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

Abstract

To provide a light-absorbing anisotropic film, a laminate, an image display device, and a liquid crystal composition, each of which has excellent adhesion and high orientation. 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 a polymerizable group, and the liquid-crystalline compound is horizontally oriented.

Description

Technical Field

[0001] This invention relates to anisotropic light absorption film, a laminate, an image display device, and a liquid crystal composition. Background Technology

[0002] In the past, when functions such as attenuation, polarization, scattering, or light blocking of laser beams or natural light were required, devices operating on different principles were used for each function. Therefore, products corresponding to these functions were manufactured using different processes for each function.

[0003] For example, in image display devices (e.g., liquid crystal display devices), linear polarizers or circular polarizers are used to control optical rotation or birefringence in the display. Furthermore, in organic light-emitting diodes (OLEDs), circular polarizers are also used to prevent reflection of external light.

[0004] In the past, iodine has been widely used as a dichroic substance in these polarizers, but research is also underway on polarizers that use organic pigments instead of iodine as dichroic substances.

[0005] For example, Patent Document 1 shows the use of a liquid crystal composition (coloring composition) containing a dichroic substance (dichroic pigment compound) having a defined structure to form a light-absorbing anisotropic film (claims 1 and 14, etc.).

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2017 / 195833 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] In recent years, there has been a growing demand for higher performance in light-absorbing anisotropic films formed using liquid crystal compositions. Specifically, there is a need for light-absorbing anisotropic films with excellent orientation and good adhesion to other components.

[0011] The inventors have studied the light-absorbing anisotropic film as described in Patent Document 1, and the results show that although it exhibits 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 in the formation of the light-absorbing anisotropic film.

[0012] Therefore, the objective of this invention is to provide a light-absorbing anisotropic film with excellent adhesion and high orientation, a laminate, an image display device, and a liquid crystal composition.

[0013] means for solving technical problems

[0014] As a result of in-depth research conducted by the inventors to solve the above-mentioned problems, they discovered that a liquid crystal composition formed from a liquid crystal compound containing a liquid crystal compound, a dichroic substance, and a boric acid compound having polymerizable groups exhibits excellent adhesion to other layers and displays a high degree of orientation, thereby completing the present invention.

[0015] That is, the inventors discovered that the above-mentioned problems can be solved by the following structure. [1]

[0017] An anisotropic light-absorbing film is formed from a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boric acid compound having polymerizable groups.

[0018] The aforementioned liquid crystal compounds are horizontally oriented. [2]

[0020] According to the light absorption anisotropic film described in [1], wherein,

[0021] The aforementioned boric acid compounds having polymerizable groups include at least one of the compounds represented by the following formula (B-1) and the compounds represented by the following formula (BX-1).

[0022] In the post-formulation (B-1), R B11 Indicates a hydrogen atom or a methyl group.

[0023] L B1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. B14 A divalent group substituted by at least one group in the group R B14 Indicates a hydrogen atom or an alkyl group.

[0024] A B1 This indicates an arylene group that may have substituents or a heteroarylene group that may have substituents.

[0025] R B12 and R B13 Each of the following can independently represent a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or a heteroaryl group that may have substituents; R B12 and R B13 This indicates that they can bond together to form a ring.

[0026] In the post-formulation (BX-1), R BX11 Represents a hydrogen atom or a methyl group, multiple RBX11 They can be the same or different.

[0027] L BX1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R). BX14 At least one group in the group consisting of divalent groups substituted by )-, and multiple L BX1 They can be the same or different, RB X14 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX14 In the case of multiple R BX14 They can be the same or different.

[0028] A BX1 This indicates an arylene group that may have substituents or a heteroarylene group that may have substituents, with multiple A groups. BX1 They can be the same or different. [3]

[0030] According to the light absorption anisotropic film described in [1] or [2], wherein,

[0031] The aforementioned boric acid compounds having polymerizable groups include at least one of the compounds represented by the formula (B-2) and the compound represented by the formula (BX-2).

[0032] In the following equation (B-2), R B21 Indicates a hydrogen atom or a methyl group.

[0033] L B2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. B25 A divalent group substituted by at least one group in the group R B25 Indicates a hydrogen atom or an alkyl group.

[0034] R B22 and R B23 Each of the following can independently represent a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or a heteroaryl group that may have substituents; R B22 and R B23 This indicates that they can bond together to form a ring.

[0035] R B24 Indicates a substituent with a 1 valence.

[0036] nb represents an integer from 0 to 4. When nb is greater than 2, multiple R... B24 They can be the same or different.

[0037] In the post-formulation (BX-2), R BX21 Represents a hydrogen atom or a methyl group, multiple R BX21 They can be the same or different.

[0038] L BX2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R). BX25 At least one group in the group consisting of divalent groups substituted by )-, and multiple L BX2 They can be the same or different, RB X25 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX25 In the case of multiple R BX25 They can be the same or different.

[0039] R BX24 Describing a substituent with a valence of 1, in the presence of multiple R... BX24 In the case of multiple R BX24 They can be the same or different.

[0040] nc represents an integer from 0 to 4. Multiple nc values ​​can be the same or different. [4]

[0042] The light-absorbing anisotropic film according to any one of [1] to [3], wherein,

[0043] The content of the aforementioned boric acid compound having polymerizable groups is 0.1 to 10% by mass relative to the total solid content of the aforementioned liquid crystal composition. [5]

[0045] According to the light absorption anisotropic film described in [2], wherein,

[0046] The aforementioned boric acid compounds with polymerizable groups include compounds represented by formula (B-1) and compounds represented by formula (BX-1).

[0047] The mass ratio of the content of the compound represented by the above formula (B-1) to the content of the compound represented by the above formula (BX-1) is 5 to 500. [6]

[0049] According to the light absorption anisotropic film described in [3], wherein,

[0050] The aforementioned boric acid compounds with polymerizable groups include compounds represented by formula (B-2) and compounds represented by formula (BX-2).

