating process, and the like, but is not limited to these, and can be performed by a known alignment process.

< Other procedure >

The method of forming the light absorbing anisotropic layer may include a step of curing the light absorbing anisotropic layer after the above-described orientation step (hereinafter, also referred to as a "curing step").

For example, when the light absorbing anisotropic layer has a crosslinkable group (polymerizable group), the curing step is performed by heating and/or light irradiation (exposure). Among them, the curing step is preferably performed by light irradiation.

The light source used for curing may be any of various light sources such as infrared light, visible light and ultraviolet light, but ultraviolet light is preferable. The ultraviolet ray may be irradiated while heating during curing, or may be irradiated through a filter transmitting only a specific wavelength.

In the case of performing exposure while heating, the heating temperature at the time of exposure depends on the transition temperature of the liquid crystalline component contained in the liquid crystal film to the liquid crystal phase, but is preferably 25 to 140 ℃.

Also, the exposure may be performed under a nitrogen atmosphere. When curing the liquid crystal film by radical polymerization, the inhibition of polymerization by oxygen is reduced, and therefore, exposure under a nitrogen atmosphere is preferable.

The thickness of the light absorbing anisotropic layer of the present invention is preferably 1.5 μm or more and preferably 4.0 μm or less for the reason of suppressing the change in hue with respect to the original image with respect to the reflected image to the surrounding.

The light absorbing anisotropic layer of the present invention preferably exhibits a nematic liquid crystal phase, from the reason that the occurrence of alignment defects or precipitation of a liquid crystal composition is suppressed in the above-described alignment step, and the planar uniformity is improved.

[ Patterning of light absorbing Anisotropic layer ]

The light absorbing anisotropic layer of the present invention can be a light absorbing anisotropic layer having a region a and a region B in a plane and having a transmittance central axis different in each region. If the light emitting pixels are controlled by patterning each pixel of the liquid crystal, the viewing angle center of the narrow viewing angle can be switched.

The light absorbing anisotropic layer of the present invention can be the following light absorbing anisotropic layer: there are a region C and a region D in the plane, and in the region C and the region D, the transmittance inclined by 30 ° from the transmittance center axis to the normal direction is different in a plane including the transmittance center axis and the normal to the surface of the light absorbing anisotropic layer. In this case, the following light absorbing anisotropic layer is preferable: the transmittance of the region C inclined by 30 ° from the transmittance center axis normal direction is 50% or less, and the transmittance of the region D inclined by 30 ° from the transmittance center axis normal direction is 80% or more.

By performing the patterning described above, the viewing angle dependence can be enhanced or reduced in a local area. Thus, highly confidential information can be displayed only in the area where viewing angle dependence is enhanced. Further, by controlling the viewing angle dependence for each display position as a display device, a design excellent in design can be achieved. In addition, if the light emitting pixels are controlled by patterning each pixel of the liquid crystal, a narrow viewing angle/a wide viewing angle can be switched.

< Method of Forming Pattern >

The method for forming the patterned light-absorbing anisotropic layer having 2 or more regions differing in plane is not limited, and various known methods described in, for example, W02019/176818 can be used. Examples of the method include a method of forming a pattern by changing an irradiation angle of ultraviolet light to be irradiated to the photo-alignment film, a method of controlling a thickness of the patterned light-absorbing anisotropic layer in a plane, a method of unevenly providing a dichroic dye compound in the patterned light-absorbing anisotropic layer, and a method of post-processing an optically uniform patterned light-absorbing anisotropic layer.

Examples of the method for controlling the thickness of the patterned light-absorbing anisotropic layer in the plane include a method using photolithography, a method using imprinting, and a method for forming the patterned light-absorbing anisotropic layer on a substrate having a concave-convex structure. As a method for unevenly providing the dichroic dye compound in the patterned light-absorbing anisotropic layer, a method (bleaching) of extracting a dichroic dye by solvent impregnation is exemplified. Further, as a method of post-processing the optically uniform patterned light-absorbing anisotropic layer, a method of cutting a part of the flat light-absorbing anisotropic layer by laser processing or the like is exemplified.

[ Optical film ]

The optical film of the present invention has a transparent film substrate and the above-described light absorbing anisotropic layer of the present invention provided on the transparent film substrate.

Hereinafter, each member constituting the optical film of the present invention will be described.

