Light-absorbing anisotropic film, laminate, image display device, and liquid crystal composition

Abstract

The present invention addresses the problem of providing: a light absorption anisotropic film having excellent adhesiveness and a high degree of orientation; a laminate; an image display device; and a liquid crystal composition. A light absorption anisotropic film according to the present invention is formed from a liquid crystal composition that contains a liquid crystalline compound, a dichroic substance, and a boronic acid compound having a polymerizable group, wherein the liquid crystalline compound is horizontally oriented.

Description

[Technical Field]

[0001] The present invention relates to a light-absorbing anisotropic film, a laminate, an image display device, and a liquid crystal composition. [Background technology]

[0002] Traditionally, when functions such as attenuation, polarization, scattering, or light shielding of laser light or ambient light were required, devices operating on different principles were used for each function. Therefore, products corresponding to these functions were manufactured using different manufacturing processes for each function. For example, in image display devices (such as liquid crystal displays), linear or circular polarizers are used to control optical rotation or birefringence in the display. Similarly, in organic light-emitting diodes (OLEDs), circular polarizers are used to prevent reflection of ambient light.

[0003] Traditionally, iodine has been widely used as the dichroic material in these polarizers, but polarizers that use organic dyes as the dichroic material instead of iodine are also being investigated. For example, Patent Document 1 shows that a light-absorbing anisotropic film is formed using a liquid crystal composition (colored composition) containing a dichroic substance (dichroic dye compound) having a predetermined structure (Claim 1 and Claim 14, etc.). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2017 / 195833 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In recent years, there has been a growing demand for further performance improvements in light-absorbing anisotropic films formed using liquid crystal compositions. Specifically, there is a need for light-absorbing anisotropic films that exhibit excellent orientation and superior adhesion to other components. The present inventors investigated light-absorbing anisotropic films as described in Patent Document 1 and found that although they exhibit a high degree of orientation, there is room for improvement in the adhesion between the light-absorbing anisotropic film and other components depending on the type of liquid crystal composition used to form the light-absorbing anisotropic film.

[0006] Therefore, the object of the present invention is to provide a light-absorbing anisotropic film, laminate, image display device, and liquid crystal composition that have excellent adhesion and a high degree of orientation. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that a light-absorbing anisotropic film formed from a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boronic acid compound having polymerizable groups, in which the liquid crystal compound is horizontally oriented, exhibits excellent adhesion to other layers and a high degree of orientation, thus completing the present invention. In other words, the inventors have found that the above problem can be solved by the following configuration.

[0008] [1] A light-absorbing anisotropic film formed from a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boronic acid compound having polymerizable groups, A light-absorbing anisotropic film in which the above-mentioned liquid crystalline compound is horizontally oriented. [2] The light-absorbing anisotropic film according to [1], wherein the boronic acid compound having the polymerizable group described above comprises at least one of the compound represented by formula (B-1) described below and the compound represented by formula (BX-1) described below. In equation (B-1) described below, R B11 This represents a hydrogen atom or a methyl group. L B1represents a single bond, a divalent aliphatic hydrocarbon group, or a divalent group in which one or more -CH2- constituting the divalent aliphatic hydrocarbon group are substituted with at least one group selected from the group consisting of -O-, -C(=O)-, and -N(R B14 ), where R B14 represents a hydrogen atom or an alkyl group, A B1 represents an arylene group which may have a substituent, or a heteroarylene group which may have a substituent, R B12 and R B13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R B12 and R B13 may be bonded to each other to form a ring. In the formula (BX-1) described below, R BX11 represents a hydrogen atom or a methyl group, and a plurality of R BX11 may be the same or different from each other, L BX1 represents a single bond, a divalent aliphatic hydrocarbon group, or a divalent group in which one or more -CH2- constituting the divalent aliphatic hydrocarbon group are substituted with at least one group selected from the group consisting of -O-, -C(=O)-, and -N(R BX14 ), and a plurality of L BX1 may be the same or different from each other, R BX14 represents a hydrogen atom or an alkyl group, and when a plurality of R BX14 are present, the plurality of R BX14 may be the same or different from each other, A BX1 represents an arylene group which may have a substituent, or a heteroarylene group which may have a substituent, and a plurality of A BX1 may be the same or different from each other. [3] The light-absorbing anisotropic film according to [1] or [2], wherein the boronic acid compound having the polymerizable group described above comprises at least one of the compound represented by formula (B-2) described below and the compound represented by formula (BX-2) described below. In equation (B-2) described below, R B21 This represents a hydrogen atom or a methyl group. L B2 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) B25 ) represents a divalent group substituted with at least one group selected from the group consisting of ) and R B25 This represents a hydrogen atom or an alkyl group. R B22 and R B23 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R B22 and R B23 They may be joined to each other to form a ring. R B24 This represents a monovalent substituent, nb represents an integer between 0 and 4, and if nb is 2 or greater, multiple R B24 These may be the same or different. In equation (BX-2) described later, R BX21 R represents a hydrogen atom or a methyl group, and there are multiple R BX21 These may be the same or different. L BX2 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) BX25 Represents a divalent group substituted with at least one group selected from the group consisting of )-, and multiple L BX2 These may be the same or different, R BX25 R represents a hydrogen atom or alkyl group, and there are multiple R BX25 If multiple R BX25 These may be the same or different. RBX24 represents a monovalent substituent, and multiple R BX24 If multiple R BX24 These may be the same or different. nc represents an integer between 0 and 4, and multiple nc values ​​may be the same or different. [4] The light-absorbing anisotropic film according to any one of [1] to [3], wherein the content of the boronic acid compound having the polymerizable group described above is 0.1 to 10% by mass relative to the total solid content mass of the liquid crystal composition. [5] The boronic acid compound having the polymerizable group described above includes the compound represented by formula (B-1) and the compound represented by formula (BX-1). The light-absorbing anisotropic film according to [2], wherein the mass ratio of the content of the compound represented by formula (B-1) to the content of the compound represented by formula (BX-1) is 5 to 500. [6] The boronic acid compound having the polymerizable group described above includes the compound represented by formula (B-2) and the compound represented by formula (BX-2). The light-absorbing anisotropic film according to [3], wherein the mass ratio of the content of the compound represented by formula (B-2) to the content of the compound represented by formula (BX-2) is 5 to 500. [7] The light-absorbing anisotropic film according to any one of [1] to [6], wherein the above-mentioned liquid crystalline compound comprises a polymer liquid crystalline compound. [8] A laminate comprising a light-absorbing anisotropic film described in any of [1] to [7], and a layer containing a polyvinyl alcohol-based resin disposed in contact with the light-absorbing anisotropic film. [9] Furthermore, the laminate according to [8] has a λ / 4 plate on the side of the light-absorbing anisotropic film opposite to the layer containing the polyvinyl alcohol-based resin.

[10] An image display device having a light-absorbing anisotropic film as described in any of [1] to [7], or a laminate as described in [8] or [9].

[11] A liquid crystal composition comprising a liquid crystal compound, a dichroic substance, and a boronic acid compound having a polymerizable group, A liquid crystal composition comprising a boronic acid compound having the polymerizable group described above, which includes at least one of the compound represented by formula (B-2) and the compound represented by formula (BX-1) described below. In equation (B-2) described below, R B21 This represents a hydrogen atom or a methyl group. L B2 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) B25 ) represents a divalent group substituted with at least one group selected from the group consisting of ) and R B25 This represents a hydrogen atom or an alkyl group. R B22 and R B23 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R B22 and R B23 They may be joined to each other to form a ring. R B24 This represents a monovalent substituent, nb represents an integer between 0 and 4, and if nb is 2 or greater, multiple R B24 These may be the same or different. In equation (BX-1) described later, R BX11 R represents a hydrogen atom or a methyl group, and there are multiple R BX11 These may be the same or different. L BX1 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) BX14 Represents a divalent group substituted with at least one group selected from the group consisting of )-, and multiple L BX1 These may be the same or different, R BX14 R represents a hydrogen atom or alkyl group, and there are multiple R BX14 If multiple RBX14 These may be the same or different. A BX1 represents an optionally substituted arylene group, or an optionally substituted heteroarylene group, and multiple A BX1 These may be the same or different.

[12] The liquid crystal composition according to

[11] , wherein the compound represented by the above formula (BX-1) is the compound represented by the formula (BX-2) described later. In equation (BX-2) described later, R BX21 R represents a hydrogen atom or a methyl group, and there are multiple R BX21 These may be the same or different. L BX2 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) BX25 Represents a divalent group substituted with at least one group selected from the group consisting of )-, and multiple L BX2 These may be the same or different, R BX25 R represents a hydrogen atom or alkyl group, and there are multiple R BX25 If multiple R BX25 These may be the same or different. R BX24 represents a monovalent substituent, and multiple R BX24 If multiple R BX24 These may be the same or different. nc represents an integer between 0 and 4, and multiple nc values ​​may be the same or different.

[13] The liquid crystal composition according to

[11] or

[12] , wherein the content of the boronic acid compound having the polymerizable group is 0.1 to 10% by mass with respect to the total solid content mass of the liquid crystal composition.

[14] The boronic acid compound having the polymerizable group described above includes the compound represented by formula (B-2) and the compound represented by formula (BX-1). A liquid crystal composition according to any one of

[11] to

[13] , wherein the mass ratio of the content of the compound represented by formula (B-2) to the content of the compound represented by formula (BX-1) is 5 to 500. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a light-absorbing anisotropic film, a laminate, an image display device, and a liquid crystal composition that have excellent adhesion and a high degree of orientation. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. Furthermore, in this specification, each component may be represented by a single substance or by a combination of two or more substances. When two or more substances are used in combination for each component, the content of that component refers to the total content of the combined substances unless otherwise specified. Furthermore, in this specification, "(meth)acrylate" refers to "acrylate" or "methacrylate," "(meth)acrylic" refers to "acrylic" or "methacrylic," "(meth)acryloyl" refers to "acryloyl" or "methacryloyl," and "(meth)acrylic acid" refers to "acrylic acid" or "methacrylic acid."

[0011] [Light-absorbing anisotropic film] The light-absorbing anisotropic film of the present invention is formed from a liquid crystal composition containing a liquid crystalline compound, a dichroic substance, and a boronic acid compound having polymerizable groups (hereinafter also referred to as "polymerizable boronic acid compound"), wherein the liquid crystalline compound is horizontally oriented. The light-absorbing anisotropic film of the present invention exhibits excellent adhesion and a high degree of orientation. As described later, polymerizable boronic acid compounds are compounds having a polymerizable group and at least one of a boronic acid group and a boronic acid ester group. It is presumed that these groups (polymerizable group, boronic acid group, boronic acid ester group) of polymerizable boronic acid compounds interact with other components, improving the adhesion between the light-absorbing anisotropic film and the other components. Furthermore, polymerizable boronic acid compounds are widely used as vertical alignment agents to vertically align liquid crystalline compounds. However, for reasons that are not entirely clear, in this invention, it is thought that the polymerizable boronic acid compound did not function sufficiently as a vertical alignment agent and therefore did not inhibit the horizontal alignment of the liquid crystalline compound. This is presumed to be the reason why a light-absorbing anisotropic film with a high degree of orientation was obtained.

[0012] [Liquid crystal composition] The liquid crystal composition used for forming the light-absorbing anisotropic film of the present invention contains a liquid crystal compound, a dichroic substance, and a polymerizable boronic acid compound. The liquid crystal composition may optionally contain a solvent, an interface modifier, a polymerization initiator, and other components. The following explains each component.

[0013] <Liquid crystal compounds> The liquid crystal composition contains a liquid crystalline compound. By including a liquid crystalline compound, the precipitation of dichroic substances can be suppressed while the dichroic substances can be oriented with a high degree of orientation. Both low-molecular-weight liquid crystalline compounds and high-molecular-weight liquid crystalline compounds can be used as liquid crystalline compounds, but high-molecular-weight liquid crystalline compounds are more preferable for obtaining a high degree of orientation. Here, "low-molecular-weight liquid crystalline compound" refers to a liquid crystalline compound that does not have repeating units in its chemical structure. "High-molecular-weight liquid crystalline compound" refers to a liquid crystalline compound that has repeating units in its chemical structure. Examples of low-molecular-weight liquid crystalline compounds include the liquid crystalline compounds described in Japanese Patent Publication No. 2013-228706. Examples of polymeric liquid crystalline compounds include the thermotropic liquid crystalline polymer described in Japanese Patent Publication No. 2011-237513. Furthermore, the polymeric liquid crystalline compound may have crosslinkable groups (e.g., acryloyl groups and methacryloyl groups) at its terminals. Liquid crystalline compounds may be used individually or in combination of two or more. The liquid crystalline compound preferably includes a polymer liquid crystalline compound because it provides superior orientation and adhesion of the light-absorbing anisotropic film.

[0014] The liquid crystalline compound is preferably a polymer liquid crystalline compound containing a repeating unit represented by the following formula (3-1) (hereinafter also referred to as "repeating unit (3-1)"), because it exhibits a superior degree of orientation of dichroic substances (especially dichroic azo dye compounds).