[0051] The mass ratio of the content of the compound represented by the above formula (B-2) to the content of the compound represented by the above formula (BX-2) is 5 to 500. [7]

[0053] The light-absorbing anisotropic film according to any one of [1] to [6], wherein,

[0054] The aforementioned liquid crystal compounds include high molecular weight liquid crystal compounds. [8]

[0056] A laminated body having:

[0057] The light-absorbing anisotropic film described in any one of [1] to [7]; and

[0058] The layer is configured to be in contact with the aforementioned light-absorbing anisotropic film and contains polyvinyl alcohol resin. [9]

[0060] According to the laminate described in [8], it also has a λ / 4 plate on the side of the light-absorbing anisotropic film opposite to the layer containing the polyvinyl alcohol resin.

[10]

[0062] An image display device having a light-absorbing anisotropic film as described in any one of [1] to [7] or a laminate as described in [8] or [9].

[11]

[0064] A liquid crystal composition comprising a liquid crystal compound, a dichroic substance, and a boric acid compound having polymerizable groups.

[0065] The aforementioned boric acid compounds having polymerizable groups include at least one of the compounds represented by the formula (B-2) and the compounds represented by the formula (BX-1).

[0066] In the following equation (B-2), R B21 Indicates a hydrogen atom or a methyl group.

[0067] L B2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=o)-, and -N(R). B25 A divalent group substituted by at least one group in the group R B25 Indicates a hydrogen atom or an alkyl group.

[0068] R B22 and R B23 Each of the following can independently represent a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or a heteroaryl group that may have substituents; R B22and R B23 This indicates that they can bond together to form a ring.

[0069] R B24 Indicates a substituent with a 1 valence.

[0070] nb represents an integer from 0 to 4. When nb is greater than 2, multiple R... B24 They can be the same or different.

[0071] In the post-formulation (BX-1), R BX11 Represents a hydrogen atom or a methyl group, multiple R BX11 They can be the same or different.

[0072] L BX1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R). BX14 At least one group in the group consisting of divalent groups substituted by )-, and multiple L BX1 They can be the same or different, R BX14 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX14 In the case of multiple R BX14 They can be the same or different.

[0073] A BX1 This indicates an arylene group that may have substituents or a heteroarylene group that may have substituents, with multiple A groups. BX1 They can be the same or different.

[12]

[0075] According to the liquid crystal composition described in

[11] , wherein,

[0076] The compound represented by the above formula (BX-1) is the same compound represented by the formula (BX-2) described later.

[0077] In the post-formulation (BX-2), R BX21 Represents a hydrogen atom or a methyl group, multiple R BX21 They can be the same or different.

[0078] L BX2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R). BX25 At least one group in the group consisting of divalent groups substituted by )-, and multiple L BX2 They can be the same or different, RB X25 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX25 In the case of multiple R BX25They can be the same or different.

[0079] R BX24 Describing a substituent with a valence of 1, in the presence of multiple R... BX24 In the case of multiple R BX24 They can be the same or different.

[0080] nc represents an integer from 0 to 4. Multiple nc values ​​can be the same or different.

[13]

[0082] According to the liquid crystal composition described in

[11] or

[12] , wherein,

[0083] The content of the aforementioned boric acid compound having polymerizable groups is 0.1 to 10% by mass relative to the total solid content of the aforementioned liquid crystal composition.

[14]

[0085] The liquid crystal composition according to any one of

[11] to

[13] , wherein,

[0086] The aforementioned boric acid compounds with polymerizable groups include compounds represented by formula (B-2) and compounds represented by formula (BX-1).

[0087] The mass ratio of the content of the compound represented by the above formula (B-2) to the content of the compound represented by the above formula (BX-1) is 5 to 500.

[0088] Invention Effects

[0089] According to the present invention, it is possible to provide a light absorption anisotropic film with excellent adhesion and high orientation, a laminate, an image display device, and a liquid crystal composition. Detailed Implementation

[0090] The present invention will now be described in detail.

[0091] The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

[0092] In addition, the numerical range indicated by “~” in this specification refers to the range including the lower limit and upper limit values ​​of the values ​​recorded before and after “~”.

[0093] Furthermore, in this specification, each component may use a single substance corresponding to that component, or two or more substances may be used in combination. Where two or more substances are used in combination for each component, the content of that component, unless otherwise stated, refers to the total content of the substances used in combination.

[0094] Furthermore, in this specification, "(meth)acrylate" is the expression for "acrylate" or "methacrylate", "(meth)acrylate group" is the expression for "acrylic group" or "methacrylic group", "(meth)acryloyl group" is the expression for "acryloyl group" or "methacryloyl group", and "(meth)acrylic acid" is the expression for "acrylic acid" or "methacrylic acid".

[0095] [Anisotropic light absorption film]

[0096] The light-absorbing anisotropic film of the present invention is a light-absorbing anisotropic film formed from a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boric acid compound having polymeric groups (hereinafter also referred to as "polymeric boric acid compound"). The liquid crystal compound is horizontally oriented.

[0097] The light-absorbing anisotropic film of the present invention exhibits excellent adhesion and high orientation.

[0098] As described later, polymerizable boric acid compounds are compounds having at least one polymerizable group and a boric acid group or a borate ester group. It can be inferred that these groups (polymerizable group, boric acid group, borate ester group) of polymerizable boric acid compounds interact with other components, improving the adhesion between the light-absorbing anisotropic film and other components.

[0099] Furthermore, polymeric boric acid compounds are widely used as vertical alignment agents to vertically align liquid crystal compounds. However, while the reasons for this are uncertain, it is believed that in this invention, the polymeric boric acid compound did not fully function as a vertical alignment agent and did not hinder the horizontal alignment of the liquid crystal compound. It can be inferred that this resulted in a light-absorbing anisotropic film with a high degree of alignment.