[ Transparent film substrate ]

As the transparent film base material, a known transparent resin film, a transparent resin plate, a transparent resin sheet, or the like can be used, and is not particularly limited. As the transparent resin film, a cellulose acylate film (for example, a triacetate film (refractive index 1.48), a diacetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film), a polyethylene terephthalate film, a polyether sulfone film, a polyacrylic resin film, a polyurethane resin film, a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyetherketone film, a (meth) acrylonitrile film, or the like can be used.

Among them, cellulose acylate films which have high transparency, low optical birefringence, and are easy to manufacture and are generally used as protective films for polarizing plates are preferable, and cellulose triacetate (also referred to as triacetyl cellulose (TAC)) films are particularly preferable.

The thickness of the transparent film substrate is usually 20 μm to 100. Mu.m.

In the present invention, it is particularly preferable that the transparent film base material is a cellulose ester film and has a thickness of 20 to 70. Mu.m.

[ Light absorbing Anisotropic layer ]

The light absorbing anisotropic layer of the present invention is the light absorbing anisotropic layer of the present invention described above, and therefore, the description thereof will be omitted.

[ Oriented film ]

The optical film of the present invention preferably has an orientation film between the transparent film base material and the light absorbing anisotropic layer.

Specifically, the alignment film may be a layer of polyvinyl alcohol, polyimide, or the like, with or without rubbing treatment; and a photo-alignment film of polyvinyl cinnamate with or without polarization exposure treatment and azo dyes.

The thickness of the alignment film is preferably 0.01 to 10. Mu.m, more preferably 0.01 to 1. Mu.m.

[ Barrier layer ]

The optical film of the present invention preferably has a barrier layer together with the transparent film substrate and the light absorbing anisotropic layer.

The barrier layer is also referred to as a gas barrier layer (oxygen barrier layer) herein, and has a function of protecting the polarizing element of the present invention from gas such as oxygen in the atmosphere, moisture, or a compound contained in an adjacent layer.

For example, the barrier layer can be described in paragraphs [0014] to [0054] of Japanese patent application laid-open No. 2014-159724, paragraphs [0042] to [0075] of Japanese patent application laid-open No. 2017-121721, paragraphs [0045] to [0054] of Japanese patent application laid-open No. 2017-115076, paragraphs [0010] to [0061] of Japanese patent application laid-open No. 2012-213938, and paragraphs [0021] to [0031] of Japanese patent application laid-open No. 2005-169994.

[ Refractive index adjusting layer ]

The optical film of the present invention preferably has a refractive index adjustment layer from the viewpoint of suppressing the influence of internal reflection caused by the high refractive index of the light absorbing anisotropic layer.

The refractive index adjustment layer is arranged in contact with the light absorbing anisotropic layer, and has an in-plane average refractive index of 1.55 to 1.70 at a wavelength of 550 nm. A refractive index adjustment layer for performing so-called refractive index matching is preferable.

[ Tone adjusting layer ]

The optical film of the present invention preferably contains a color tone adjustment layer having at least 1 pigment compound. The pigment compound contained in the color tone adjustment layer is preferably in a non-oriented state.

When the amount of the pigment in the light-absorbing anisotropic layer is adjusted, the change in the color tone observed from the direction inclined from the transmittance central axis becomes larger, but by adjusting the color tone using the color tone adjusting layer, the change in the color tone from the inclined direction with respect to the change in the color tone of the transmittance central axis can be suppressed.

The tone adjustment layer may have a function alone or in combination with other layers.

The absorption peak wavelength of the pigment compound contained in the color tone adjustment layer used in the present invention is preferably 500nm to 650nm, more preferably 550nm to 600 nm. By setting the absorption of the dye compound within this range, the color tone of the optical film of the present invention can be adjusted to be more neutral.

Examples of the dye compound contained in the color tone adjustment layer include azo, methine, anthraquinone, triarylmethane, oxazine, azomethine, phthalocyanine, porphyrin, perylene, pyrrolopyrrole, squaraine, and the like, but azo, phthalocyanine, and anthraquinone are preferable, and anthraquinone is particularly preferable, from the viewpoint of excellent absorption waveform, heat resistance, and light resistance. Examples thereof include pigment compounds described in Dachuan original, songgangxian, ping Daoheng Liang, bei Yuan Tang co-worker, functional pigments, kodansha Ltd., 1992, time Tian Chengnan master, electronic-related materials, CMC Publishing Co., ltd., 1998, and the like.