[0015] [ka]

[0016] In formula (3-1) above, P1 represents the repeating main chain, L1 represents a single bond or a divalent linking group, SP1 represents a spacer group, M1 represents a mesogenic group, and T1 represents a terminal group.

[0017] In the repeating unit (3-1), it is preferable that the difference between the logP values ​​of P1, L1, and SP1 and the logP value of M1 is 4 or more. More preferably, it is 4.5 or more. Since the logP values ​​of the main chain, L1, and spacer groups and the log value of the mesogenic group are separated by a predetermined value or more, the compatibility between the structure from the main chain to the spacer group and the mesogenic group is low. This is presumed to increase the crystallinity of the polymeric liquid crystalline compound and increase the degree of orientation of the polymeric liquid crystalline compound. Thus, it is presumed that when the degree of orientation of the polymeric liquid crystalline compound is high, the compatibility between the polymeric liquid crystalline compound and organic dichroic substances (especially dichroic azo dye compounds) decreases (i.e., the crystallinity of the dichroic azo dye compound improves), and the degree of orientation of the dichroic azo dye compound improves. As a result, it is thought that the degree of orientation of the resulting light-absorbing anisotropic film will be high.

[0018] Specifically, the main chain of the repeating unit represented by P1 can be, for example, a group represented by the following formulas (P1-A) to (P1-D), and among these, the group represented by the following formula (P1-A) is preferred from the viewpoint of the diversity of monomers used as raw materials and ease of handling.

[0019] [ka]

[0020] In equations (P1-A) to (P1-D), "*" represents the bonding position with L1 in equation (3-1). In the above equations (P1-A) to (P1-D), R 1 , R 2 , R 3 and R 4 Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or a C1-C10 alkyl group, or a C1-C10 alkoxy group. The alkyl group may be a linear or branched alkyl group, or a cyclic alkyl group (cycloalkyl group). The number of carbon atoms in the alkyl group is preferably 1 to 5. The group represented by the above formula (P1-A) is preferably a unit of the partial structure of a poly(meth)acrylic acid ester obtained by polymerization of (meth)acrylic acid esters. The group represented by the above formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of a compound having an epoxy group. The group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of the oxetane group of a compound having an oxetane group. The group represented by the above formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by condensation polymerization of a compound having at least one of an alkoxysilyl group and a silanol group. Here, the compound having at least one of an alkoxysilyl group and a silanol group is a compound of the formula SiR 14 (OR15 Examples include compounds having a group represented by )2-. In the formula, R 14 R in (P1-D) 14 It is synonymous with multiple R 15 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0021] L1 is a single bond or a divalent linking group. The divalent linking groups represented by L1 include -C(O)O-, -OC(O)-, -O-, -S-, and -C(O)NR 3 -, -NR 3 C(O)-, -SO2-, and -NR 3 R 4 - are some examples. In the formula, R 3 and R 4 Each of these independently represents a hydrogen atom or a C1-C6 alkyl group which may have substituents (described later). When P1 is a group represented by formula (P1-A), L1 is preferably a group represented by -C(O)O- because it results in a better degree of orientation of the light-absorbing anisotropic film. When P1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond because it results in a better degree of orientation of the light-absorbing anisotropic film.

[0022] The spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of oxyethylene structure, oxypropylene structure, polysiloxane structure, and fluorinated alkylene structure, due to reasons such as its tendency to exhibit liquid crystalline properties and the availability of raw materials. Here, the oxyethylene structure represented by SP1 is *-(CH2-CH2O) n1 A group represented by -* is preferred. In the formula, n1 represents an integer from 1 to 20, and * represents the bonding position with L1 or M1 in formula (3-1) above. n1 is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, and most preferably 3, because it provides a better degree of orientation of the light-absorbing anisotropic film. In addition, the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH(CH3)-CH2O) n2 -*, where n2 represents an integer from 1 to 3, and * represents the bonding position with L1 or M1. In addition, the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH3)2-O) n3 -*, where n3 represents an integer from 6 to 10, and * represents the bonding position with L1 or M1. In addition, the alkylene fluoride structure represented by SP1 is preferably a group represented by *-(CF2-CF2) n4 -*, where n4 represents an integer from 6 to 10, and * represents the bonding position with L1 or M1.

[0023] The mesogenic group represented by M1 is a group that indicates the main skeleton of a liquid crystal molecule that contributes to liquid crystal formation. A liquid crystal molecule exhibits liquid crystallinity, which is an intermediate state (mesophase) between the crystalline state and the isotropic liquid state. There are no particular restrictions on the mesogenic group. For example, reference can be made to "Flussige Kristalle in Tabellen II" (published by VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), particularly the descriptions on pages 7 to 16, and "Liquid Crystal Handbook" edited by the Liquid Crystal Handbook Editorial Committee (published by Maruzen, 2000), particularly the descriptions in Chapter 3. As the mesogenic group, a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferable. The mesogenic group preferably has an aromatic hydrocarbon group, more preferably has 2 to 4 aromatic hydrocarbon groups, and even more preferably has 3 aromatic hydrocarbon groups, because the alignment degree of the light absorption anisotropic film is more excellent.

[0024] As for the mesogenic group, a group represented by the following formula (M1-A) or formula (M1-B) is preferred, and the group represented by formula (M1-B) is more preferred, from the viewpoint of exhibiting liquid crystalline properties, adjusting the liquid crystal phase transition temperature, availability of raw materials, and suitability for synthesis, as well as because it provides a superior degree of orientation of the light-absorbing anisotropic film.

[0025] [ka]

[0026] In formula (M1-A), A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. These groups may be substituted with alkyl groups, alkyl fluoride groups, alkoxy groups, or substituents. The divalent group represented by A1 is preferably a 4- to 6-membered ring. Furthermore, the divalent group represented by A1 may be a monoring or a fused ring. * indicates the binding site with SP1 or T1.

[0027] Examples of the divalent aromatic hydrocarbon group represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetracene-diyl groups. From the viewpoint of the diversity of mesogenic skeleton design and the availability of raw materials, a phenylene or naphthylene group is preferred, with a phenylene group being more preferred.

[0028] The divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but from the viewpoint of improving the degree of orientation, it is preferable that it be a divalent aromatic heterocyclic group. Atoms other than carbon that constitute a divalent aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. If an aromatic heterocyclic group has multiple atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of divalent aromatic heterocyclic groups include, for example, pyridylene (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene (quinoline-diyl group), isoquinolylene (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolothiazole-diyl group, thienothiophene-diyl group, and thienoxazole-diyl group.

[0029] Specific examples of the divalent alicyclic group represented by A1 include the cyclopentylene group and the cyclohexylene group.

[0030] In equation (M1-A), a1 represents an integer between 1 and 10. If a1 is 2 or greater, multiple A1s may be the same or different.

[0031] In formula (M1-B), A2 and A3 are each independently divalent groups selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as those for A1 in formula (M1-A), so their explanation is omitted. In formula (M1-B), a2 represents an integer from 1 to 10. When a2 is 2 or greater, multiple A2s may be the same or different, multiple A3s may be the same or different, and multiple LA1s may be the same or different. a2 is preferably an integer of 2 or greater, and more preferably 2, because it results in a better degree of orientation of the light-absorbing anisotropic film. In formula (M1-B), when a2 is 1, LA1 is a divalent linking group. When a2 is 2 or more, each of the multiple LA1s is independently either a single bond or a divalent linking group, and at least one of the multiple LA1s is a divalent linking group. When a2 is 2, it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond, for a better degree of orientation of the light-absorbing anisotropic film.

[0032] In formula (M1-B), the divalent linking group represented by LA1 is -O-, -(CH2) g -,-(CF2) g -, -Si(CH3)2-, -(Si(CH3)2O) g -,-(OSi(CH3)2) g -(g represents an integer from 1 to 10.), -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-, -OC(O)O-, -N(Z) C(O)-, -C(O)N(Z)-, -C(Z)=C(Z')-C(O)O-, -OC(O)-C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z')-C(O)N(Z'')-, -N(Z'')-C(O Examples include -C(Z)=C(Z')-, -C(Z)=C(Z')-C(O)-S-, -SC(O)-C(Z)=C(Z')-, -C(Z)=NN=C(Z')- (where Z, Z', and Z'' independently represent hydrogen, a C1-C4 alkyl group, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom), -C≡C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-. Among these, -C(O)O- is preferred because it provides a superior degree of orientation for the light-absorbing anisotropic film. LA1 may be a group formed by combining two or more of these groups.

[0033] An example of M1 is the following structure. In the example below, "Ac" represents an acetyl group.

[0034] [ka] [ka] [ka]

[0035] [ka] [ka] [ka] [ka]

[0036] Examples of terminal groups represented by T1 include hydrogen atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, C1-C10 alkyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, C1-C10 alkoxycarbonyloxy groups, C1-C10 alkoxycarbonyl groups (ROC(O)-: R is an alkyl group), C1-C10 acyloxy groups, C1-C10 acylamino groups, C1-C10 alkoxycarbonylamino groups, C1-C10 sulfonylamino groups, C1-C10 sulfamoyl groups, C1-C10 carbamoyl groups, C1-C10 sulfinyl groups, and C1-C10 ureido groups and (meth)acryloyloxy group-containing groups. Examples of the (meth)acryloyloxy group-containing groups mentioned above include the group represented by -LA (where L represents a single bond or a linking group; specific examples of linking groups are the same as those for L1 and SP1 above; A represents a (meth)acryloyloxy group). T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group, because it provides a superior degree of orientation of the light-absorbing anisotropic film. These terminal groups may be further substituted with these groups or with polymerizable groups described in Japanese Patent Application Publication No. 2010-244038. The number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, and particularly preferably 1 to 7, for the reason that it results in a better degree of orientation of the light-absorbing anisotropic film. The degree of orientation of the light-absorbing anisotropic film is further improved when the number of atoms in the main chain of T1 is 20 or less. Here, "main chain" in T1 refers to the longest molecular chain bonded to M1, and hydrogen atoms are not counted in the number of atoms in the main chain of T1. For example, if T1 is an n-butyl group, the number of atoms in the main chain is 4, and if T1 is a sec-butyl group, the number of atoms in the main chain is 3.

[0037] The content of repeating units (3-1) is preferably 20 to 100% by mass relative to 100% by mass of the total repeating units of the polymeric liquid crystalline compound, because this results in a superior degree of orientation of the light-absorbing anisotropic film. In this invention, the content of each repeating unit in the polymeric liquid crystalline compound is calculated based on the amount (mass) of each monomer used to obtain each repeating unit. The repeating unit (3-1) may be present alone or in combination of two or more types in the polymeric liquid crystalline compound. When the polymeric liquid crystalline compound contains two or more types of repeating units (3-1), there are advantages such as improved solubility of the polymeric liquid crystalline compound in the solvent and easier adjustment of the liquid crystal phase transition temperature. When two or more types of repeating units (3-1) are present, it is preferable that their total amount is within the above range.

[0038] When a polymeric liquid crystalline compound contains two types of repeating units (3-1), it is preferable that the terminal group represented by T1 in one repeating unit (repeating unit A) is an alkoxy group, and the terminal group represented by T1 in the other repeating unit (repeating unit B) is a group other than an alkoxy group, for the reason that the degree of orientation of the light-absorbing anisotropic film is superior. In the repeating unit B described above, the terminal group represented by T1 is preferably an alkoxycarbonyl group, a cyano group, or a (meth)acryloyloxy group-containing group, and more preferably an alkoxycarbonyl group or a cyano group, because it provides a superior degree of orientation of the light-absorbing anisotropic film. The ratio (A / B) of the content of repeating unit A in the polymeric liquid crystalline compound to the content of repeating unit B in the polymeric liquid crystalline compound is preferably 50 / 50 to 95 / 5, more preferably 60 / 40 to 93 / 7, and even more preferably 70 / 30 to 90 / 10, for the reason that the degree of orientation of the light-absorbing anisotropic film is superior.

[0039] <Repeating Unit (3-2)> The polymeric liquid crystalline compound of the present invention may further contain a repeating unit represented by the following formula (3-2) (hereinafter also referred to as "repeating unit (3-2)"). This offers advantages such as improved solubility of the polymeric liquid crystalline compound in solvents and easier adjustment of the liquid crystal phase transition temperature. The repeating unit (3-2) differs from the repeating unit (3-1) in that it does not have at least a mesogenic group. If the polymeric liquid crystalline compound contains repeating units (3-2), the polymeric liquid crystalline compound is a copolymer of repeating units (3-1) and repeating units (3-2) (it may also be a copolymer containing repeating units A and B), and may be any polymer such as a block polymer, an alternating polymer, a random polymer, or a graft polymer.

[0040] [ka]

[0041] In formula (3-2), P3 represents the repeating main chain, L3 represents a single bond or a divalent linking group, SP3 represents a spacer group, and T3 represents a terminal group. The specific examples of P3, L3, SP3, and T3 in equation (3-2) are the same as those of P1, L1, SP1, and T1 in equation (3-1) above. Here, in formula (3-2), T3 preferably has a polymerizable group from the viewpoint of improving the strength of the light-absorbing anisotropic film.