[0100] [Liquid Crystal Composition]

[0101] The liquid crystal composition used in the formation of the light-absorbing anisotropic film of the present invention contains a liquid crystal compound, a dichroic substance, and a polymerizable boric acid compound. The liquid crystal composition may also contain solvents, surface modifiers, polymerization initiators, and other components as needed.

[0102] The following is a description of each component.

[0103] <Liquid Crystal Compounds>

[0104] The liquid crystal composition contains a liquid crystal compound. By containing the liquid crystal compound, the precipitation of dichroic substances can be suppressed, and the dichroic substances can be oriented with a high degree of orientation.

[0105] As a liquid crystal compound, either a low-molecular-weight liquid crystal compound or a high-molecular-weight liquid crystal compound can be used, but a high-molecular-weight liquid crystal compound is more preferred for obtaining a high degree of orientation. Here, "low-molecular-weight liquid crystal compound" refers to a liquid crystal compound that does not have repeating units in its chemical structure. And "high-molecular-weight liquid crystal compound" refers to a liquid crystal compound that has repeating units in its chemical structure.

[0106] Examples of low-molecular-weight liquid crystal compounds include those described in Japanese Patent Application Publication No. 2013-228706.

[0107] Examples of polymeric liquid crystal compounds include the thermotropic liquid crystal polymer described in Japanese Patent Application Publication No. 2011-237513. Furthermore, the polymeric liquid crystal compound may have crosslinking groups (e.g., acryloyl and methacryloyl groups) at its ends.

[0108] Liquid crystal compounds can be used alone or in combination of two or more.

[0109] From the perspective of superior orientation and adhesion of the light absorption anisotropic film, the liquid crystal compound preferably contains a polymeric liquid crystal compound.

[0110] Considering the superior orientation of dichroic substances (especially dichroic azo dye compounds), liquid crystal compounds are preferably polymeric liquid crystal compounds containing repeating units (hereinafter also referred to as "repeating units (3-1)") represented by the following formula (3-1).

[0111] [Chemical Formula 1]

[0112]

[0113] In the above formula (3-1), P1 represents the main chain of the repeating unit, L1 represents the single bond or divalent linker, SP1 represents the spacer group, M1 represents the mesocrystalline group, and T1 represents the terminal group.

[0114] In the repeating unit (3-1), the difference between the logP values ​​of P1, L1, and SP1 and the logP value of M1 is preferably 4 or more. More preferably, it is 4.5 or more. Since the logP values ​​of the main chain, L1, and spacer groups differ from the log value of the mesocrystalline group by a predetermined value or more, the structure from the main chain to the spacer groups is in a state of low compatibility with the mesocrystalline groups. Therefore, it can be inferred that the crystallinity of the polymeric liquid crystal compound is high, and it is in a state of high orientation of the polymeric liquid crystal compound. Thus, it can be inferred that if the orientation of the polymeric liquid crystal compound is high, the compatibility of the polymeric liquid crystal compound with organic dichroic substances (especially dichroic azo dye compounds) decreases (i.e., the crystallinity of the dichroic azo dye compound increases), thereby increasing the orientation of the dichroic azo dye compound. As a result, it is believed that the orientation of the obtained light absorption anisotropic film is high.

[0115] As the main chain of the repeating unit represented by P1, specifically, for example, groups represented by the following formulas (P1-A) to (P1-D) can be cited, wherein, from the viewpoint of the diversity of monomers that can be used as raw materials and ease of handling, groups represented by the following formula (P1-A) are preferred.

[0116] [Chemical Formula 2]

[0117]

[0118] In equations (P1-A) to (P1-D), "*" indicates the bonding position with L1 in equation (3-1).

[0119] In the above formulas (P1-A) to (P1-D), R 1 R 2 R 3 and R 4 Each of the above-mentioned alkyl groups independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group can be a straight-chain or branched alkyl group, or an alkyl group having a cyclic structure (cycloalkyl). Furthermore, the alkyl group preferably has 1 to 5 carbon atoms.

[0120] The group represented by the above formula (P1-A) is preferably a unit of a partial structure of poly(meth)acrylate obtained by polymerization of (meth)acrylate.

[0121] 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.

[0122] The group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetane compound having an oxetane.

[0123] The group represented by the above formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one of alkoxysilyl and silanol groups. Here, as a compound having at least one of alkoxysilyl and silanol groups, an example is a compound having the formula SiR 14 (OR 15 Compounds containing a group represented by )2-. In the formula, R 14 The meaning of R in (P1-D) 14 The meanings are the same, multiple R 15 Alkyl groups, which can be independently represented by 1 to 10 hydrogen or carbon atoms respectively.

[0124] L1 represents a single bond or a divalent linker.

[0125] Examples of divalent linker bases 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 - etc. In the formula, R 3 and R 4 Each of the following can be independently represented: a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, which may have substituents (described later).

[0126] When P1 is a group represented by formula (P1-A), considering the superior orientation of the light absorption anisotropic film, L1 is preferably a group represented by -C(O)O-.

[0127] When P1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond, considering the superior orientation of the light absorption anisotropic film.

[0128] For reasons such as ease of liquid crystal properties or availability of raw materials, the spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of ethylene oxide structure, propylene oxide structure, polysiloxane structure and fluorinated alkylene structure.

[0129] Here, the oxyethylene structure represented by SP1 is preferably composed of *-(CH2-CH2O). n1 -* indicates a group. In the formula, n1 represents an integer from 1 to 20, and * indicates the bonding position with L1 or M1 in the above formula (3-1). Considering the superior orientation degree of the light absorption anisotropic film, n1 is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, and most preferably 3.

[0130] Furthermore, considering the superior orientation of the anisotropic light absorption film, the oxypropylene structure represented by SP1 is preferably composed of *-(CH(CH3)-CH2O). n2 -* indicates a group. In the formula, n2 represents an integer from 1 to 3, and * indicates the bonding position with L1 or M1.

[0131] Furthermore, considering the superior orientation of the anisotropic light absorption film, the polysiloxane structure represented by SP1 is preferably composed of *-(Si(CH3)2-O). n3 -* indicates a group. In the formula, n3 represents an integer from 6 to 10, and * indicates the bonding position with L1 or M1.