Specific examples of the pigment compound used in the present invention are shown below, but the present invention is not limited to these.

Anthraquinone

[ Chemical formula 40]

Azo compounds

[ Chemical formula 41]

/>

Triarylmethane

[ Chemical formula 42]

Oxazines

[ Chemical formula 43]

Phthalocyanine (Phthalocyanine)

[ Chemical formula 44]

[ Viewing angle control System ]

The viewing angle control system of the present invention has a polarizer having an absorption axis in the in-plane direction, and the light absorbing anisotropic layer of the present invention or the optical film of the present invention described above.

Specifically, the absorption axis is a direction perpendicular to a direction in which transmittance is the lowest at a wavelength of 550nm when transmittance is measured by changing an inclination angle (polar angle) and an inclination direction (azimuth angle) with respect to a normal direction in a plane in various ways. Regarding the transmittance in which the inclination angle and the inclination direction with respect to the in-plane normal direction are changed, for example, axoScan OPMF-1 (manufactured by Opto Science, inc.) can be used for measurement.

[ Polarizer ]

The polarizer included in the viewing angle control system of the present invention is not particularly limited as long as it has an absorption axis in the plane and a function of converting light into specific linearly polarized light, and a conventionally known polarizer can be used.

As the polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a multi-olefin-based polarizer, and the like can be used. Iodine-based polarizers and dye-based polarizers include coating-type polarizers and stretching-type polarizers, and either one can be applied. As the coating type polarizer, a polarizer in which a dichroic organic dye is aligned by alignment of a liquid crystalline compound is preferable, and as the stretching type polarizer, a polarizer produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching is preferable.

As a method of obtaining a polarizer by stretching and dyeing a laminate film having a polyvinyl alcohol layer formed on a substrate, japanese patent No. 5048120, japanese patent No. 5143918, japanese patent No. 5048120, japanese patent No. 4691205, japanese patent No. 4751481, and japanese patent No. 4751486 can be cited, and a known technique related to these polarizers can be preferably used.

Among them, a polarizer containing a polyvinyl alcohol resin (a polymer containing-CH ₂ -CHOH-as a repeating unit, particularly at least 1 selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) is preferable from the viewpoints of easy availability and excellent polarization degree.

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 20 μm, and still more preferably 5 μm to 10 μm.

In the viewing angle control system of the present invention, the angle Φ1 between the direction Φ1 in which the transmittance center of the light-absorbing anisotropic layer is orthographically projected onto the film surface and the absorption axis Φ2 of the polarizer is preferably 45 ° to 90 °, more preferably 80 ° to 90 °, and even more preferably 88 ° to 90 °. The closer the angle is to 90 °, the more the illuminance contrast in the direction in which the image display device is easily seen and in the direction in which the image display device is difficult to see can be increased.

In the viewing angle control system of the present invention, the light-absorbing anisotropic layer and the polarizer may be laminated via an adhesive layer or an adhesive layer described later, or the alignment film and the light-absorbing anisotropic layer may be directly coated on the polarizer to be laminated.

[ Adhesive layer ]

The adhesive layer is preferably a transparent and optically isotropic adhesive similar to the adhesive used in a general image display device, and a pressure sensitive adhesive is generally used.

In addition to the base material (binder), the conductive particles, and the thermally expandable particles used if necessary, the adhesive layer may be blended with a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or the like), a tackifier (for example, a rosin derivative resin, a polyterpene resin, a petroleum resin, an oil-soluble phenol resin, or the like), a plasticizer, a filler, an anti-aging agent, a surfactant, an ultraviolet absorber, a light stabilizer, an antioxidant, or other suitable additives.

The thickness of the adhesive layer is usually 20 to 500. Mu.m, preferably 20 to 250. Mu.m. When the thickness is 20 μm or more, the adhesion and reworkability become good, and when the thickness is 500 μm or less, the adhesive agent is easily prevented from overflowing from the peripheral edge of the image display device.

In the formation of the adhesive layer, for example, a method of directly applying a coating liquid containing a base material, conductive particles, and optionally, thermally expandable particles, additives, solvents, and the like to the protective member support 110 and pressure-bonding the protective member support with a release liner interposed therebetween can be used; and a method in which a coating liquid is applied to an appropriate release liner (release paper or the like) to form a thermally expandable adhesive layer and the layer is pressure-bonded and transferred (transferred) to the protective member support 110.