[0042] When repeating units (3-2) are present, the content is preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass, relative to 100% by mass of the total repeating units of the polymeric liquid crystalline compound. The repeating unit (3-2) may be present alone or in combination of two or more types in the polymeric liquid crystalline compound. When two or more types of repeating units (3-2) are present, it is preferable that their total amount is within the above range.

[0043] (Weight average molecular weight) The weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably between 1,000 and 500,000, and more preferably between 2,000 and 300,000, because it results in a superior degree of orientation of the light-absorbing anisotropic film. If the Mw of the polymeric liquid crystalline compound is within the above range, the polymeric liquid crystalline compound becomes easier to handle. In particular, from the viewpoint of suppressing cracks during coating, the weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably 10,000 or more, and more preferably between 10,000 and 300,000. Furthermore, from the viewpoint of the temperature latitude of the degree of orientation, the weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably less than 10,000, and preferably between 2,000 and less than 10,000. Here, the weight-average molecular weight and number-average molecular weight in this invention are values ​​measured by gel permeation chromatography (GPC). • Solvent (eluent): N-methylpyrrolidone ·Device name: TOSOH HLC-8220GPC • Column: Three TOSOH TSKgelSuperAWM-H (6mm x 15cm) columns connected together are used. • Column temperature: 25℃ • Sample concentration: 0.1% by mass ·Flow rate: 0.35mL / min • Calibration curve: A calibration curve was used based on 7 samples of TOSOH TSK standard polystyrene with Mw=2,800,000 to 1,050 (Mw / Mn=1.03 to 1.06).

[0044] (Content of liquid crystalline compounds) The content of the liquid crystalline compound is preferably 10 to 97% by mass, more preferably 40 to 95% by mass, and particularly preferably 60 to 95% by mass, based on the total solid content mass of the liquid crystal composition. Having the liquid crystalline compound content within the above range further improves the orientation of the light-absorbing anisotropic film. Preferably, the content of the liquid crystalline compound in the light-absorbing anisotropic film relative to the total mass of the light-absorbing anisotropic film is the same as the content of the liquid crystalline compound relative to the total solid content mass of the liquid crystal composition described above.

[0045] <Dichroic substances> There are no particular limitations on the dichroic substances included in the liquid crystal composition. As the dichroic substance, a dichroic azo dye compound is preferred, and dichroic azo dye compounds commonly used in so-called coated polarizers can be used. The dichroic azo dye compound is not particularly limited, and conventionally known dichroic azo dyes can be used, but the compounds described below are preferred. In a light-absorbing anisotropic film, the dichroic substance may be polymerized.

[0046] In this invention, a dichroic azo dye compound means a dye whose absorbance differs depending on the direction. The dichroic azo dye compound may or may not exhibit liquid crystalline properties. When a dichroic azo dye compound exhibits liquid crystalline properties, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystalline phase is exhibited is preferably room temperature (approximately 20°C to 28°C) to 300°C, and more preferably 50°C to 200°C from the viewpoint of handling and manufacturing suitability.

[0047] In the present invention, from the viewpoint of color adjustment, it is preferable that the light-absorbing anisotropic film has at least one dye compound having a maximum absorption wavelength in the range of 560 to 700 nm (hereinafter also referred to as the "first dichroic azo dye compound") and at least one dye compound having a maximum absorption wavelength in the range of 455 nm or more and less than 560 nm (hereinafter also referred to as the "second dichroic azo dye compound"). More specifically, it is more preferable that it has at least a dichroic azo dye compound represented by formula (1) described later and a dichroic azo dye compound represented by formula (2) described later.

[0048] In the present invention, three or more dichroic azo dye compounds may be used in combination. For example, from the viewpoint of making the light-absorbing anisotropic film closer to black, it is preferable to use a first dichroic azo dye compound, a second dichroic azo dye compound, and at least one dye compound having a maximum absorption wavelength in the range of 380 nm to less than 455 nm (preferably in the range of 380 to 454 nm) in combination (hereinafter also referred to as the "third dichroic azo dye compound").

[0049] In the present invention, it is preferable that the dichroic azo dye compound has a crosslinking group for the reason that it provides better resistance to pressure. Examples of crosslinkable groups include (meth)acryloyl groups, epoxy groups, oxetanyl groups, and styryl groups, with (meth)acryloyl groups being preferred.

[0050] (First dichroic azo dye compound) The first dichroic azo dye compound is preferably a compound having a chromophore as a core and side chains bound to the ends of the chromophore. Specific examples of chromophores include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups) and azo groups. Structures having both aromatic ring groups and azo groups are preferred, and bis-azo structures having an aromatic heterocyclic group (preferably a thienothiazole group) and two azo groups are more preferred. The side chain is not particularly limited and may include groups represented by L3, R2, or L4 in formula (1) described below.

[0051] The first dichroic azo dye compound is preferably a dichroic azo dye compound having a maximum absorption wavelength in the range of 560 nm to 700 nm (more preferably 560 to 650 nm, and particularly preferably 560 to 640 nm) from the viewpoint of adjusting the color of the light-absorbing anisotropic film. In this specification, the maximum absorption wavelength (nm) of a dichroic azo dye compound is determined from the ultraviolet-visible light spectrum in the wavelength range of 380 to 800 nm, measured by a spectrophotometer using a solution of the dichroic azo dye compound dissolved in a good solvent.

[0052] In the present invention, the first dichroic azo dye compound is preferably a compound represented by the following formula (1) because it further improves the degree of orientation of the light-absorbing anisotropic film that is formed.

[0053] [ka]

[0054] In formula (1), Ar1 and Ar2 each independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group, with the phenylene group being preferred.

[0055] In formula (1), R1 represents a hydrogen atom, a linear or branched alkyl group which may have substituents having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an acylamino group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureido group, an alkylphosphate amide group, an alkylimino group, or an alkylsilyl group. The -CH2- group constituting the above alkyl group may also be substituted with -O-, -CO-, -C(O)-O-, -OC(O)-, -Si(CH3)2-O-Si(CH3)2-, -N(R1')-, -N(R1')-CO-, -CO-N(R1')-, -N(R1')-C(O)-O-, -OC(O)-N(R1')-, -N(R1')-C(O)-N(R1')-, -CH=CH-, -C≡C-, -N=N-, -C(R1')=CH-C(O)-, or -OC(O)-O-. If R1 is a group other than a hydrogen atom, the hydrogen atoms in each group may be substituted with a halogen atom, a nitro group, a cyano group, -N(R1')2, an amino group, -C(R1')=C(R1')-NO2, -C(R1')=C(R1')-CN, or -C(R1')=C(CN)2. R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. If multiple R1' elements exist in each group, they may be the same or different from one another.

[0056] In formula (1), R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group which may have substituents having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylamide group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamide group. The -CH2- constituting the above alkyl group may be substituted with -O-, -S-, -C(O)-, -C(O)-O-, -OC(O)-, -C(O)-S-, -SC(O)-, -Si(CH3)2-O-Si(CH3)2-, -NR2'-, -NR2'-CO-, -CO-NR2'-, -NR2'-C(O)-O-, -OC(O)-NR2'-, -NR2'-C(O)-NR2'-, -CH=CH-, -C≡C-, -N=N-, -C(R2')=CH-C(O)-, or -OC(O)-O-. If R2 and R3 are groups other than hydrogen atoms, the hydrogen atoms in each group may be substituted with halogen atoms, nitro groups, cyano groups, -OH groups, -N(R2')2, amino groups, -C(R2')=C(R2')-NO2, -C(R2')=C(R2')-CN, or -C(R2')=C(CN)2. R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. If multiple R2' elements exist in each group, they may be identical or different from one another. R2 and R3 may bond to each other to form a ring, or R2 or R3 may bond to Ar2 to form a ring.

[0057] From the viewpoint of lightfastness, R1 is preferably an electron-withdrawing group, and R2 and R3 are preferably groups with low electron-donating properties. Specific examples of such groups include alkylsulfonyl groups, alkylcarbonyl groups, alkyloxycarbonyl groups, acyloxy groups, alkylsulfonylamino groups, alkylsulfamoyl groups, alkylsulfinyl groups, and alkylureido groups for R1, and groups with the following structures for R2 and R3. Note that the groups with the following structures are shown in formula (1) above in a form that includes the nitrogen atom to which R2 and R3 are bonded.

[0058] [ka]

[0059] Specific examples of the first dichroic azo dye compound are shown below, but are not limited to these.

[0060] [ka] JPEG0007863517000015.jpg161127 JPEG0007863517000016.jpg1295

[0061] (Second dichroic azo dye compound) The second dichroic azo dye compound is a different compound from the first dichroic azo dye compound, specifically in its chemical structure. The second dichroic azo dye compound is preferably a compound having a chromophore, which is the core of the dichroic azo dye compound, and a side chain bound to the end of the chromophore. Specific examples of chromophores include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups) and azo groups. Structures having both aromatic hydrocarbon groups and azo groups are preferred, and bisazo or trisazo structures having an aromatic hydrocarbon group and two or three azo groups are more preferred. The side chain is not particularly limited and may include groups represented by R4, R5, or R6 in formula (2) described below.

[0062] The second dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the range of 455 nm to less than 560 nm. From the viewpoint of adjusting the color of the light-absorbing anisotropic film, it is preferable that the dichroic azo dye compound has a maximum absorption wavelength in the range of 455 to 555 nm, and more preferably that it has a maximum absorption wavelength in the range of 455 to 550 nm. In particular, using a first dichroic azo dye compound with a maximum absorption wavelength of 560-700 nm and a second dichroic azo dye compound with a maximum absorption wavelength of 455 nm or more and less than 560 nm makes it easier to adjust the color of the light-absorbing anisotropic film.

[0063] The second dichroic azo dye compound is preferably the compound represented by formula (2) because it further improves the degree of orientation of the light-absorbing anisotropic film.

[0064] [ka]

[0065] In equation (2), n represents either 1 or 2. In formula (2), Ar3, Ar4, and Ar5 each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted heterocyclic group. The heterocyclic group may be either aromatic or non-aromatic. Atoms other than carbon that constitute an aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. If an aromatic heterocyclic group has multiple atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of aromatic heterocyclic groups include pyridylene (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene (quinoline-diyl group), isoquinolylene (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolothiazole-diyl group, thienothiophene-diyl group, and thienoxazole-diyl group.

[0066] In equation (2), the definition of R4 is the same as that of R1 in equation (1). In equation (2), the definitions of R5 and R6 are the same as those of R2 and R3 in equation (1), respectively.

[0067] From the viewpoint of lightfastness, R4 is preferably an electron-withdrawing group, and R5 and R6 are preferably groups with low electron-donating properties. Among these groups, a specific example when R4 is an electron-withdrawing group is the same as a specific example when R1 is an electron-withdrawing group, and a specific example when R5 and R6 are groups with low electron-donating properties is the same as a specific example when R2 and R3 are groups with low electron-donating properties.

[0068] Specific examples of the second type of dichroic azo dye compound are shown below, but are not limited to these.

[0069] [ka] JPEG0007863517000019.jpg155111 JPEG0007863517000020.jpg160105 JPEG0007863517000021.jpg167111 JPEG0007863517000022.jpg1490

[0070] (Difference in logP values) The logP value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure. The absolute difference between the logP value of the side chain of the first dichroic azo dye compound and the logP value of the side chain of the second dichroic azo dye compound (hereinafter also referred to as the "logP difference") is preferably 2.30 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.0 or less. If the logP difference is 2.30 or less, the affinity between the first dichroic azo dye compound and the second dichroic azo dye compound increases, making it easier to form a sequence structure, and thus the degree of orientation of the light-absorbing anisotropic film is further improved. Furthermore, if the first dichroic azo dye compound or the second dichroic azo dye compound has multiple side chains, it is preferable that at least one logP difference satisfies the above value. Here, the side chains of the first dichroic azo dye compound and the second dichroic azo dye compound refer to the groups that bind to the ends of the chromophore described above. For example, if the first dichroic azo dye compound is the compound represented by formula (1), then R1, R2, and R3 in formula (1) are the side chains, and if the second dichroic azo dye compound is the compound represented by formula (2), then R4, R5, and R6 in formula (2) are the side chains. In particular, if the first dichroic azo dye compound is the compound represented by formula (1) and the second dichroic azo dye compound is the compound represented by formula (2), it is preferable that at least one of the logP differences among the difference in logP values ​​between R1 and R4, the difference in logP values ​​between R1 and R5, the difference in logP values ​​between R2 and R4, and the difference in logP values ​​between R2 and R5 satisfies the above value.

[0071] Here, the logP value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure, and is sometimes called the hydrophilic / hydrophobic parameter. The logP value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver. 4.1.07). It can also be determined experimentally by methods such as those described in OECD Guidelines for the Testing of Chemicals, Sections 1, Test No. 117. In this invention, unless otherwise specified, the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07) will be adopted as the logP value.