[0132] Furthermore, considering the superior orientation of the anisotropic light absorption film, the fluorinated alkylene structure represented by SP1 is preferably composed of *-(CF2-CF2). 114 -* indicates a group. In the formula, n4 represents an integer from 6 to 10, and * indicates the bonding position with L1 or M1.

[0133] The mesocrystalline group represented by M1 refers to the group that represents the main framework of liquid crystal molecules that contribute to the formation of liquid crystals. Liquid crystal molecules exhibit liquid crystal properties, exhibiting an intermediate state (intermediate phase) between the crystalline state and the isotropic liquid state. There are no particular limitations regarding the mesocrystalline group; for example, one can refer to "Flussige Kristalle in Tabellen II" (VEB Deutsche Verlagfur Grundstoff Industrie, Leipzig, 1984), especially pages 7-16, and the description in "Liquid Crystal Handbook Editorial Committee," "Liquid Crystal Handbook" (Maruzen, 2000), especially Chapter 3.

[0134] As a mesocrystalline group, it is preferred, for example, to have at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups.

[0135] Considering the superior orientation of the anisotropic light absorption film, the mesocrystalline group preferably has aromatic hydrocarbon groups, more preferably has 2 to 4 aromatic hydrocarbon groups, and even more preferably has 3 aromatic hydrocarbon groups.

[0136] From the viewpoints of liquid crystal properties, liquid crystal phase transition temperature adjustment, raw material availability and synthetic applicability, and superior orientation of light absorption anisotropic films, groups represented by the following formula (M1-A) or the following formula (M1-B) are preferred as mesocrystalline groups, and groups represented by formula (M1-B) are more preferred.

[0137] [Chemical Formula 3]

[0138]

[0139] 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, fluorinated alkyl, alkoxy, or substituents.

[0140] The divalent group represented by A1 is preferably a 4- to 6-membered ring. Furthermore, the divalent group represented by A1 can be a monocyclic ring or a fused ring.

[0141] * indicates the bonding position with SP1 or T1.

[0142] Examples of divalent aromatic hydrocarbon groups represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetraphenyl-diyl. From the perspective of the diversity of mesocrystalline framework design or the availability of raw materials, phenylene or naphthylene is preferred, and phenylene is more preferred.

[0143] The divalent heterocyclic group represented by A1 can be either aromatic or non-aromatic, but from the viewpoint of further improving the degree of orientation, a divalent aromatic heterocyclic group is preferred.

[0144] Examples of atoms other than carbon that constitute a divalent aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. In cases where an aromatic heterocyclic group has multiple atoms constituting the ring other than carbon, these atoms can be the same or different.

[0145] Specific examples of divalent aromatic heterocyclic groups include pyridinyl (pyridin-diyl), pyridazinyl (pyridinyl), imidazole-diyl, thiophene (thiophene-diyl), quinolineyl (quinoline-diyl), isoquinolineyl (isoquinoline-diyl), oxazole-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thienothiazole-diyl, thiazonothiazole-diyl, thienothiphene-diyl, and thienooxazole-diyl.

[0146] Specific examples of the divalent alicyclic group represented by A1 include cyclopentylene and cyclohexylene.

[0147] In formula (M1-A), a1 represents an integer from 1 to 10. When a1 is 2 or higher, multiple A1 values ​​can be the same or different.

[0148] In formula (M1-B), A2 and A3 are each independently a divalent group 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 A1 in formula (M1-A), therefore their description is omitted.

[0149] In formula (M1-B), a2 represents an integer from 1 to 10. When a2 is 2 or more, multiple A2s can be the same or different, multiple A3s can be the same or different, and multiple LA1s can be the same or different. Considering the superior orientation of the light absorption anisotropic film, a2 is preferably an integer of 2 or more, and more preferably 2.

[0150] In formula (M1-B), when a2 is 1, LA1 is a divalent linker. When a2 is 2 or more, the plurality of LA1s are independently either single bonds or divalent linkers, and at least one of the plurality of LA1s is a divalent linker. When a2 is 2, considering the superior orientation of the light absorption anisotropic film, it is preferable that one of the two LA1s is a divalent linker and the other is a single bond.

[0151] In formula (M1-B), examples of divalent linkers represented by LA1 include -O- and -(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)-C(Z)=C(Z')-, -C(Z)=C(Z')-C(O)-S-, -SC(O)-C(Z)=C(Z')-, -C(Z)=NN=C(Z')- (Z, Z', Z” independently represent hydrogen, C1-C4 alkyl, cycloalkyl, aryl, cyano or 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-, etc.

[0152] Among them, considering the superior orientation of the light absorption anisotropic film, -C(O)O- is preferred.

[0153] LA1 can also be a group composed of two or more of these groups.

[0154] Specific examples of M1 include the following structures. Additionally, in the following specific examples, "Ac" represents an acetyl group.

[0155] [Chemical Formula 4]

[0156]

[0157] [Chemical Formula 5]

[0158]

[0159] [Chemical Formula 6]

[0160]

[0161] [Chemical Formula 7]

[0162]

[0163] [Chemical Formula 8]

[0164]

[0165] [Chemical Formula 9]

[0166]

[0167] [Chemical Formula 10]

[0168]

[0169] Examples of terminal groups represented by T1 include hydrogen atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms (ROC(O)-: R is an alkyl group), acyloxy groups with 1 to 10 carbon atoms, acylamino groups with 1 to 10 carbon atoms, alkoxycarbonylamino groups with 1 to 10 carbon atoms, sulfonylamino groups with 1 to 10 carbon atoms, aminosulfonyl groups with 1 to 10 carbon atoms, carbamoyl groups with 1 to 10 carbon atoms, sulfinyl groups with 1 to 10 carbon atoms, urea groups with 1 to 10 carbon atoms, and groups containing (meth)acryloyloxy groups. Examples of groups containing (meth)acryloyloxy groups include those represented by -LA (L represents a single bond or a linker. Specific examples of linkers are the same as L1 and SP1 described above. A represents a group represented by (meth)acryloyloxy).