Further, as the protective member, a structure in which conductive particles are added to a structure of a heat peelable adhesive sheet described in, for example, japanese unexamined patent publication No. 2003-292916 can be applied.

Further, as the protective member, a member in which conductive particles are dispersed on the surface of the adhesive layer in a commercially available product such as "revapha" manufactured by Nitto Denko Corporation may be used.

[ Adhesive layer ]

The adhesive exhibits adhesion by drying or reaction after bonding.

The polyvinyl alcohol-based adhesive (PVA-based adhesive) exhibits adhesiveness by drying, and can bond materials to each other.

Specific examples of the curable adhesive exhibiting adhesiveness by the reaction include an active energy ray curable adhesive such as a (meth) acrylate adhesive and a cationic polymerization curable adhesive. In addition, (meth) acrylate means acrylate and/or methacrylate. Examples of the curable component in the (meth) acrylate adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. As the cationic polymerization curable adhesive, a compound having an epoxy group or an oxetane group can be used. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various conventionally known curable epoxy compounds can be used. Preferable examples of the epoxy compound include a compound having at least 2 epoxy groups and at least 1 aromatic ring in the molecule (aromatic epoxy compound), a compound having at least 2 epoxy groups in the molecule and at least 1 of them being formed between adjacent 2 carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), and the like.

Among them, an ultraviolet-curable adhesive cured by ultraviolet irradiation is preferably used from the viewpoint of heat distortion resistance.

The adhesive layer and each layer of the adhesive layer may be a layer having ultraviolet absorption ability by treating with an ultraviolet absorber such as a salicylate compound, a phenol compound, a benzotriazole compound, a cyanoacrylate compound, or a nickel complex salt compound.

The adhesive layer and the adhesive layer can be attached by an appropriate method. Examples thereof include the following modes: a method of preparing a binder solution of about 10 to 40% by weight, which is obtained by dissolving or dispersing a base polymer or a composition thereof in a solvent comprising a single or a mixture of a suitable solvent such as toluene or ethyl acetate, and directly attaching the binder solution to a film by a suitable development method such as a casting method or a coating method; or in such a manner that an adhesive layer is formed on the separator and is transferred as described above.

The adhesive layer and the adhesive layer may be provided on one or both sides of the film as overlapping layers of different compositions, types, or the like. When the adhesive layers are provided on both sides, adhesive layers having different compositions, types, thicknesses, and the like can be formed on the front and back sides of the film.

[ Other layers ]

In order to control the angle dependence of the viewing angle, the viewing angle control system of the present invention can also use the above-described light absorbing anisotropic layer in combination with an optically anisotropic film or a rotator. For example, as the transparent base film, a resin film having optical anisotropy composed of a polymer containing carbonate, cycloolefin, cellulose acylate, methyl methacrylate, styrene, maleic anhydride, or the like is also preferably used.

[ Image display device ]

The image display device of the present invention is an image display device having a display element and the above-described viewing angle control system of the present invention, and the viewing angle control system is disposed on at least one main surface of the display element.

The image display device of the present invention is preferably an image display device in which the light-absorbing anisotropic layer included in the viewing angle control system is disposed on the viewing side of the polarizer included in the viewing angle control system, that is, an image display device having the light-absorbing anisotropic layer, the polarizer, and the display element in this order from the viewing side.

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

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

Some image display devices are thin and can be shaped as curved surfaces. The optically anisotropic absorbing film used in the present invention is thin and is easily bendable, and therefore can be preferably applied to an image display device having a curved display surface.

Also, some image display devices have a pixel density exceeding 250ppi and are capable of high-definition display. The optically anisotropic absorbing film used in the present invention can also be preferably applied to such a high-definition image display device without producing moire.

[ Liquid Crystal display device ]

As an example of the display device of the present invention, a liquid crystal display device including an optical film having the polarizer and a liquid crystal cell is preferable.

Specifically, the optical film of the present invention is arranged on the front polarizing plate or the rear polarizing plate. In these configurations, the viewing angle control for shielding light in the up-down direction or the left-right direction can be performed.

The optical film of the present invention may be disposed on both the front polarizing plate and the rear polarizing plate. With this configuration, the viewing angle can be controlled by shielding the light in all directions and transmitting only the light in the front direction.