[0072] (Third dichroic azo dye compound) The third dichroic azo dye compound is a dichroic azo dye compound other than the first and second dichroic azo dye compounds, and specifically, it has a different chemical structure from the first and second dichroic azo dye compounds. If the light-absorbing anisotropic film contains the third dichroic azo dye compound, it has the advantage of making it easier to adjust the color of the light-absorbing anisotropic film. The maximum absorption wavelength of the third dichroic azo dye compound is 380 nm or more and less than 455 nm, with 385 to 454 nm being preferred. Specific examples of the third dichroic azo dye compound include compounds represented by formula (1) described in International Publication No. 2017 / 195833, other than the first dichroic azo dye compound and the second dichroic azo dye compound.

[0073] The following are specific examples of the third dichroic azo dye compound, but the present invention is not limited to these. In the following examples, n represents an integer from 1 to 10, and Me represents a methyl group.

[0074] [ka]

[0075] [ka] JPEG0007863517000025.jpg11120

[0076] (Content of dichroic substances) The content of the dichroic substance is preferably 1 to 70% by mass, more preferably 2 to 60% by mass, and particularly preferably 3 to 50% by mass, relative to the total solid content mass of the liquid crystal composition. If the content of the dichroic substance is within the above range, a highly oriented light-absorbing anisotropic film can be obtained even when the light-absorbing anisotropic film is made into a thin film. Therefore, a light-absorbing anisotropic film with excellent flexibility can be easily obtained. Preferably, the content of dichroic substance in the light-absorbing anisotropic film relative to the total mass of the light-absorbing anisotropic film is the same as the content of dichroic substance relative to the total solid content mass of the liquid crystal composition described above.

[0077] The content of the first dichroic azo dye compound is preferably 40 to 90 parts by mass, and more preferably 45 to 75 parts by mass, based on 100 parts by mass of the total content of dichroic substances in the liquid crystal composition. The content of the second dichroic azo dye compound is preferably 6 to 50 parts by mass, and more preferably 8 to 35 parts by mass, based on 100 parts by mass of the total content of dichroic substances in the liquid crystal composition. The content of the third dichroic azo dye compound is preferably 3 to 35 parts by mass, and more preferably 5 to 30 parts by mass, based on 100 parts by mass of the total content of dichroic substances in the liquid crystal composition. The content ratio of the first dichroic azo dye compound, the second dichroic azo dye compound, and the third dichroic azo dye compound, which may be used as needed, can be arbitrarily set to adjust the color of the light-absorbing anisotropic film. However, the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound (second dichroic azo dye compound / first dichroic azo dye compound) is preferably 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8 in molar terms. If the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound is within the above range, the degree of orientation can be increased.

[0078] <Coincident boronic acid compound> The polymerizable boronic acid compound is a compound having at least one group selected from the group consisting of a boronic acid group, a boronic acid ester group, and a boroxine ring group formed by dehydration condensation of boronic acid groups, and a polymerizable group. The boroxine ring group is formed by dehydration trimerization of boronic acid groups. In the light absorption anisotropic film, the polymerizable boronic acid compound may be polymerized.

[0079] As the polymerizable group, an acryloyl group, a methacryloyl group, an epoxy group, an oxetanyl group, and a styryl group are preferable, and an acryloyl group and a methacryloyl group are more preferable from the viewpoint of better adhesion. The polymerizable boronic acid compound may have one or more polymerizable groups, and may have two or more polymerizable groups, but it is preferable to have one polymerizable group from the viewpoint of better adhesion and orientation degree.

[0080] The boronic acid group is a group represented by -B(OH)2. As the boronic acid ester group, among the groups represented by -B(-OR B12 )(-OR B13 ) in the following formula (B-1), those in which at least one of R B12 and R B13 is a group other than a hydrogen atom are included. As the boroxine ring group, a group represented by the following formula (BX) is included. In the formula (BX), * means a bond with another group. The polymerizable boronic acid compound may have at least one group selected from the group consisting of a boronic acid group, a boronic acid ester group, and a boroxine ring group, and may have two or more such groups, but it is preferable to have only one group from the viewpoint of better adhesion and orientation degree.

[0081]

Chemical formula

[0082] Polymerizable boronic acid compounds are preferably those that have an aromatic ring, as this results in a superior degree of orientation. Examples of aromatic rings include aromatic hydrocarbon groups and aromatic heterocyclic groups. Among these, aromatic hydrocarbon groups are preferred because they offer superior adhesion and at least one of the degrees of orientation. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 4 to 20, and more preferably 6 to 12. Examples of aromatic hydrocarbon groups include benzene ring groups. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5. Examples of atoms other than carbon atoms that constitute the aromatic heterocyclic group include oxygen atoms, nitrogen atoms, and sulfur atoms. Aromatic hydrocarbon groups and aromatic heterocyclic groups may be substituted with substituents. When a polymerizable boronic acid compound has an aromatic ring, the number of aromatic rings may be one or two or more, but it is preferable to have one ring from the viewpoint of superior orientation.

[0083] The polymerizable boronic acid compound preferably contains at least one of the compound represented by formula (B-1) and the compound represented by formula (BX-1) because it exhibits superior adhesion and degree of orientation. The compound represented by formula (BX-1) can be obtained, for example, by dehydration condensation of the compound represented by formula (B-1).

[0084] [ka]

[0085] In formula (B-1), R B11 represents a hydrogen atom or a methyl group.

[0086] L B1 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) B14This represents a divalent group (hereinafter also referred to as "divalent linking group B1") that is substituted with at least one group selected from the group consisting of )- (hereinafter also referred to as "specific group B1"). Among these, the divalent linking group B1 is preferred because it has superior orientation and adhesion. R B14 represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is particularly preferred. The divalent aliphatic hydrocarbon group may be saturated or unsaturated, but it is preferably saturated. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but it is preferably linear or branched. The divalent aliphatic hydrocarbon group is preferably an alkylene group because it offers superior orientation and adhesion. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, and particularly preferably 1 to 5. The divalent linking group B1 may consist of a single -CH2- group that constitutes a divalent aliphatic hydrocarbon group, or it may consist of two or more -CH2- groups that are substituted with the specific group B1. Preferred embodiments of the divalent linking group B1 include -C(=O)-O-alkylene group-, -C(=O)-O-alkylene group-N(R B14 )-C(=O)-O-, -C(=O)-O-alkylene group-O-, -C(=O)-N(R B14 )-,-alkylene group-N(R B14 Examples include )-C(=O)-O- and the alkylene group-O-.

[0087] A B1 This represents an optionally substituted arylene group or an optionally substituted heteroarylene group. Among these, an optionally substituted arylene group is preferred because it offers superior adhesion and at least one of the degree of orientation, and an arylene group (i.e., an unsubstituted arylene group) is particularly preferred. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 4 to 20, and more preferably 6 to 12. An example of an arylene group is a phenylene group. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5. Examples of heteroatoms included in the heteroaryl group include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0088] R B12 and R B13 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. Among these, a hydrogen atom or an optionally substituted alkyl group is preferred, and a hydrogen atom is more preferred, from the viewpoint of having better adhesion and degree of orientation. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Examples of alkyl groups include methyl, ethyl, and propyl groups. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 4 to 20, and more preferably 6 to 12. An example of an aryl group is the phenyl group. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5. Examples of heteroatoms included in the heteroaryl group include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0089] R B12 and R B13 These atoms may be bonded to each other to form a ring. Examples of the rings that may be formed include aliphatic hydrocarbon rings containing boron atoms.

[0090] Of the compounds represented by formula (B-1), the compound represented by formula (B-2) is preferred because it exhibits superior adhesion and at least one of the degrees of orientation.

[0091] [ka]

[0092] In formula (B-2), R B21 represents a hydrogen atom or a methyl group.

[0093] L B2 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) B25 This represents a divalent group (hereinafter also referred to as "divalent linking group B2") that is substituted with at least one group selected from the group consisting of )- (hereinafter also referred to as "specific group B2"). Among these, the divalent linking group B2 is preferred because it has superior orientation and adhesion. R B25 represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is particularly preferred. L B2 In this, the divalent aliphatic hydrocarbon group, the divalent linking group B2, and the specific group B2 are each L of formula (B-1) B1 The divalent aliphatic hydrocarbon group, the divalent linking group B1, and the specific group B1 are the same as in the above, so their explanation is omitted.

[0094] R B22 and R B23 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. Among these, a hydrogen atom or an optionally substituted alkyl group is preferred, and a hydrogen atom is more preferred, from the viewpoint of having better adhesion and degree of orientation. R B22 Each group in is R in formula (B-1) B12 Since it is the same as each of the groups in [the relevant section], the explanation will be omitted. R B23 Each group in is R in formula (B-1) B13 Since it is the same as each of the groups in [the relevant section], the explanation will be omitted. R B22 and R B23 These atoms may be bonded to each other to form a ring. Examples of the rings that may be formed include aliphatic hydrocarbon rings containing boron atoms.

[0095] R B24The symbol represents a monovalent substituent. Specific examples of monovalent substituents are described below. Preferred monovalent substituents are alkyl groups, halogen atoms, alkoxy groups, or aryl groups. nb represents an integer between 0 and 4. Among these, 0 or 1 is preferred, and 0 is more preferred, as it offers superior adhesion and orientation. If nb is 2 or more, multiple R B24 These may be the same or different.

[0096] In the compound represented by formula (B-2), -B(OR B22 )(OR B23 The position of the group represented by ) is not particularly limited, but L is preferred in terms of superior adhesion and degree of orientation. B2 It is preferable that the compound is positioned at the meta or para position relative to the binding site.

[0097] Specific examples of compounds represented by formula (B-1) are shown below, but the examples are not limited to these. In the formula, Me represents a methyl group.

[0098] [ka]

[0099] [ka]

[0100] In formula (BX-1), R BX11 R represents a hydrogen atom or a methyl group. Multiple R BX11 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior.

[0101] L BX1 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) BX14This represents a divalent group (hereinafter also called "divalent linking group BX1") substituted with at least one group selected from the group consisting of )- (hereinafter also called "specific group BX1"). Among these, the divalent linking group BX1 is preferred because it has superior orientation and adhesion. Multiple L BX1 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior. R BX14 R represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is particularly preferred. Multiple R BX14 If multiple R BX14 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior. L BX1 In this, the divalent aliphatic hydrocarbon group, the divalent linking group BX1, and the specific group BX1 are each L of formula (B-1) B1 The divalent aliphatic hydrocarbon group, the divalent linking group B1, and the specific group B1 are the same as in the above, so their explanation is omitted.

[0102] A BX1 This represents an optionally substituted arylene group or an optionally substituted heteroarylene group. Among these, an optionally substituted arylene group is preferred because it offers superior adhesion and at least one of the degree of orientation, and an arylene group (i.e., an unsubstituted arylene group) is particularly preferred. Multiple A BX1 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 4 to 20, and more preferably 6 to 12. Examples of arylene groups include phenylene groups and naphthalene groups. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5. Examples of heteroatoms included in the heteroaryl group include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0103] The compound represented by formula (BX-2) is preferred over the compound represented by formula (BX-1) because it exhibits superior adhesion and at least one of the degrees of orientation.

[0104] [ka]

[0105] In formula (BX-2), R BX21 R represents a hydrogen atom or a methyl group. Multiple R BX21 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior.

[0106] L BX2 This refers to a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group that are -O-, -C(=O)-, and -N(R) BX25 This represents a divalent group (hereinafter also called "divalent linking group BX2") substituted with at least one group selected from the group consisting of )- (hereinafter also called "specific group BX2"). Among these, the divalent linking group BX2 is preferred because it has superior orientation and adhesion. Multiple L BX2 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior. R BX25 R represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is particularly preferred. Multiple R BX25 If multiple R BX25 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior. L BX2In this, the divalent aliphatic hydrocarbon group, the divalent linking group BX2, and the specific group BX2 are each L of formula (B-1) B1 The divalent aliphatic hydrocarbon group, the divalent linking group B1, and the specific group B1 are the same as in the above, so their explanation is omitted.

[0107] R BX24 This represents a monovalent substituent. Multiple R BX24 If multiple R BX24 These may be the same or different, but it is preferable that they be the same in that at least one of the adhesion and degree of orientation is superior. R BX24 Specific examples of monovalent substituents are described below. Preferred monovalent substituents are alkyl groups, halogen atoms, alkoxy groups, or aryl groups. nc represents an integer from 0 to 4. Among these, 0 or 1 is preferred, with 0 being more preferred, from the viewpoint of having better adhesion and orientation. Multiple nc values ​​may be the same or different, but it is preferable that they be the same from the viewpoint of having better adhesion and orientation.

[0108] Specific examples of compounds represented by formula (BX-1) are shown below, but the formula is not limited to these examples. In the formula, Me represents a methyl group.