[0170] Considering the superior orientation of the anisotropic light absorption film, T1 is preferably an alkoxy group with 1 to 10 carbon atoms, more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably a methoxy group. These terminal groups can be further replaced by these groups or polymerizable groups described in Japanese Patent Application Publication No. 2010-244038.

[0171] Considering the superior orientation of the anisotropic light absorption film, 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. By having the number of atoms in the main chain of T1 be 20 or less, the orientation of the anisotropic light absorption film is further improved. Here, "main chain" in T1 refers to the longest molecular chain bonded to M1, and hydrogen atoms are not included in the number of atoms in the main chain of T1. For example, when T1 is n-butyl, the number of atoms in the main chain is 4, and when T1 is sec-butyl, the number of atoms in the main chain is 3.

[0172] Considering the superior orientation of the light-absorbing anisotropic film, the content of the repeating unit (3-1) is preferably 20 to 100% by mass relative to 100% by mass of all repeating units in the polymeric liquid crystal compound.

[0173] In this invention, the content of each repeating unit contained in the polymeric liquid crystal compound is calculated based on the loading amount (mass) of each monomer used to obtain each repeating unit.

[0174] The polymeric liquid crystal compound may contain a single repeating unit (3-1) or two or more repeating units. If the polymeric liquid crystal compound contains two or more repeating units (3-1), it has advantages such as improved solubility in solvents and easier adjustment of the liquid crystal phase transition temperature. When it contains two or more repeating units (3-1), it is preferable that their total amount is within the above-mentioned range.

[0175] In the case where the polymeric liquid crystal compound contains two repeating units (3-1), considering the superior orientation of the light absorption anisotropic film, it is preferable that the terminal group represented by T1 in one (repeating unit A) is alkoxy and the terminal group represented by T1 in the other (repeating unit B) is a group other than alkoxy.

[0176] Considering the superior orientation of the light absorption anisotropic film, the terminal group represented by T1 in the repeating unit B is preferably an alkoxy carbonyl, a cyano, or a group containing (meth)acryloyloxy, more preferably an alkoxy carbonyl or a cyano.

[0177] Considering the superior orientation of the light-absorbing anisotropic film, the ratio (A / B) of the content of the repeating unit A in the polymeric liquid crystal compound to the content of the repeating unit B in the polymeric liquid crystal compound is preferably 50 / 50 to 95 / 5, more preferably 60 / 40 to 93 / 7, and even more preferably 70 / 30 to 90 / 10.

[0178] <Repeating Unit (3-2)>

[0179] The polymeric liquid crystal compound of the present invention may further comprise a repeating unit represented by the following formula (3-2) (also referred to as "repeating unit (3-2)" in this specification). This provides advantages such as improved solvent solubility and ease of adjustment of the liquid crystal phase transition temperature.

[0180] The repeating unit (3-2) differs from the repeating unit (3-1) mentioned above in that it at least does not have a mesocrystalline group.

[0181] When the polymeric liquid crystal compound contains repeating units (3-2), the polymeric liquid crystal compound is a copolymer of repeating units (3-1) and repeating units (3-2) (or a copolymer that also contains repeating units A and B), and can be any kind of polymer such as block polymer, alternating polymer, random polymer and graft polymer.

[0182] [Chemical Formula 11]

[0183]

[0184] In equation (3-2), P3 represents the main chain of the repeating unit, L3 represents a single bond or a divalent linker, SP3 represents a spacer group, and T3 represents a terminal group.

[0185] 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.

[0186] From the viewpoint of improving the intensity of the light-absorbing anisotropic film, T3 in formula (3-2) preferably has polymerizable groups.

[0187] The content of repeating units (3-2) is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, relative to 100% by mass of all repeating units in the polymeric liquid crystal compound.

[0188] The polymeric liquid crystal compound may contain a single repeating unit (3-2) or two or more repeating units. When two or more repeating units (3-2) are contained, it is preferable that their total amount is within the above-mentioned range.

[0189] (weight-average molecular weight)

[0190] Considering the superior orientation of anisotropic light absorption films, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. As long as the Mw of the polymeric liquid crystal compound is within the above range, it is easy to process.

[0191] In particular, from the viewpoint of suppressing cracks during coating, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 10,000 or more, and more preferably 10,000 to 300,000.

[0192] Furthermore, from the viewpoint of temperature tolerance of orientation, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably less than 10,000, and preferably more than 2,000 and less than 10,000.

[0193] In this invention, the weight-average molecular weight and number-average molecular weight are values ​​determined by gel permeation chromatography (GPC).

[0194] • Solvent (eluent): N-methylpyrrolidone

[0195] • Device Name: TOSOH HLC-8220GPC

[0196] • Column: Connect 3 TOSOH TSKgelSuperAWM-H (6mm×15cm) for use.

[0197] Column temperature: 25℃

[0198] • Sample concentration: 0.1% by mass

[0199] • Flow rate: 0.35 ml / min

[0200] • Calibration curve: The calibration curve was obtained using seven samples of TSK standard polystyrene prepared by TOSOH with Mw = 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06).

[0201] (Content of liquid crystal compounds)

[0202] The content of the liquid crystal compound relative to the total solid content of the liquid crystal composition is preferably 10-97% by mass, more preferably 40-95% by mass, and particularly preferably 60-95% by mass. By keeping the content of the liquid crystal compound within the above range, the orientation degree of the light absorption anisotropic film is further improved.

[0203] The content of liquid crystal compound in the light-absorbing anisotropic film is preferably the same as the content of liquid crystal compound relative to the total solid content of the liquid crystal composition described above.

[0204] <Dichromatic substances>

[0205] There are no particular limitations on the dichroic substance contained in the liquid crystal composition.