Further, a plurality of optical films of the present invention may be laminated with a retardation layer interposed therebetween. By controlling the phase difference value and the optical axis direction, the transmission performance and the light shielding performance can be controlled. For example, by disposing the polarizer, the optical film, the λ/2 wavelength plate (the axial angle is an angle that deviates from the orientation direction of the polarizer by 45 °) and the optical film, it is possible to perform viewing angle control that shields all-directional light and transmits only light in the front direction. As the retardation layer, a positive a plate, a negative a plate, a positive C plate, a negative C plate, a B plate, a 0 plate, or the like can be used. From the viewpoint of reducing the thickness of the viewing angle control system, the thickness of the retardation layer is preferably small, more preferably 1 to 150 μm, still more preferably 1 to 70 μm, and still more preferably 1 to 30 μm, as long as the optical characteristics, mechanical properties, and manufacturing suitability are not impaired.

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

< Liquid Crystal cell >

The liquid crystal cell used In the liquid crystal display device is preferably a VA (VERTICAL ALIGNMENT: vertical alignment) mode, an OCB (Optically Compensated Bend: optically compensatory bend) mode, an IPS (In-Plane-SWI TCHING: in-Plane switching) mode, or a TN (TWISTED NEMATIC: twisted nematic) mode, but is not limited thereto.

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

In the VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. The VA mode liquid crystal cell includes (1) a narrow VA mode liquid crystal cell in which rod-like liquid crystal molecules are substantially vertically aligned when no voltage is applied and substantially horizontally aligned when a voltage is applied (described in japanese patent application laid-open No. h 2-176825), a VA mode multi-domain (MVA mode) liquid crystal cell in which the rod-like liquid crystal molecules are substantially vertically aligned when no voltage is applied (described in SID97, digest of tech papers 28 (1997) 845), and (3) a multi-domain mode (n-ASM mode) liquid crystal cell in which the rod-like liquid crystal molecules are twisted and multi-domain aligned when a voltage is applied (described in japanese discussion 58-59 (1998)) and (4) a SURVIVAL mode liquid crystal cell in which the rod-like liquid crystal molecules are multi-domain aligned when a voltage is applied (disclosed in LCD International). Further, the Polymer may be of any of PVA (PATTERNED VERTICAL ALIGNMENT: image homeotropic alignment), photo-alignment type (Optical Alignment: optical alignment) and PSA (Polymer-Sustained Alignment: polymer stable alignment). Details of these modes are described in Japanese patent application laid-open No. 2006-215326 and Japanese patent application laid-open No. 2008-538819.

In the IPS mode liquid crystal cell, a liquid crystal compound is aligned substantially parallel to a substrate, and an electric field parallel to a substrate surface is applied to cause a liquid crystal molecule to respond in plane. That is, the liquid crystalline compound is aligned in-plane in a state where no electric field is applied. The IPS mode displays black in a state where no electric field is applied, and absorption axes of a pair of upper and lower polarizers are orthogonal. Methods for reducing light leakage at the time of black display in an oblique direction and improving viewing angle using an optical compensation sheet are disclosed in JP-A-10-54982, JP-A-11-202323, JP-A-9-292522, JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.

[ Organic EL display device ]

As an example of the display device of the present invention, for example, an organic EL display device having the above polarizer, a λ/4 plate, and an organic EL display panel in this order from the viewing side is preferable.

In addition, as in the case of the liquid crystal display device described above, a plurality of optical films according to the present invention may be laminated via a retardation layer and disposed on an organic EL display panel. By controlling the phase difference value and the optical axis direction, the transmission performance and the light shielding performance can be controlled.

The organic EL display panel is a display panel configured using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure may be employed.

Examples

The present invention will be described in further detail with reference to examples. The materials, amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed in a limiting manner by the examples shown below.

Example 1

The optical film a of example 1 was produced as follows.

[ Formation of oriented film 1]

The following composition 1 for forming an alignment film was continuously coated on a cellulose acylate film (TAC substrate having a thickness of 40 μm: TG40, FUJIFILM Corporation) with a bar. The cellulose acylate film having the coating film formed thereon was dried with warm air at 140 ℃ for 120 seconds to form an alignment film 1, thereby obtaining a TAC film 1 with an alignment film. The film thickness of the alignment film 1 was 0.5. Mu.m.

Polymer PA1

[ Chemical formula 45]

Acid generator PAG-1

[ Chemical formula 46]

Stabilizer DIPEA

[ Chemical formula 47]

[ Production of light absorbing Anisotropic layer 1 ]

The following liquid crystal composition 1 was continuously coated on the obtained alignment film 1 with a bar, and after heating at 120℃for 60 seconds, cooled to room temperature (23 ℃).