[0109] [ka] JPEG0007863517000033.jpg85148

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] The content of the polymerizable boronic acid compound is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and particularly preferably 0.3 to 6% by mass, based on the total solid content mass of the liquid crystal composition. If the content of the polymerizable boronic acid compound is above the lower limit, the adhesion of the light-absorbing anisotropic film is better. If the content of the polymerizable boronic acid compound is below the upper limit, the degree of orientation of the light-absorbing anisotropic film is better. Polymerizable boronic acid compounds may be used individually or in combination of two or more. When two or more polymerizable boronic acid compounds are included, it is preferable that their total amount is within the above range. The content of the polymerizable boronic acid compound in the light-absorbing anisotropic film relative to the total mass of the light-absorbing anisotropic film is preferably the same as the content of the polymerizable boronic acid compound relative to the total solid content mass of the liquid crystal composition described above.

[0115] The liquid crystal composition preferably contains both the compound represented by formula (B-1) (preferably the compound represented by formula (B-2)) and the compound represented by formula (BX-1) (preferably the compound represented by formula (BX-2)), in terms of excellent storage stability of the liquid crystal composition. In this case, in terms of superior storage stability of the liquid crystal composition, the mass ratio of the content of the compound represented by formula (B-1) to the content of the compound represented by formula (BX-1) (content of the compound represented by formula (B-1) / content of the compound represented by formula (BX-1)) is preferably 0.1 to 2000, more preferably 1 to 1000, and even more preferably 5 to 500.

[0116] <Solvent> From the viewpoint of workability and other factors, the liquid crystal composition preferably contains a solvent. Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, and cyclopentyl methyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), and halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, and chlorotoluene). Examples of solvents include organic solvents such as methyl acetate, ethyl acetate, butyl acetate, and diethyl carbonate, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, and 1,2-dimethoxyethane), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone), and heterocyclic compounds (e.g., pyridine), as well as water. These solvents may be used individually or in combination of two or more. Of these solvents, organic solvents are preferred, and halogenated carbons or ketones are more preferred, because they provide superior effects for the present invention.

[0117] If the liquid crystal composition contains a solvent, the solvent content is preferably 80 to 99% by mass, more preferably 83 to 97% by mass, and particularly preferably 85 to 95% by mass, based on the total mass of the liquid crystal composition. The solvent may be used alone or in combination of two or more. When two or more solvents are included, it is preferable that their total amount is within the above range.

[0118] <Interface modifier> The liquid crystal composition preferably contains an interface modifier (hereinafter also referred to as "surfactant"). By including an interface modifier, the smoothness of the coated surface is improved, the degree of orientation is improved, and repulsion and unevenness are suppressed, resulting in improved uniformity within the surface. As the interface modifier, one that horizontally aligns the liquid crystalline compound is preferred, and the compounds (horizontal alignment agents) described in paragraphs

[0253] to

[0293] of Japanese Patent Application Publication No. 2011-237513 can be used. In addition, fluorine (meth)acrylate polymers described in paragraphs

[0018] to

[0043] , etc., of Japanese Patent Application Publication No. 2007-272185 can also be used. Other compounds may also be used as interface modifiers. When the liquid crystal composition contains an interface modifier, the content of the interface modifier in the liquid crystal composition is preferably 0.1 to 2.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total solid content mass of the liquid crystal composition. The interface modifier may be used alone or in combination of two or more types. When two or more interface modifiers are included, it is preferable that their total amount is within the above range. When the light-absorbing anisotropic film contains an interface modifier, it is preferable that the content of the interface modifier relative to the total mass of the light-absorbing anisotropic film is the same as the content of the interface modifier relative to the total solid content mass of the liquid crystal composition.

[0119] <Polymerization initiator> The liquid crystal composition preferably contains a polymerization initiator. The polymerization initiator used is preferably a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation. Examples of photopolymerization initiators include α-carbonyl compounds (as described in U.S. Patent Nos. 2367661 and 2367670), acyloin ethers (as described in U.S. Patent No. 2448828), α-hydrocarbon-substituted aromatic acyloin compounds (as described in U.S. Patent No. 2722512), polynuclear quinone compounds (as described in U.S. Patent Nos. 3046127 and 2951758), triarylimidazole dimers and p-aminophenyl ketones. Examples include combinations of these compounds (as described in U.S. Patent No. 3,549,367), acridine and phenazine compounds (as described in Japanese Patent Publication No. 60-105667 and U.S. Patent No. 4,239,850) and oxadiazole compounds (as described in U.S. Patent No. 4,212,970), and acylphosphine oxide compounds (as described in Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Publication No. 10-95788 and Japanese Patent Publication No. 10-29997). Furthermore, in the present invention, it is also preferable that the polymerization initiator is an oxime-type polymerization initiator, and a specific example thereof is the initiator described in paragraphs

[0049] to

[0052] of International Publication No. 2017 / 170443.

[0120] When the liquid crystal composition contains a polymerization initiator, the amount of polymerization initiator is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the total of the dichroic substance and the liquid crystalline compound in the liquid crystal composition. A polymerization initiator content of 0.01 parts by mass or more results in good durability of the light-absorbing anisotropic film, and a content of 30 parts by mass or less results in better orientation of the light-absorbing anisotropic film. Polymerization initiators may be used individually or in combination of two or more. When two or more polymerization initiators are included, it is preferable that their total amount is within the above range.

[0121] <Substituent> In this specification, substituents mean the following groups unless otherwise specified. Examples of substituents include alkyl groups (preferably C1-C20, more preferably C1-C12, and particularly preferably C1-C8 alkyl groups, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl groups), alkenyl groups (preferably C2-C20, more preferably C2-C12, and particularly preferably C2-C8 alkenyl groups, such as vinyl, aryl, and 2-butenyl groups), Examples include C13 groups and 3-pentenyl groups), alkynyl groups (preferably C2-C20, more preferably C2-C12, and particularly preferably C2-C8 alkynyl groups, such as propargyl and 3-pentinyl groups), and aryl groups (preferably C6-C30, more preferably C6-C20, and particularly preferably C6-C12 aryl groups, such as phenyl, 2,6-diethylphenyl, 3,5-ditrifluoromethylphenyl, styryl, naphthyl, and biphenyl groups). ), substituted or unsubstituted amino groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as unsubstituted amino groups, methylamino groups, dimethylamino groups, diethylamino groups, and anilino groups), alkoxy groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as methoxy groups, ethoxy groups, and butoxy groups), oxycarbonyl groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, particularly preferably 2 to 10, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and a phenoxycarbonyl group), an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, an acetoxy group, a benzoyloxy group, an acryloyl group, and a methacryloyl group), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, an acetylamino group and a benzoylamino group),Alkoxycarbonylamino groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino groups), aryloxycarbonylamino groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example, phenyloxycarbonylamino groups), sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methanesulfonylamino groups) Examples include the phenylsulfamylamino group and the benzenesulfonylamino group), sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, and phenylsulfamoyl group), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, and phenylsulfamoyl group) Examples include a bamold group, alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, such as a methylthio group and an ethylthio group), arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, such as a mesyl group and a tosyl group). ), sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methanesulfinyl group and benzenesulfinyl group), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, unsubstituted ureido group, methylureido group and phenylureido group), phosphate amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example,Examples include diethyl phosphate amide groups and phenyl phosphate amide groups), hydroxyl groups, mercapto groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, imino groups, azo groups, heterocyclic groups (preferably heterocyclic groups having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example heterocyclic groups having heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms, for example epoxy groups, oxy Examples of carbon atoms include cetanyl groups, imidazolyl groups, pyridyl groups, quinolyl groups, furyl groups, piperidyl groups, morpholino groups, maleimide groups, benzoxazolyl groups, benzimidazolyl groups, and benzthiazolyl groups), silyl groups (preferably silyl groups having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl groups), carboxyl groups, sulfonic acid groups, and phosphate groups.

[0122] [Horizontal orientation] As described above, in the light-absorbing anisotropic film of the present invention, the liquid crystalline compound is horizontally oriented. Furthermore, in the light-absorbing anisotropic film of the present invention, it is preferable that the dichroic substance is also horizontally oriented along the liquid crystalline compound. Here, horizontal orientation refers to the fact that the molecular axis of the liquid crystalline compound (for example, the long axis in the case of a rod-shaped liquid crystalline compound) is parallel to the main surface of the light-absorbing anisotropic film. However, it does not require strict parallelism; rather, it means that the inclination angle between the average molecular axis of the liquid crystalline compound in the light-absorbing anisotropic film and the main surface of the light-absorbing anisotropic film is less than ±10 degrees. This inclination angle can be measured using AxoScan OPMF-1 (OptoScience Co., Ltd.). Specifically, using AxoScan OPMF-1 (manufactured by OptoSciences), at room temperature, the Mueller matrix of the light absorption anisotropic film at wavelength λ is measured every 10 degrees from a polar angle of -50 degrees to 50 degrees. After removing the influence of surface reflection, the attenuation coefficients ko[λ] (in-plane direction) and ke[λ] (thickness direction) are calculated by fitting the following theoretical formula considering Snell's law and Fresnel's law. Unless otherwise specified, the wavelength λ is 550 nm. k = -log(T) × λ / (4πd) Here, T represents the transmittance, and d represents the thickness of the polarizer. From the calculated ko[λ] and ke[λ], it is possible to confirm whether it is horizontally oriented by calculating the absorbance and dichroic ratio in the in-plane direction and thickness direction.

[0123] [Manufacturing method of light absorption anisotropic film] The method for manufacturing the light absorption anisotropic film of the present invention is not particularly limited. However, for the reason that the degree of orientation of the obtained light absorption anisotropic film becomes higher, a step of applying the above-described liquid crystal composition on an alignment film to form a coating film (hereinafter, also referred to as "coating film formation step"), and a step of aligning the liquid crystal components contained in the coating film (hereinafter, also referred to as "alignment step") are preferably provided in this order (hereinafter, also referred to as "this manufacturing method"). Note that the liquid crystal component is a component that includes not only the above-described liquid crystal compound but also a dichroic substance having liquid crystallinity. Hereinafter, each step will be described.

[0124] [Coating film formation step] The coating film formation step is a step of applying the above-described liquid crystal composition on an alignment film to form a coating film. The liquid crystal compound in the coating film is horizontally aligned by the interaction between the alignment film and (when the liquid crystal composition contains an interface modifier) the interface modifier. By using the above-described liquid crystal composition containing a solvent, or using a liquid crystal composition made into a liquid substance such as a melt by heating the liquid crystal composition, etc., it becomes easy to apply the liquid crystal composition on the alignment film. Known methods for coating liquid crystal compositions include roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0125] (Orientation film) The alignment film can be any film that horizontally aligns the liquid crystalline compounds contained in the liquid crystal composition. This can be achieved by means of rubbing an organic compound (preferably a polymer) onto the film surface, oblique deposition of an inorganic compound, formation of a layer having microgrooves, or accumulation of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate) by the Langmuir-Bludget method (LB film). Furthermore, orientation films that exhibit orientation function upon application of an electric field, magnetic field, or light irradiation are also known. Among these, in the present invention, orientation films formed by rubbing are preferred from the viewpoint of ease of controlling the pre-tilt angle of the orientation film, and photo-alignment films formed by light irradiation are also preferred from the viewpoint of uniformity of orientation.

[0126] (1) Rubbing-treated orientation film Numerous polymer materials are described in various publications and many commercially available products can be used for the orientation film formed by the rubbing process. In this invention, polyvinyl alcohol or polyimide, and their derivatives, are preferably used. For the orientation film, refer to the description on pages 43, line 24 to 49, line 8 of International Publication No. 2001 / 88574A1. The thickness of the orientation film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

[0127] (2) Photoalignment film Numerous publications describe photo-alignment materials used in alignment films formed by light irradiation. In this invention, for example, azo compounds described in Japanese Patent Publication No. 2006-285197, Japanese Patent Publication No. 2007-76839, Japanese Patent Publication No. 2007-138138, Japanese Patent Publication No. 2007-94071, Japanese Patent Publication No. 2007-121721, Japanese Patent Publication No. 2007-140465, Japanese Patent Publication No. 2007-156439, Japanese Patent Publication No. 2007-133184, Japanese Patent Publication No. 2009-109831, Japanese Patent No. 3883848, Japanese Patent No. 4151746, and Japanese Patent Publication No. 2002-229039 are used. Preferred examples include aromatic ester compounds, maleimide and / or alkenyl-substituted nadiimide compounds having photo-orienting units as described in Japanese Patent Publication No. 2002-265541 and Japanese Patent Publication No. 2002-317013, photocrosslinkable silane derivatives as described in Japanese Patent No. 4205195 and Japanese Patent No. 4205198, Japanese Patent Publication No. 2003-520878 and Japanese Patent Publication No. 2004-529220, or photocrosslinkable polyimide, polyamide, or ester as described in Japanese Patent No. 4162850. More preferably are azo compounds, photocrosslinkable polyimide, polyamide, or ester.