[0206] As a dichroic material, a dichroic azo dye compound is preferred, and dichroic azo dye compounds commonly used in so-called coated polarizers can be used. There are no particular limitations on the dichroic azo dye compound; conventionally known dichroic azo dyes can be used, but compounds described later are preferred.

[0207] In anisotropic light-absorbing films, dichroic substances can polymerize.

[0208] In this invention, dichroic azo pigment compounds refer to pigments whose absorbance varies depending on the direction.

[0209] Dichroic azo dye compounds may or may not exhibit liquid crystal properties.

[0210] When a dichroic azo dye compound exhibits liquid crystal properties, it can exhibit either nematic or smectic properties. The preferred temperature range for displaying the liquid crystal phase is room temperature (approximately 20°C to 28°C) to 300°C, and more preferably 50°C to 200°C from the viewpoint of processability and manufacturing suitability.

[0211] In this invention, from the viewpoint of adjusting hue, the light-absorbing anisotropic film preferably has at least one pigment compound (hereinafter also referred to as "first dichroic azo pigment compound") having a maximum absorption wavelength in the wavelength range of 560 to 700 nm and at least one pigment compound (hereinafter also referred to as "second dichroic azo pigment compound") having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm. More preferably, it has at least the dichroic azo pigment compound represented by formula (1) described later and the dichroic azo pigment compound represented by formula (2) described later.

[0212] In this invention, three or more dichroic azo pigment compounds may be used together. For example, from the viewpoint of making the light absorption anisotropic film close to black, it is preferable to use a first dichroic azo pigment compound, a second dichroic azo pigment compound, and at least one pigment compound (hereinafter also referred to as "the third dichroic azo pigment compound") that has a maximum absorption wavelength in the range of 380 nm or more and less than 455 nm (preferably the range of 380 to 454 nm).

[0213] In this invention, for the sake of better compressive strength, it is preferable that the dichromatic azo dye compound has crosslinking groups.

[0214] As a crosslinking group, examples include (meth)acryloyl, epoxy, oxocyclobutyl, styryl, etc., with (meth)acryloyl being preferred.

[0215] (First dichroic azo pigment compound)

[0216] The first dichroic azo dye compound is preferably a compound having a chromophore as a core and a side chain bonded to the end of the chromophore.

[0217] Specific examples of chromophores include aromatic cyclic groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups, etc., preferably having both an aromatic cyclic group and an azo group, and more preferably having a bisazo structure having an aromatic heterocyclic group (preferably thienothiazolyl) and two azo groups.

[0218] As a side chain, there are no particular limitations, and examples can be groups represented by L3, R2 or L4 of formula (1) described later.

[0219] From the viewpoint of adjusting the hue of the light absorption anisotropic film, the first dichroic azo dye compound is preferably a dichroic azo dye compound having a maximum absorption wavelength in the range of 560 nm or more and 700 nm or less (more preferably 560 to 650 nm, especially preferably 560 to 640 nm).

[0220] The maximum absorption wavelength (nm) of the dichroic azo dye compound in this specification is determined by using a solution prepared by dissolving the dichroic azo dye compound in a good solvent and measuring the ultraviolet-visible spectrum in the wavelength range of 380–800 nm using a spectrophotometer.

[0221] In this invention, considering the need to further improve the orientation of the formed light-absorbing anisotropic film, the first dichroic azo dye compound is preferably a compound represented by the following formula (1).

[0222] [Chemical Formula 12]

[0223]

[0224] In formula (1), Ar1 and Ar2 independently represent either a phenylene group that may have substituents or a naphthylene group that may have substituents, with phenylene being preferred.

[0225] In formula (1), R1 represents a straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkyl carbonate, alkylamino, acylamino, alkylcarbonylamino, alkoxycarbonylamino, alkylsulfonylamino, alkylaminosulfonyl, alkylcarbamoyl, alkylsulfinyl, alkylurea, alkylphosphamide, alkylimino or alkylsilyl.

[0226] The -CH2- group constituting the above alkyl group can 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')-C(O)-N(R1')-, -CH=CH-, -C≡C-, -N=N-, -C(R1')=CH-C(O)- or -OC(O)-O-.

[0227] When R1 is a group other than a hydrogen atom, the hydrogen atom in each group can be replaced by a halogen atom, nitro group, cyano group, -N(R1')2, amino group, -C(R1')=C(R1')-NO2, -C(R1')=C(R1')-CN, or -C(R1')=C(CN)2.

[0228] R1' represents a straight-chain or branched alkyl group with 1 to 6 carbon atoms or hydrogen atoms. When multiple R1's exist in various groups, they can be the same or different.

[0229] In formula (1), R2 and R3 independently represent hydrogen atoms and straight-chain or branched alkyl, alkoxy, acyl, alkoxycarbonyl, alkylamide, alkylsulfonyl, aryl, arylcarbonyl, arylsulfonyl, aryloxycarbonyl or arylamide groups with 1 to 20 carbon atoms that may have substituents.

[0230] The -CH2- group constituting the above alkyl group can be replaced by -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-.

[0231] When R2 and R3 are groups other than hydrogen atoms, the hydrogen atoms in each group can be replaced by 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.

[0232] R2' represents a straight-chain or branched alkyl group with 1 to 6 carbon atoms or hydrogen atoms. When multiple R2's exist in various groups, they can be the same or different.

[0233] R2 and R3 can bond with each other to form a ring, and R2 or R3 can also bond with Ar2 to form a ring.

[0234] From the viewpoint of lightfastness, R1 is preferably an electron-withdrawing group, and R2 and R3 are preferably groups with low electron-donating properties.

[0235] Specific examples of such groups include alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkylsulfonylamino, alkylaminosulfonyl, alkylsulfinyl, and alkylurea groups as R1, and groups with the following structures as R2 and R3. Furthermore, the groups with the following structures are represented in the above formula (1) in the form of containing the nitrogen atoms bonded to R2 and R3.