Then, the mixture was heated at 85℃for 60 seconds and cooled again to room temperature.

Then, an LED (LIGHT EMITTING diode: light emitting diode) lamp (center wavelength 365 nm) was used, and the alignment film 1 was irradiated with light of 200mW/cm ² for 2 seconds, thereby producing a light absorbing anisotropic layer 1. The film thickness of the light absorbing anisotropic layer 1 was 3.5. Mu.m.

[ Formation of Barrier B1 ]

A composition B1 for forming a barrier layer described below was continuously coated on the obtained light absorbing anisotropic layer 1 with a bar to form a coating film.

Subsequently, the support having the coating film formed thereon was dried with warm air at 60 ℃ for 60 seconds, and further dried with warm air at 100 ℃ for 120 seconds to form a barrier layer B1, which was used as the optical film 1. The film thickness of the barrier layer was 0.5. Mu.m.

Modified polyvinyl alcohol PVA-1

[ Chemical formula 48]

Using the produced optical film 1, the transmittance central axis angle θ was measured by the above-described method and found to be 0 °. Since the layer structure other than the light absorption anisotropic layer 1 of the optical film 1 does not have absorption anisotropy, the transmittance central axis angle θ calculated above can be replaced with the value of the light absorption anisotropic layer 1 of the optical film 1.

Examples 2 to 14 and comparative examples 1 to 3

Light-absorbing anisotropic layers and optical films of examples 2 to 14 and comparative examples 1 to 3 were produced in the same manner as in example 1 except that the composition of the liquid crystal composition 1 was changed to the composition shown in table 1 below.

The transmittance central axis angle θ of the light absorbing anisotropic layers produced in examples 2 to 14 and comparative examples 1 to 3 was 0 °.

[ Evaluation ]

[ Contrast ratio ]

The mueller matrix of the optical film at the wavelength λ was measured at 10-degree intervals from polar angle-60 degrees to 60 degrees using each of the optical films produced in examples and comparative examples and AxoScan OPMF-1 (manufactured by Opto Science, inc.). After the influence of the surface reflection was removed, the transmittance (TmO) of the front surface and the transmittance (Tm 30) of 30 ° were calculated, and the Contrast (CR) was evaluated by the following formula. The results are shown in table 1 below.

CR＝TmO/Tm30

< Evaluation criterion >

AA: cr is 6.08 or more

A: cr is less than 6.08 and more than 2.20

B: cr is less than 2.20 and more than 1.69

C: cr is less than 1.69 and more than 1.27

D: cr is less than 1.27

[ Planar uniformity (non-uniformity) ]

A polarizer is placed in an X-ray film reading lamp (Schaukasten) device.

Next, each of the optical films produced in examples and comparative examples was placed on an X-ray reading lamp with a polarizing plate, and each of the optical films was visually observed from the front at an angle of 75 ℃ in a direction orthogonal to the absorption axis of the polarizing plate, and evaluated according to the following criteria.

< Evaluation criterion >

A: no unevenness in the shade was found in the range of 10cm×10cm

B: the unevenness of the shade was found at 15 to 20 in the range of 10cm X10 cm

C: the unevenness of the shade was found at 21 to 25 in the range of 10cm X10 cm

D: the unevenness of the shading was found at 26 or more in the range of 10cm X10 cm

[ Adhesion ]

Each of the optical films produced in examples and comparative examples was cut to a size of 25mm×150mm, and a polyester adhesive tape (No. 31 b) manufactured by Nitto Denko corporation was attached to the surface of the side of each optical film having the barrier layer, and then peeled off.

The polarizing layer release surface (surface from which the barrier layer was released) was observed and evaluated according to the following criteria. The results are shown in table 1 below.

< Evaluation criterion >

A: unpeeled

B: peeling residues were observed, but the area was less than 5%

C: the peeling residue was observed to be 5% or more in area

In table 1, the components represented by symbols are as follows.