[0128] A photo-alignment film is manufactured by irradiating a photo-alignment film formed from the above materials with linearly polarized or unpolarized light. In this specification, "linearly polarized irradiation" and "unpolarized irradiation" refer to operations for causing a photoreaction in a photo-oriented material. The wavelength of light used varies depending on the photo-oriented material used and is not particularly limited as long as it is the wavelength necessary for the photoreaction. The peak wavelength of the light used for irradiation is preferably 200 nm to 700 nm, and ultraviolet light with a peak wavelength of 400 nm or less is more preferred.

[0129] Light sources used for light irradiation include commonly used light sources such as lamps like tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps; various lasers [e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG (yttrium-aluminum-garnet) lasers]; light-emitting diodes; and cathode ray tubes.

[0130] Methods for obtaining linearly polarized light include using polarizers (e.g., iodine polarizers, dichroic polarizers, and wire grid polarizers), using prism-type elements (e.g., Grant-Thomson prisms) or reflective polarizers utilizing the Brewster angle, or using light emitted from a polarized laser light source. Alternatively, filters or wavelength conversion elements may be used to selectively irradiate only the light of the required wavelength.

[0131] When linearly polarized light is used, the light is irradiated from the top or back surface of the alignment film, perpendicular or oblique to the surface of the alignment film. The angle of incidence of the light varies depending on the photo-alignment material, but is preferably 0 to 90° (perpendicular), and preferably 40 to 90°. In the case of non-polarized light, the orientation film is irradiated with non-polarized light from an oblique angle. The incident angle is preferably 10 to 80°, more preferably 20 to 60°, and particularly preferably 30 to 50°. The irradiation time is preferably 1 to 60 minutes, and more preferably 1 to 10 minutes.

[0132] If patterning is required, a method can be employed in which light irradiation using a photomask is performed the number of times necessary to create the pattern, or a method can be employed in which the pattern is written by laser scanning.

[0133] <Orientation Process> The orientation step is a process of aligning the dichroic substances contained in the coated film. This yields the light-absorbing anisotropic film of the present invention. In the orientation step, it is believed that the dichroic substances are oriented along the liquid crystalline compound oriented by the orientation film. The orientation step may include a drying process. The drying process can remove components such as solvents from the coating film. The drying process may be carried out by leaving the coating film at room temperature for a predetermined time (e.g., natural drying), or by heating and / or blowing air. Here, the dichroic substances contained in the liquid crystal composition may be oriented by the coating film formation process or drying process described above. For example, in embodiments in which the liquid crystal composition is prepared as a coating solution containing a solvent, drying the coating film to remove the solvent from the coating film may cause the dichroic substances contained in the coating film to be oriented, thereby obtaining the light-absorbing anisotropic film of the present invention.

[0134] The orientation step preferably includes a heat treatment. This further orients the dichroic substances contained in the coating film, resulting in a higher degree of orientation of the resulting light-absorbing anisotropic film. The heat treatment is preferably performed at 10 to 250°C, and more preferably at 25 to 190°C, from the standpoint of suitability for manufacturing. The heating time is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.

[0135] The orientation step may include a cooling process performed after the heat treatment. The cooling process involves cooling the heated coating film to room temperature (approximately 20-25°C). This further fixes the orientation of the dichroic substances contained in the coating film, resulting in a higher degree of orientation of the resulting light-absorbing anisotropic film. The cooling method is not particularly limited and can be carried out by known methods. The light-absorbing anisotropic film of the present invention can be obtained through the above steps.

[0136] [Other processes] This manufacturing method may include a step of curing the light-absorbing anisotropic film after the orientation step (hereinafter also referred to as the "curing step"). The curing process is carried out, for example, by heating and / or light irradiation (exposure). Among these, the curing process is preferably carried out by light irradiation. As the light source used for curing, various light sources such as infrared rays, visible light, or ultraviolet rays can be used, but ultraviolet rays are preferable. Also, ultraviolet rays may be irradiated while heating during curing, or ultraviolet rays may be irradiated through a filter that transmits only a specific wavelength. Also, the exposure may be carried out in a nitrogen atmosphere. When the curing of the photoabsorptive anisotropic film proceeds by radical polymerization, it is preferable to carry out the exposure in a nitrogen atmosphere because the inhibition of polymerization by oxygen is reduced.

[0137] [Liquid crystal composition] The liquid crystal composition of the present invention is a liquid crystal composition containing a liquid crystalline compound, a dichroic substance, and a boronic acid compound having a polymerizable group, wherein the boronic acid compound having a polymerizable group is a compound represented by the formula (B-2). The components contained and that can be contained in the liquid crystal composition of the present invention are the same as the components contained and that can be contained in the above-described liquid crystal composition used for forming the photoabsorptive anisotropic film of the present invention, and their preferred embodiments are also the same, so the description thereof is omitted. The liquid crystal composition of the present invention is preferably used for forming the above-described photoabsorptive anisotropic film.

[0138] [Laminate] The laminate of the present invention has the above-described photoabsorptive anisotropic film of the present invention and a layer containing a polyvinyl alcohol-based resin disposed so as to be in contact with the photoabsorptive anisotropic film. Also, the laminate of the present invention may have a λ / 4 plate on the side opposite to the layer containing the polyvinyl alcohol-based resin of the photoabsorptive anisotropic film. Further, the laminate of the present invention may have a barrier layer between the photoabsorptive anisotropic film and the λ / 4 plate. Also, the laminate of the present invention may have a substrate on the side opposite to the photoabsorptive anisotropic film of the layer containing the polyvinyl alcohol-based resin. Hereinafter, each layer constituting the laminate of the present invention will be described.

[0139] [Base material] The substrate can be selected as appropriate, and examples include glass and polymer films. The light transmittance of the substrate is preferably 80% or higher. When using a polymer film as a substrate, it is preferable to use an optically isotropic polymer film. Specific examples of polymers and preferred embodiments can be found in paragraph

[0013] of Japanese Patent Application Publication No. 2002-22942. Furthermore, even with conventionally known polymers that readily exhibit birefringence, such as polycarbonates and polysulfones, it is possible to use those whose birefringence is reduced by modifying them with the molecules described in International Publication No. 2000 / 26705.

[0140] [Layer containing polyvinyl alcohol-based resin] The layer containing the polyvinyl alcohol-based resin is preferably an orientation film. The orientation film is as described above, so its explanation will be omitted.

[0141] Polyvinyl alcohol-based resins are resins containing a repeating unit of -CH2-CHOH-, and examples include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Polyvinyl alcohol-based resins can be obtained, for example, by saponifying polyvinyl acetate-based resins. Examples of polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as copolymers of vinyl acetate with other monomers copolymerizable with vinyl acetate. Other monomers copolymerizable with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. At least one hydroxyl group of the polyvinyl alcohol resin may be modified with a functional group such as an acetoacetyl group, a sulfonic acid group, a carboxyl group, or an oxyalkylene group. In other words, the polyvinyl alcohol resin may be a so-called modified polyvinyl alcohol resin. Furthermore, modified polyvinyl alcohol resins also include polyvinyl alcohol resins having polymerizable groups (for example, (meth)acryloyl groups, vinyl groups). Therefore, polyvinyl alcohol-based resins include unmodified polyvinyl alcohol-based resins and modified polyvinyl alcohol-based resins.

[0142] The content of polyvinyl alcohol-based resin in the orientation film is not particularly limited, but it is preferable that the polyvinyl alcohol-based resin is included as the main component in the orientation film. "Main component" means that the content of polyvinyl alcohol-based resin is 50% by mass or more of the total mass of the orientation film. Preferably, the content of polyvinyl alcohol-based resin is 90% by mass or more of the total mass of the orientation film. There is no particular upper limit, but it is often 99.9% by mass or less.

[0143] [Light-absorbing anisotropic film] As described above, the optical absorption anisotropy film (optical absorption anisotropy layer) of the present invention is as described above, so its explanation will be omitted. In the present invention, the optical absorption anisotropy film is sometimes referred to as a polarizer.

[0144] [λ / 4 plate] A "λ / 4 plate" is a plate that has λ / 4 functionality, specifically a plate that has the function of converting linearly polarized light of a certain wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). For example, a single-layer structure of the λ / 4 plate can be a stretched polymer film or a phase difference film on which a light-absorbing anisotropic film having λ / 4 functionality is provided on a support. A multi-layer structure of the λ / 4 plate can be a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate. The λ / 4 plate and the polarizer of the present invention may be in contact with each other, or other layers may be provided between the λ / 4 plate and the light-absorbing anisotropic film of the present invention. Examples of such layers include an adhesive layer or bonding layer for ensuring adhesion, and a barrier layer.

[0145] [Barrier layer] If the laminate of the present invention includes a barrier layer, the barrier layer is provided between the polarizer and the λ / 4 plate of the present invention. If another layer other than the barrier layer (for example, an adhesive layer or bonding layer) is provided between the polarizer and the λ / 4 plate of the present invention, the barrier layer can be provided, for example, between the light-absorbing anisotropic film of the present invention and the other layer. The barrier layer, also known as the gas barrier layer (oxygen barrier layer), has the function of protecting the light-absorbing anisotropic film of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. For information regarding the barrier layer, see, for example, paragraphs

[0014] to

[0054] of Japanese Patent Publication No. 2014-159124, paragraphs

[0042] to

[0075] of Japanese Patent Publication No. 2017-121721, paragraphs

[0045] to

[0054] of Japanese Patent Publication No. 2017-115076, paragraphs

[0010] to

[0061] of Japanese Patent Publication No. 2012-213938, and paragraphs

[0021] to

[0031] of Japanese Patent Publication No. 2005-169994.

[0146] [Application] The laminate of the present invention can be used, for example, as a polarizing element (polarizing plate), and can be used, for example, as a linear polarizing plate or a circular polarizing plate. If the laminate of the present invention does not have an optically anisotropic layer such as the λ / 4 plate, the laminate can be used as a linear polarizing plate. On the other hand, if the laminate of the present invention has the above-mentioned λ / 4 plate, the laminate can be used as a circular polarizing plate.

[0147] [Image display device] The image display device of the present invention has the above-described light-absorbing anisotropic film of the present invention or the above-described laminate of the present invention. The display elements used in the image display device of the present invention are not particularly limited, and examples include liquid crystal cells, organic electroluminescent (hereinafter abbreviated as "EL") display panels, and plasma display panels. Of these, a liquid crystal cell or an organic EL display panel is preferred, and a liquid crystal cell is more preferred. In other words, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and preferably an organic EL display device using an organic EL display panel as a display element, and more preferably a liquid crystal display device.

[0148] [Liquid crystal display device] A preferred example of a liquid crystal display device, which is an image display device of the present invention, is one having the light-absorbing anisotropic film of the present invention described above and a liquid crystal cell. More preferably, it is a liquid crystal display device having the laminate of the present invention described above (however, not including a λ / 4 plate) and a liquid crystal cell. In this invention, it is preferable to use the laminate of the present invention as the front polarizing element among the polarizing elements provided on both sides of the liquid crystal cell, and it is more preferable to use the laminate of the present invention as both the front and rear polarizing elements. The following provides a detailed description of the liquid crystal cells that make up a liquid crystal display device.

[0149] <Liquid crystal cell> The liquid crystal cells used in liquid crystal display devices are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode, but are not limited to these. In TN mode liquid crystal cells, when no voltage is applied, the rod-shaped liquid crystal molecules are substantially horizontally oriented and further twisted to a 60-120° angle. TN mode liquid crystal cells are the most widely used in color TFT (Thin Film Transistor) liquid crystal display devices and are described in numerous publications. In VA mode liquid crystal cells, rod-shaped liquid crystalline molecules are substantially oriented vertically when no voltage is applied. VA mode liquid crystal cells include (1) narrowly defined VA mode liquid crystal cells in which rod-shaped liquid crystalline molecules are substantially oriented vertically when no voltage is applied and substantially oriented horizontally when voltage is applied (described in Japanese Patent Publication No. 2-176625), (2) multi-domain liquid crystal cells (MVA mode) in which the VA mode is multi-domain to expand the viewing angle (described in SID97, Digest of tech.Papers (Proceedings) 28 (1997) 845), (3) liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystalline molecules are substantially oriented vertically when no voltage is applied and twisted multi-domain orientation when voltage is applied (described in the Proceedings of the Japan Liquid Crystal Symposium 58-59 (1998)), and (4) SURVIVAL mode liquid crystal cells (presented at LCD International 98). Furthermore, it may be any of the following types: PVA (Patterned Vertical Alignment), Optical Alignment, or PSA (Polymer-Sustained Alignment). Details of these modes are described in detail in Japanese Patent Publication No. 2006-215326 and Japanese Patent Publication No. 2008-538819. In IPS mode liquid crystal cells, rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and when an electric field parallel to the substrate surface is applied, the liquid crystal molecules respond in a planar manner. In IPS mode, black is displayed when no electric field is applied, and the absorption axes of the pair of upper and lower polarizers are orthogonal. Methods for reducing light leakage when displaying black at an oblique angle and improving the viewing angle using an optical compensation sheet are disclosed in Japanese Patent Publication No. 10-54982, Japanese Patent Publication No. 11-202323, Japanese Patent Publication No. 9-292522, Japanese Patent Publication No. 11-133408, Japanese Patent Publication No. 11-305217, and Japanese Patent Publication No. 10-307291, among others.