[0236] [Chemical Formula 13]

[0237]

[0238] The following are specific examples of the first dichroic azo dye compound, but are not limited thereto.

[0239] [Chemical Formula 14]

[0240]

[0241]

[0242] (Second dichroic azo pigment compound)

[0243] The second dichroic azo dye compound is a different compound from the first dichroic azo dye compound; specifically, it has a different chemical structure.

[0244] The second dichroic azo pigment compound is preferably a compound having a chromophore as the core of the dichroic azo pigment compound and a side chain bonded to the end of the chromophore.

[0245] Specific examples of chromophores include aromatic cyclic groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups, etc., preferably having both an aromatic hydrocarbon group and an azo group, and more preferably having a diazo or triazo structure having an aromatic hydrocarbon group and 2 or 3 azo groups.

[0246] As a side chain, there are no particular limitations, and examples can be the groups represented by R4, R5 or R6 of formula (2) described later.

[0247] The second dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the range of 455 nm or higher and less than 560 nm. From the viewpoint of adjusting the hue of the light absorption anisotropic film, it is preferable to be a dichroic azo dye compound having a maximum absorption wavelength in the range of 455 to 555 nm, and more preferably a dichroic azo dye compound having a maximum absorption wavelength in the range of 455 to 550 nm.

[0248] In particular, it is easier to adjust the hue of the light absorption anisotropic film by 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 but less than 560 nm.

[0249] From the perspective of further improving the orientation degree of the light absorption anisotropic film, the second dichroic azo dye compound is preferably a compound represented by formula (2).

[0250] [Chemical Formula 15]

[0251]

[0252] In equation (2), n represents 1 or 2.

[0253] In formula (2), Ar3, Ar4 and Ar5 independently represent phenylene, naphthylene, or heterocyclic group that can have substituents, respectively.

[0254] As a heterocyclic group, it can be either aromatic or non-aromatic.

[0255] Examples of atoms other than carbon that constitute an aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. In the case of an aromatic heterocyclic group having multiple atoms that constitute the ring other than carbon, these atoms can be the same or different.

[0256] Specific examples of aromatic heterocyclic groups include pyridinyl (pyridine-diyl), pyridazine-diyl, imidazole-diyl, thiophene (thiophene-diyl), quinolineyl (quinoline-diyl), isoquinolineyl (isoquinoline-diyl), oxazole-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thienothiazole-diyl, thiazonothiazole-diyl, thienothiphene-diyl, and thienooxazole-diyl.

[0257] In equation (2), R4 is defined in the same way as R1 in equation (1).

[0258] In equation (2), the definitions of R5 and R6 are the same as those of R2 and R3 in equation (1).

[0259] From the viewpoint of lightfastness, R4 is preferably an electron-withdrawing group, and R5 and R6 are preferably groups with low electron-donating properties.

[0260] In this group, the specific examples of R4 being an electron-withdrawing group are the same as those of R1 being an electron-withdrawing group, and the specific examples of R5 and R6 being groups with low electron-donating properties are the same as those of R2 and R3 being groups with low electron-donating properties.

[0261] The following are specific examples of second dichroic azo dye compounds, but are not limited to them.

[0262] [Chemical Formula 16]

[0263]

[0264]

[0265]

[0266]

[0267] (Difference in logP values)

[0268] The logP value is an indicator of the hydrophilicity and hydrophobicity of the chemical structure. The absolute value of the 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 "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 is increased, making it easier to form an alignment structure, thereby further improving the orientation degree of the light absorption anisotropic film.

[0269] Furthermore, when there are multiple side chains of the first or second dichroic azo dye compound, it is preferable that at least one logP difference satisfies the above value.

[0270] Here, the side chains of the first and second dichroic azo pigment compounds refer to the groups bonded to the ends of the chromophores. For example, when the first dichroic azo pigment compound is a compound represented by formula (1), R1, R2, and R3 in formula (1) are side chains, and when the second dichroic azo pigment compound is a compound represented by formula (2), R4, R5, and R6 in formula (2) are side chains. In particular, when the first dichroic azo pigment compound is a compound represented by formula (1) and the second dichroic azo pigment compound is a compound represented by formula (2), it is preferable that at least one logP difference among the differences in logP values ​​of R1 and R4, R1 and R5, R2 and R4, and R2 and R5 satisfies the above-mentioned value.

[0271] Here, the logP value is an indicator of the hydrophilicity and hydrophobicity of a chemical structure, sometimes referred to as 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 experimentally determined using methods such as those described in OECD Guidelines for the Testing of Chemicals, Section 1, Test No. 117. In this invention, unless otherwise specified, the logP value is the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07).

[0272] (Third dichroic azo pigment compound)

[0273] The third dichroic azo pigment compound is a dichroic azo pigment compound other than the first and second dichroic azo pigment compounds. Specifically, its chemical structure differs from that of the first and second dichroic azo pigment compounds. As long as the light-absorbing anisotropic film contains the third dichroic azo pigment compound, it has the advantage of easily adjusting the hue of the light-absorbing anisotropic film.

[0274] The maximum absorption wavelength of the third dichroic azo dye compound is above 380 nm and below 455 nm, preferably 385 to 454 nm.

[0275] As a specific example of the third dichroic azo dye compound, the compound represented by formula (1) as described in International Publication No. 2017 / 195833 may be cited. Among the compounds, compounds other than the first dichroic azo dye compound and the second dichroic azo dye compound described above may be cited.

[0276] The following are specific examples of the third dichroic azo dye compound, but the present invention is not limited thereto. Furthermore, in the following specific examples, n represents an integer from 1 to 10. And Me represents a methyl group.

[0277] [Chemical Formula 17]

[0278]

[0279] [Chemical Formula 18]

[0280]

[0281] (Content of dichroic substances)

[0282] The content of the dichroic substance relative to the total solid content of the liquid crystal composition is preferably 1 to 70% by mass, more preferably 2 to 60% by mass, and particularly preferably 3 to 50% by mass. As long as the content of the dichroic substance is within the above range, a light absorption anisotropy film with high orientation can be obtained even when the light absorption anisotropy film is a thin film. Therefore, it is easy to obtain a light absorption anisotropy film with excellent flexibility.