Liquid crystalline compound L1

[ Chemical formula 49]

Liquid crystalline compound L2

[ Chemical formula 50]

Liquid crystalline compound L3

[ Chemical formula 51]

Liquid crystalline compound L4

[ Chemical formula 52]

Dichromatic substance Y1

[ Chemical formula 53]

Dichromatic substance Y2

[ Chemical formula 54]

Dichroic substance M1

[ Chemical formula 55]

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Dichroic substance M2

[ Chemical formula 56]

Dichromatic substance C1

[ Chemical formula 57]

Dichromatic substance C2

[ Chemical formula 58]

Surfactant B1

[ Chemical formula 59]

Surfactant B2

[ Chemical formula 60]

Surfactant B3

[ Chemical formula 61]

Surfactant B4

[ Chemical formula 62]

Surfactant B5

[ Chemical formula 63]

Surfactant B6

[ Chemical formula 64]

Surfactant B7

[ Chemical formula 65]

Surfactant B8

[ Chemical formula 66]

Surfactant B9

[ Chemical formula 67]

Surfactant B10

[ Chemical formula 68]

Orientation agent D1

[ Chemical formula 69]

Orientation agent D2

[ Chemical formula 70]

From the results shown in table 1, it is clear that when the surfactant B10 which is not a specific surfactant is used, the uniformity of the surface is poor (comparative example 1).

Further, it was found that when the surfactant B8 which is not a specific surfactant was used, the contrast and the uniformity of the surface area were poor (comparative example 2).

It was also found that the contrast and the surface uniformity were poor without blending the surfactant (comparative example 3).

On the other hand, it was found that when a specific surfactant was blended, the contrast was high and the uniformity of the surface was also good (examples 1 to 14)

In particular, as is clear from the comparison of examples 1, 5 and 8, if the specific surfactant is a copolymer satisfying the above condition 2, the contrast ratio becomes high.

Further, as is clear from the comparison between example 6 and example 8, the contrast is further improved when the content of the repeating unit B is 5 to 50 mass% with respect to the total mass of the specific surfactant (specific copolymer).

Further, as is clear from the comparison between example 2 and example 8, if the specific surfactant has a repeating unit C containing a polymerizable group, the adhesiveness becomes good.

Further, as is clear from the comparison between example 8 and example 9, when the content of the specific surface modifier is 0.001 to 5 mass% relative to the total solid content mass of the liquid crystal composition, the contrast is higher and the planar uniformity is also better.

Further, as is clear from the comparison of examples 2, 10 and 11, when the content of the dichroic material is 5 mass% or more, the contrast ratio becomes higher, and when the content of the dichroic material is 30 mass% or less, the planar uniformity becomes better.

[ Production of display device ]

[ Formation of tone adjustment layer G1 ]

The composition G1 for forming a color tone adjustment layer was continuously coated on the light absorbing anisotropic layer 1 obtained in example 1 with a bar to form a coating film.

Subsequently, the support having the coating film formed thereon was dried with warm air at 60 ℃ for 60 seconds, and further dried with warm air at 100 ℃ for 120 seconds to form the color tone adjustment layer G1, which was used as the optical film 1a. The film thickness of the tone adjustment layer was 0.5. Mu.m.

Pigment Compound G-1

[ Chemical formula 71]

[ Production of optical laminate A1 ]

In the same manner as in the polarizer 02 with a single-sided protective film described in International publication No. 2015/166991, a polarizer 1 having a polarizer thickness of 8 μm and one side of the polarizer exposed was produced.

The polarizer exposed surface of the polarizer 1 and the surface of the color tone adjustment layer of the produced optical film 1a were subjected to corona treatment, and bonded using the PVA adhesive 1 described below to produce an optical laminate A1.

< Preparation of PVA adhesive 1 >

An aqueous solution having a solid content of 3.7% was prepared by dissolving 20 parts of methylolmelamine in 100 parts of an acetoacetyl group-containing polyvinyl alcohol resin (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) at a temperature of 30 ℃.

[ Production of image display device A1 ]

IPADAIR WI-Fi model 16GB (manufactured by Apple inc.) as an IPS mode liquid crystal display device was disassembled and a liquid crystal cell was taken out.

The viewing-side polarizing plate was peeled off from the liquid crystal cell, and the optical laminate A1 produced in the above was bonded to the surface from which the viewing-side polarizing plate was peeled off using the following adhesive sheet 1, so that the polarizing plate 1 side became the liquid crystal cell side. At this time, the direction of the absorption axis of the polarizing plate 1 is the same as the absorption axis of the viewing side polarizing plate attached to the product. After bonding, the image display device A1 was assembled again.

< Production of adhesive sheet 1>

The acrylic polymer was prepared as follows.