[0150] [Organic EL display device] As an example of an organic EL display device, which is an image display device of the present invention, a preferred embodiment is one in which, from the viewing side, the above-described light-absorbing anisotropic film of the present invention, a λ / 4 plate, and an organic EL display panel are arranged in this order. More preferably, the laminate of the present invention having a λ / 4 plate and an organic EL display panel are arranged in this order from the viewing side. In this case, the laminate is arranged in the following order from the viewing side: a substrate provided as necessary, an alignment film (a layer containing a polyvinyl alcohol-based resin), a light-absorbing anisotropic film of the present invention, a barrier layer provided as necessary, and a λ / 4 plate. Furthermore, an organic EL display panel is a display panel constructed using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between the cathode and the anode). The configuration of the organic EL display panel is not particularly limited, and known configurations can be adopted. [Examples]

[0151] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0152] [Example 1] Laminate A of Example 1 was manufactured as follows.

[0153] [Preparation of Cellulose Acrylate Film 1] Cellulose acylate film 1 was prepared as follows.

[0154] <Preparation of cellulose acylate-doped core layer> The following compositions were placed in a mixing tank and stirred to dissolve each component, preparing a cellulose acetate solution to be used as a cellulose acylate dope for the core layer. ------------------------------------------------------------------ Core layer cellulose acylate doped ------------------------------------------------------------------ • 100 parts by mass of cellulose acetate with an acetyl substitution degree of 2.88 • Examples in Japanese Patent Publication No. 2015-227955 12 parts by mass of the listed polyester compound B • Compound F below: 2 parts by mass • Methylene chloride (first solvent) 430 parts by mass • Methanol (second solvent) 64 parts by mass ------------------------------------------------------------------

[0155] Compound F [ka]

[0156] <Preparation of outer layer cellulose acylate doped> A cellulose acetate solution to be used as the outer layer cellulose acylate dope was prepared by adding 10 parts by mass of the following mat agent solution to 90 parts by mass of the above-mentioned core layer cellulose acylate dope.

[0157] ------------------------------------------------------------------ Mat solution ------------------------------------------------------------------ • Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass • Methylene chloride (first solvent) 76 parts by mass • Methanol (second solvent) 11 parts by mass • 1 part by mass of the above-mentioned core layer cellulose acylate doped ------------------------------------------------------------------

[0158] <Preparation of Cellulose Acrylate Film 1> The core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered using filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm. Then, the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides were simultaneously cast into three layers from the casting port onto a drum at 20°C (band casting machine). Next, the film was peeled off with a solvent content of approximately 20% by mass, and both ends in the width direction of the film were fixed with tenter clips. The film was then dried while being stretched transversely at a stretching ratio of 1.1 times. Subsequently, the film was further dried by transporting it between the rolls of a heat treatment apparatus to produce an optical film with a thickness of 40 μm, which was designated as cellulose acylate film 1. The in-plane retardation of the obtained cellulose acylate film 1 was 0 nm.

[0159] [Fabrication of Laminate A] A laminate A was fabricated comprising the cellulose acylate film 1, the photo-orientation layer PA1, the light-absorbing anisotropic layer P1, and the oxygen barrier layer B1 adjacent to each other in the following order.

[0160] <Fabrication of TAC film with photo-alignment layer> The orientation layer forming coating liquid PA1, described later, was continuously applied onto the cellulose acylate film 1 using a wire bar. The support with the coated film was dried with 140°C hot air for 120 seconds, and then polarized ultraviolet light (10 mJ / cm²) was irradiated onto the coating film. 2 By using an ultra-high pressure mercury lamp, a photo-alignment layer PA1 was formed, and a TAC film with a photo-alignment layer was obtained.

[0161] ------------------------------------------------------------------ (PA1 coating solution for forming an orientation layer) ------------------------------------------------------------------ 100.00 parts by mass of the following polymer A1 Acid generator San-Aid SI-B3A 12.00 parts by mass DIPEA (N,N-diisopropylethylamine) 0.6 parts by mass Methyl ethyl ketone 665.00 parts by mass Butyl acetate 166.00 parts by mass ------------------------------------------------------------------

[0162] 1 [ka]

[0163] San-Aid SI-B3A [ka]

[0164] DIPEA

[0165] [ka]

[0166] <Formation of light-absorbing anisotropic layer P1> The following liquid crystal composition P1 was continuously applied to the photo-alignment layer PA1 of the obtained TAC film with a photo-alignment layer using a wire bar to form a coated layer P1. Next, the coated layer P1 was heated at 140°C for 30 seconds, and then cooled to room temperature (23°C). Next, it was heated at 80°C for 60 seconds and then cooled again to room temperature. Subsequently, an illuminance of 200 mW / cm was achieved using an LED (Light Emitting Diode) lamp (center wavelength 365 nm). 2 By irradiating the photo-alignment layer PA1 for 2 seconds under the specified irradiation conditions, a light-absorbing anisotropic layer P1 (light-absorbing anisotropic film) was formed on the photo-alignment layer PA1. The thickness of the light-absorbing anisotropic layer P1 was 2.0 μm. ------------------------------------------------------------------ Composition of liquid crystal composition P1 ------------------------------------------------------------------ • 0.090 parts by mass of the polymerizable boronic acid compound B1 below • 3.280 parts by mass of the following polymeric liquid crystalline compound L1 • 1.406 parts by mass of the following low molecular weight liquid crystalline compound LM1 • The following dichroic substance Y1: 0.181 parts by mass • The following dichroic substance M1: 0.278 parts by mass • The following dichroic substance C1: 0.742 parts by mass • Surfactant F1 (listed below): 0.060 parts by mass • Polymerization initiator I1 (IRGACUREOXE-02, manufactured by BASF) 0.054 parts by mass • Tetrahydrofuran 47,000 parts by mass Cyclopentanone 47,000 parts by mass ------------------------------------------------------------------

[0167] B1 [ka]

[0168] L1 [ka]

[0169] LM1 [ka]

[0170] Y1 [ka]

[0171] M1 [ka]

[0172] C1 [ka]

[0173] Surfactant F1 [ka]

[0174] <Formation of oxygen barrier layer B1> A coating solution with the following composition was continuously applied to the formed light-absorbing anisotropic layer P1 using a wire bar. Subsequently, a 1.1 μm thick polyvinyl alcohol (PVA) oriented layer (oxygen barrier layer B1) was formed on the light-absorbing anisotropic layer P1 by drying with hot air at 100°C for 2 minutes. ------------------------------------------------------------------ Composition of oxygen barrier layer forming composition B1 ------------------------------------------------------------------ • 3.80 parts by mass of the following modified polyvinyl alcohol • Initiator Irgcure2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass ------------------------------------------------------------------

[0175] Modified polyvinyl alcohol [ka]

[0176] In this way, a laminate A of Example 1 was obtained, comprising a cellulose acylate film 1, a photo-orientation layer PA1, a light-absorbing anisotropic layer P1, and an oxygen barrier layer B1 adjacent to each other in this order.

[0177] [Examples 2-13, Comparative Examples 1-6] Laminates for Examples 2-9 and Comparative Examples 1-5 were prepared in the same manner as laminate A in Example 1, except that the liquid crystal composition was changed to a liquid crystal composition with the composition described in Table 1 below. Laminates for Examples 10-13 and Comparative Example 6 were prepared in the same manner as laminate A in Example 1, except that the liquid crystal composition was changed to a liquid crystal composition with the composition described in Table 2 below. The following is an overview of the components contained in the liquid crystal compositions used to prepare the laminates of Examples 2-13 and Comparative Examples 1-6.

[0178] Polymerizable boronic acid compounds (structure shown below) [ka]

[0179] Compounds other than polymerizable boronic acid compounds (i.e., compounds that do not have polymerizable groups but have boronic acid groups or boronic acid ester groups, or compounds that have polymerizable groups but do not have boronic acid groups or boronic acid ester groups) [ka]

[0180] Liquid crystal compound (structure shown below) [ka] JPEG0007863517000053.jpg44147 JPEG0007863517000054.jpg14146

[0181] Dichroic substance (structure below) [ka] JPEG0007863517000056.jpg48130 JPEG0007863517000057.jpg64147

[0182] Surfactants (structure shown below) [ka]

[0183] Polymerization initiator I1: IRGACUREOXE-02, manufactured by BASF.

[0184] Tetrahydrofuran (solvent) Cyclopentanone (solvent)

[0185] (Synthesis of polymerizable boronic acid compound B1) The polymerizable boronic acid compound B1 described above was synthesized as follows. In the following formula, Et represents an ethyl group.

[0186] [ka]

[0187] 30.0 g of m-hydroxymethylphenylboronic acid (see formula (B1A) above), 0.308 g of 2,2,6,6-tetramethylpiperidine 1-oxy free radical (TEMPO, Wako Pure Chemical Industries), 65 mL of DMAc (N,N-dimethylacetoamide, Wako Pure Chemical Industries), and 100 mL of methyl isobutyl ketone were placed in a three-necked flask. 50.13 g of 3-chloropropionyl chloride was added dropwise to this solution, ensuring the internal temperature did not exceed 30°C. The mixture was then stirred at an internal temperature of 30-40°C for 4 hours. The reaction mixture was washed with 100 g of 5% saline solution and then with 120 g of 5% saline solution at an internal temperature of 30-35°C. After washing, 0.154 g of 2,2,6,6-tetramethylpiperidine 1-oxy free radical (TEMPO, Wako Pure Chemical Industries, Ltd.) was added to the organic layer, and then 40.00 g of triethylamine (Wako Pure Chemical Industries, Ltd.) was added dropwise so that the internal temperature did not exceed 50°C. The mixture was then stirred at an internal temperature of 60°C for 1 hour. Next, the reaction solution was washed twice at an internal temperature of 30-35°C with 120g of 10% saline solution, followed by a mixture of 5mL of concentrated hydrochloric acid and 85mL of water, 120g of 5% sodium acetate aqueous solution, and 120g of water. To the obtained organic layer, 0.52 g of p-methoxyphenol, 90 mL of water, and 75 mL of heptane were added at an internal temperature of 30-35°C. After cooling this solution to 0-5°C over 1 hour, 150 mL of heptane was added dropwise while maintaining the internal temperature of 0-5°C to precipitate crystals. After stirring for 1 hour at the internal temperature of 0-5°C, the crystals were filtered off and washed sequentially with 150 mL of cooled heptane and 150 mL of cooled water in which 0.23 g of p-methoxyphenol was dissolved. The obtained crystals were air-dried at room temperature (23°C) to obtain polymerizable boronic acid compound B1 as a white solid (29.6 g, yield: 72%).

[0188] (Synthesis of polymerizable boronic acid compound BX1) The polymerizable boronic acid compound BX1 described above was synthesized as follows. In the following formula, Et represents an ethyl group.

[0189] [ka]

[0190] 30.0 g of m-hydroxymethylphenylboronic acid (see formula (B1A) above), 0.308 g of 2,2,6,6-tetramethylpiperidine 1-oxy free radical (TEMPO, Wako Pure Chemical Industries), 65 mL of DMAc (N,N-dimethylacetoamide, Wako Pure Chemical Industries), and 100 mL of methyl isobutyl ketone were placed in a three-necked flask. 50.13 g of 3-chloropropionyl chloride was added dropwise to this solution, ensuring the internal temperature did not exceed 30°C. The mixture was then stirred at an internal temperature of 30-40°C for 4 hours. The reaction mixture was washed with 100 g of 5% saline solution and then with 120 g of 5% saline solution at an internal temperature of 30-35°C. After washing, 0.154 g of 2,2,6,6-tetramethylpiperidine 1-oxy free radical (TEMPO, Wako Pure Chemical Industries, Ltd.) was added to the organic layer, and then 40.00 g of triethylamine (Wako Pure Chemical Industries, Ltd.) was added dropwise so that the internal temperature did not exceed 50°C. The mixture was then stirred at an internal temperature of 60°C for 1 hour. Next, the reaction solution was washed twice at an internal temperature of 30-35°C with 120g of 10% saline solution, followed by a mixture of 5mL of concentrated hydrochloric acid and 85mL of water, 120g of 5% sodium acetate aqueous solution, and 120g of water. To the obtained organic layer, 0.52 g of p-methoxyphenol, 90 mL of water, and 75 mL of heptane were added at an internal temperature of 30-35°C. After cooling this solution to 0-5°C over 1 hour, 150 mL of heptane was added dropwise while maintaining the internal temperature of 0-5°C to precipitate crystals. After stirring for 1 hour at the internal temperature of 0-5°C, the crystals were filtered off and washed sequentially with 150 mL of cooled heptane and 150 mL of cooled water in which 0.23 g of p-methoxyphenol was dissolved. The obtained crystals were air-dried at 55°C for 48 hours, and a dehydration condensation reaction was carried out to obtain polymerizable boronic acid compound BX1 as a white solid (25.5 g, yield: 68%).

[0191] [Evaluation Test] The following evaluations were performed using each of the laminates obtained in the examples and comparative examples described above. Furthermore, when the light-absorbing anisotropic layers contained in the laminates of each example were evaluated according to the horizontal orientation evaluation method described above, it was found that in all cases, the light-absorbing anisotropic layers contained in the laminates of each example were horizontally oriented polymer liquid crystalline compounds and dichroic materials.

[0192] [Orientation degree] With a linear polarizer inserted into the light source side of an optical microscope (Nikon Corporation, product name "ECLIPSE E600 POL"), each laminate of the example and comparative example was set on the sample stage. Using a multi-channel spectrometer (Ocean Optics, product name "QE65000"), the absorbance of the anisotropic light-absorbing layer in the wavelength range of 380 nm to 780 nm was measured at 1 nm intervals, and the degree of orientation in the 400 nm to 700 nm range was calculated using the following formula. Based on the obtained degree of orientation, the degree of orientation was evaluated according to the following evaluation criteria. Orientation degree: S=((Az0 / Ay0)-1) / ((Az0 / Ay0)+2) In the above formula, "Az0" represents the absorbance of the light absorption anisotropy layer for polarization in the direction of the absorption axis, and "Ay0" represents the absorbance of the light absorption anisotropy layer for polarization in the direction of the transmission axis. A: Orientation degree is 0.93 or higher B: Orientation level is 0.90 or higher, but less than 0.93. C: Orientation degree is less than 0.90

[0193] [Adhesion] Cellophane tape was applied to the oxygen barrier layer side of the laminates obtained in the examples and comparative examples, and the cellophane tape was peeled off vertically. The degree of delamination of the laminate was visually observed, and the following evaluation was performed. Cross-sectional observation with an optical microscope was performed on the measurement samples in which delamination occurred, and it was confirmed that delamination occurred at the interface between the light-absorbing anisotropic layer and the oxygen barrier layer. A: The oxygen barrier layer peeled off in less than half of the area where the cellophane tape was applied. B: The oxygen barrier layer peeled off in more than half of the area where the cellophane tape was applied, but a portion of the oxygen barrier layer did not peel off. C: The oxygen barrier layer peeled off across the entire area where the cellophane tape was applied.

[0194] [Liquid stability] The liquid stability of the liquid crystal compositions used in Examples 10-13 and Comparative Example 6 was evaluated. Specifically, the liquid crystal compositions prepared in the examples were left at room temperature (23°C) for 24 hours, and the presence or absence of crystal precipitation was visually confirmed. The evaluation criteria are as follows. A: No precipitates visible to the naked eye. B: Very small deposits are visible to the naked eye. C: Precipitates are visible throughout.

[0195] The results of the above evaluation tests are shown in Tables 1 and 2 below. In Table 1, "mass percentage of total solids (mass%)" in the column for polymerizable boronic acid compounds refers to the content (mass%) of polymerizable boronic acid compounds relative to the total solids of the liquid crystal composition. Similarly, "mass percentage of total solids (mass%)" in the column for compounds other than polymerizable boronic acid compounds refers to the content (mass%) of compounds other than polymerizable boronic acid compounds relative to the total solids of the liquid crystal composition. In Table 2, the "mass percentage of total solids (mass%)" in the columns for Polymerizable Boronic Acid Compound 1 and Polymerizable Boronic Acid Compound 2 refers to the content (mass%) of Polymerizable Boronic Acid Compound 1 or Polymerizable Boronic Acid Compound 2 relative to the total solids mass of the liquid crystal composition. Furthermore, the "mass percentage of total solids (mass%)" in the column for compounds other than polymerizable boronic acid compounds refers to the content (mass%) of compounds other than polymerizable boronic acid compounds relative to the total solids mass of the liquid crystal composition.

[0196] [Table 1]

[0197] [Table 2]

[0198] As shown in Tables 1 and 2, a light-absorbing anisotropic film formed from a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boronic acid compound having polymerizable groups, in which the liquid crystal compound is horizontally oriented, exhibited excellent adhesion to other layers and a high degree of orientation (Examples 1-13). A comparison of Examples 1-6 with Example 7 shows that using the compound represented by formula (B-2) above as the polymerizable boronic acid compound (Examples 1-6) yields a light-absorbing anisotropic film with a superior degree of orientation. A comparison of Example 1 and Example 8 demonstrates that using a polymeric liquid crystalline compound (Example 1) yields a light-absorbing anisotropic film with superior orientation and adhesion. A comparison of Examples 10 and 11 with Examples 12 and 13 shows that when the polymerizable boronic acid compound represented by formula (B-1) and the compound represented by formula (BX-1) are used in combination (Examples 10 and 11), the liquid stability of the liquid crystalline composition is excellent.

[0199] In contrast, as shown in Tables 1 and 2, when a light-absorbing anisotropic film was prepared without using a polymerizable boronic acid compound, at least one of the degree of orientation and adhesion was found to be inferior (Comparative Examples 1-6).

Claims

1. A light-absorbing anisotropic film formed from a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boronic acid compound having polymerizable groups, The liquid crystalline compound is horizontally oriented, A light-absorbing anisotropic film wherein the boronic acid compound having the polymerizable group comprises at least one of the compound represented by formula (B-1) and the compound represented by formula (BX-1). 【Chemistry 1】 In formula (B-1), R B11 represents a hydrogen atom or a methyl group. L B1 represents a single bond, a divalent aliphatic hydrocarbon group, or a divalent group in which one or more -CH2- constituting the divalent aliphatic hydrocarbon group are substituted with at least one group selected from the group consisting of -O-, -C(=O)- and -N(RB14)-, and RB14 represents a hydrogen atom or an alkyl group. A B1 represents an optionally substituted arylene group, or an optionally substituted heteroarylene group. R B12 and R B13 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R B12 and R B13 may be bonded to each other to form a ring. 【Chemistry 2】 In formula (BX-1), R BX11 represents a hydrogen atom or a methyl group, and the multiple R BX11s may be the same or different. L BX1 represents a single bond, a divalent aliphatic hydrocarbon group, or a divalent group in which one or more -CH2- constituting the divalent aliphatic hydrocarbon group are substituted with at least one group selected from the group consisting of -O-, -C(=O)-, and -N(R BX14)-, and multiple L BX1s may be the same or different, and R BX14 represents a hydrogen atom or an alkyl group, and if multiple R BX14s are present, multiple R BX14s may be the same or different. A BX1 represents an arylene group which may have a substituent, or a heteroarylene group which may have a substituent, and multiple A BX1s may be the same or different.

2. The light-absorbing anisotropic film according to claim 1, wherein the boronic acid compound having the polymerizable group comprises at least one of the compound represented by formula (B-2) and the compound represented by formula (BX-2). 【Transformation 3】 In formula (B-2), R Ｂ２１ This represents a hydrogen atom or a methyl group. L Ｂ２ This is a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH groups constituting a divalent aliphatic hydrocarbon group. ２ - is -O-, -C(=O)- and -N(R Ｂ２５ ) represents a divalent group substituted with at least one group selected from the group consisting of , R Ｂ２５ This represents a hydrogen atom or an alkyl group. R Ｂ２２ and R Ｂ２３ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, R Ｂ２２ and R Ｂ２３ may be bonded to each other to form a ring, R Ｂ２４ This represents a monovalent substituent, nb represents an integer from 0 to 4, and if nb is 2 or greater, multiple R Ｂ２４ These may be the same or different. 【Chemistry 4】 In formula (BX-2), R ＢＸ２１ represents a hydrogen atom or a methyl group, and there are multiple R ＢＸ２１ These may be the same or different. L ＢＸ２ This is a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH groups constituting a divalent aliphatic hydrocarbon group. ２ - is -O-, -C(=O)- and -N(R ＢＸ２５ Represents a divalent group substituted with at least one group selected from the group consisting of ) and multiple L ＢＸ２ These may be the same or different, R ＢＸ２５ represents a hydrogen atom or alkyl group, and multiple R ＢＸ２５ If multiple R ＢＸ２５ These may be the same or different. R ＢＸ２４ represents a monovalent substituent, and multiple R ＢＸ２４ If multiple R ＢＸ２４ These may be the same or different. nc represents an integer between 0 and 4, and multiple ncs may be the same or different.

3. The light-absorbing anisotropic film according to claim 1 or 2, wherein the content of the boronic acid compound having the polymerizable group is 0.1 to 10% by mass with respect to the total solid content mass of the liquid crystal composition.

4. The boronic acid compound having the polymerizable group includes the compound represented by formula (B-1) and the compound represented by formula (BX-1), The light-absorbing anisotropic film according to claim 1, wherein the mass ratio of the content of the compound represented by formula (B-1) to the content of the compound represented by formula (BX-1) is 5 to 500.

5. The boronic acid compound having the polymerizable group includes the compound represented by formula (B-2) and the compound represented by formula (BX-2), The light-absorbing anisotropic film according to claim 2, wherein the mass ratio of the content of the compound represented by formula (B-2) to the content of the compound represented by formula (BX-2) is 5 to 500.

6. The light-absorbing anisotropic film according to any one of claims 1 to 5, wherein the liquid crystalline compound includes a polymer liquid crystalline compound.

7. A laminate comprising a light-absorbing anisotropic film according to any one of claims 1 to 6, and a layer containing a polyvinyl alcohol-based resin disposed in contact with the light-absorbing anisotropic film.

8. Furthermore, the laminate according to claim 7, wherein the light-absorbing anisotropic film has a λ / 4 plate on the side opposite to the layer containing the polyvinyl alcohol-based resin.

9. An image display device having a light-absorbing anisotropic film according to any one of claims 1 to 6, or a laminate according to claim 7 or claim 8.

10. A liquid crystal composition comprising a liquid crystal compound, a dichroic substance, and a boronic acid compound having a polymerizable group, A liquid crystal composition in which the polymerizable boronic acid compound comprises at least one of the compound represented by formula (B-2) and the compound represented by formula (BX-1). 【Transformation 5】 In formula (B-2), R Ｂ２１ This represents a hydrogen atom or a methyl group. L Ｂ２ This is a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH groups constituting a divalent aliphatic hydrocarbon group. ２ - is -O-, -C(=O)- and -N(R Ｂ２５ ) represents a divalent group substituted with at least one group selected from the group consisting of , R Ｂ２５ This represents a hydrogen atom or an alkyl group. R Ｂ２２ and R Ｂ２３ Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, R Ｂ２２ and R Ｂ２３ They may be joined to each other to form a ring. R Ｂ２４ This represents a monovalent substituent, nb represents an integer from 0 to 4, and if nb is 2 or greater, multiple R Ｂ２４ These may be the same or different. 【Transformation 6】 In formula (BX-1), R ＢＸ１１ represents a hydrogen atom or a methyl group, and there are multiple R ＢＸ１１ These may be the same or different. L ＢＸ１ This is a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH groups constituting a divalent aliphatic hydrocarbon group. ２ - is -O-, -C(=O)- and -N(R ＢＸ１４ Represents a divalent group substituted with at least one group selected from the group consisting of ) and multiple L ＢＸ１ These may be the same or different, R ＢＸ１４ represents a hydrogen atom or alkyl group, and multiple R ＢＸ１４ If multiple R ＢＸ１４ These may be the same or different. A ＢＸ１ represents an optionally substituted arylene group, or an optionally substituted heteroarylene group, and a plurality of A ＢＸ１ These may be the same or different.

11. The liquid crystal composition according to claim 10, wherein the compound represented by formula (BX-1) is the compound represented by formula (BX-2). 【Transformation 7】 In formula (BX-2), R ＢＸ２１ represents a hydrogen atom or a methyl group, and there are multiple R ＢＸ２１ These may be the same or different. L ＢＸ２ This is a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH groups constituting a divalent aliphatic hydrocarbon group. ２ - is -O-, -C(=O)- and -N(R ＢＸ２５ Represents a divalent group substituted with at least one group selected from the group consisting of ) and multiple L ＢＸ２ These may be the same or different, R ＢＸ２５ represents a hydrogen atom or alkyl group, and multiple R ＢＸ２５ If multiple R ＢＸ２５ These may be the same or different. R ＢＸ２４ represents a monovalent substituent, and multiple R ＢＸ２４ If multiple R ＢＸ２４ These may be the same or different. nc represents an integer between 0 and 4, and multiple ncs may be the same or different.

12. The liquid crystal composition according to claim 10 or 11, wherein the content of the boronic acid compound having the polymerizable group is 0.1 to 10% by mass with respect to the total solid content mass of the liquid crystal composition.

13. The boronic acid compound having the polymerizable group includes the compound represented by formula (B-2) and the compound represented by formula (BX-1), The liquid crystal composition according to any one of claims 10 to 12, wherein the mass ratio of the content of the compound represented by formula (B-2) to the content of the compound represented by formula (BX-1) is 5 to 500.

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