In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were polymerized by a solution polymerization method to obtain an acrylic polymer A1 having an average molecular weight of 200 ten thousand and a molecular weight distribution (Mw/Mn) of 3.0.

Next, in addition to the obtained acrylic polymer A1 (100 parts by mass), CORONATE L (75% by mass ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate, number of isocyanate groups in 1 molecule: 3, nippon Polyurethane Industry co., manufactured by ltd.) (1.0 parts by mass) and a silane coupling agent KBM-403 (Shin-Etsu Chemical co., manufactured by ltd.) (0.2 parts by mass) were mixed, and finally ethyl acetate was added to make the total solid content concentration 10% by mass, to prepare a composition for forming an adhesive. The composition was applied to a release film surface-treated with a silicone-based release agent using a die coater, and dried at 90 ℃ for 1 minute to obtain an acrylic adhesive sheet. The film thickness was 25. Mu.m, and the storage modulus was 0.1MPa.

The image display device manufactured in example 1 showed white color, and as a result, the color tone from the front and the oblique sides was neutral.

Claims

1. A light absorbing anisotropic layer formed of a liquid crystal composition containing a liquid crystalline compound, a dichroic substance and a surfactant, wherein,

The surfactant is a copolymer having a repeating unit A containing a fluorine atom and not containing a polymerizable group and a repeating unit B containing no fluorine atom and not containing a polymerizable group and satisfying the following condition 1 or 2,

An angle θ formed between a transmittance central axis of the light absorbing anisotropic layer and a normal direction of a surface of the light absorbing anisotropic layer is 0 DEG or more and 45 DEG or less,

Condition 1: the repeating unit A is represented by the following formula (A-1) and the repeating unit B has a polar group at the terminal of the side chain;

Condition 2: the repeating unit B is represented by the following formula (B-1) or (B-2),

In the formula (A-1),

R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

LF ¹ represents a single bond or a divalent linking group,

RF ¹ represents a group containing a fluorine atom, wherein RF ¹ is terminated with-CF ₂ H,

In the formula (B-1),

R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

L ¹ represents a single bond or is selected from the group consisting of-O-, -S-, -COO-, -OCO-, -CONR ^L1-、-NR^L1COO-、-CR^L1 N-, a substituted or unsubstituted divalent aliphatic radical a divalent linking group of the group consisting of substituted or unsubstituted divalent aromatic groups and combinations thereof, R ^L1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

Ring a represents a ring structure having a cationized nitrogen atom,

X represents an anion and is preferably selected from the group consisting of,

L ² represents a hydrogen atom or a substituent,

In the formula (B-2),

R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

L ³ represents a single bond or is selected from the group consisting of-O-, -S-, -COO-, -OCO-, -CONR ^L1-、-NR^L1COO-、-CR^L1 N-, a substituted or unsubstituted divalent aliphatic radical a divalent linking group of the group consisting of substituted or unsubstituted divalent aromatic groups and combinations thereof, R ^L1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

R ⁴ and R ⁵ each independently represent a hydrogen atom, or a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R ⁴ and R ⁵ may be linked to each other via an alkylene linking group, an arylene linking group, or a linking group composed of a combination thereof.

2. The light absorbing anisotropic layer of claim 1, wherein,

3. The light absorbing anisotropic layer of claim 1, wherein,

4. The light absorbing anisotropic layer of claim 1, wherein,

The surfactant has a repeating unit C containing a polymerizable group.

5. The light absorbing anisotropic layer of claim 1, wherein,

The surfactant is contained in an amount of 0.001 to 5% by mass based on the total solid content mass of the liquid crystal composition.

6. The light absorbing anisotropic layer of claim 1, wherein,

The dichroic compound is contained in an amount of 5 to 30 mass% relative to the total solid content mass of the liquid crystal composition.

7. The light absorbing anisotropic layer of claim 1, wherein the light absorbing anisotropic layer exhibits a nematic liquid crystal phase.

8. An optical film having a transparent film substrate and the light absorbing anisotropic layer of any one of claims 1 to 7 disposed on the transparent film substrate.

9. The optical film according to claim 8, wherein the optical film has an orientation film between the transparent film substrate and the light absorbing anisotropic layer.

10. A viewing angle control system having a polarizer having an absorption axis in an in-plane direction and the light absorbing anisotropic layer of any of claims 1 to 7.

11. An image display device having a display element and the viewing angle control system of claim 10,

12. The image display device according to claim 11, wherein,