[0283] The content of dichroic material in the light-absorbing anisotropic film is preferably the same as the content of dichroic material relative to the total solid content of the liquid crystal composition described above.

[0284] The content of the first dichroic azo dye compound is preferably 40 to 90 parts by mass relative to the total content of dichroic substances in the liquid crystal composition, more preferably 45 to 75 parts by mass per 100 parts by mass.

[0285] The content of the second dichroic azo dye compound is preferably 6 to 50 parts by mass relative to 100 parts by mass of the total content of dichroic substances in the liquid crystal composition, more preferably 8 to 35 parts by mass.

[0286] The content of the third dichroic azo dye compound is preferably 3 to 35 parts by mass relative to 100 parts by mass of the total content of dichroic substances in the liquid crystal composition, more preferably 5 to 30 parts by mass.

[0287] To adjust the hue of the light-absorbing anisotropic film, the content ratios of the first dichroic azo dye compound, the second dichroic azo dye compound, and the third dichroic azo dye compound (if used as needed) can be arbitrarily set. 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 in molar terms, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8. As long as 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 improved.

[0288] <Polymerized boric acid compounds>

[0289] Polymerizable boric acid compounds are compounds having at least one group selected from the group consisting of a boric acid group, a borate ester group, and a boronoxane cyclic group formed by the dehydration condensation of a boric acid group, and having a polymerizable group. The boronoxane cyclic group is formed by the dehydration trimerization of the boric acid group.

[0290] Polymerizable boric acid compounds can polymerize in light-absorbing anisotropic films.

[0291] Acryloyl, methacryloyl, epoxy, oxetyl, and styrene groups are preferred as polymerizable groups, and acryloyl and methacryloyl are preferred from the perspective of better adhesion.

[0292] Polymerizable boric acid compounds may have one or more polymerizable groups, or more than two. However, considering at least one superior aspect of adhesion and orientation, it is preferred to have one polymerizable group.

[0293] The borate group is represented by -B(OH)2.

[0294] As a boronic ester group, examples include -B(-OR) in the following formula (B-1). B12 (-OR) B13 The group represented by ) contains R B12 and R B13 At least one of them is a group other than a hydrogen atom.

[0295] Examples of boronoxane cyclic groups include those represented by the following formula (BX). Furthermore, in formula (BX), * indicates a bond with other groups.

[0296] The polymeric boric acid compound may have at least one group selected from the group consisting of boric acid group, borate ester group and borooxane cyclo group, and may have two or more groups. However, it is preferred to have only one group, considering at least one aspect of superiority in terms of tightness and orientation.

[0297] [Chemical Formula 19]

[0298]

[0299] From the perspective of superior orientation, polymerizable boric acid compounds preferably have aromatic rings.

[0300] Examples of aromatic rings include aromatic hydrocarbon groups and aromatic heterocyclic groups. Among them, aromatic hydrocarbon groups are preferred when considering at least one aspect of superiority in terms of tightness and orientation.

[0301] There is no particular limitation on the number of carbon atoms in the aromatic hydrocarbon group, but 4 to 20 is preferred, and 6 to 12 is more preferred. Examples of aromatic hydrocarbon groups include benzene ring groups.

[0302] There is no particular limitation on the number of carbon atoms in the aromatic heterocyclic group, but 3 to 10 is preferred, and 3 to 5 is more preferred. Examples of atoms other than carbon atoms constituting the aromatic heterocyclic group include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0303] Aromatic hydrocarbon groups and aromatic heterocyclic groups can be substituted by substituents.

[0304] When the polymeric boric acid compound has an aromatic ring, the number of aromatic rings can be one or more, but one is preferred from the perspective of better orientation.

[0305] Considering at least one superior aspect of adhesion and orientation, the polymeric boric acid compound preferably comprises at least one of the compounds represented by formula (B-1) and the compounds represented by formula (BX-1).

[0306] Compounds represented by formula (BX-1) are obtained, for example, by dehydration condensation of compounds represented by formula (B-1).

[0307] [Chemical Formula 20]

[0308]

[0309] In equation (B-1), R B11 It represents a hydrogen atom or a methyl group.

[0310] L B1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. B14 The divalent group (hereinafter also referred to as "divalent linker B1") is substituted by at least one group (hereinafter also referred to as "specific group B1") in the group consisting of )-. Among them, the divalent linker B1 is preferred from the viewpoint of superior orientation and tightness.

[0311] R B14The symbol represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. There is no particular limitation on the number of carbon atoms in an alkyl group, but 1 to 3 are preferred, and 1 is particularly preferred.

[0312] The divalent aliphatic hydrocarbon group can be saturated or unsaturated, but saturated is preferred. The divalent aliphatic hydrocarbon group can be linear, branched, or cyclic, with linear or branched being preferred. For better orientation and tightness, the divalent aliphatic hydrocarbon group is preferably alkylene. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, and particularly preferably 1 to 5.

[0313] In the divalent linker B1, only one -CH2- group constituting the divalent aliphatic hydrocarbon group can be replaced by a specific group B1, or more than two -CH2- groups can be replaced by a specific group B1.

[0314] Preferred alternatives for the divalent linker B1 include -C(=O)-O-alkylene- and -C(=O)-O-alkylene-N(R B14 -C(=O)-O-, -C(=O)-O-alkylene-O-, -C(=O)-N(R) B14 )-、-alkylene-N(R B14 )-C(=O)-O- and -alkylene-O-.

[0315] A B1 This refers to an arylene group that may have substituents or a heteroarylene group that may have substituents. Among these, considering at least one aspect of superiority in terms of tightness and orientation, an arylene group that may have substituents is preferred, and an arylene group (i.e., an arylene group without substituents) is particularly preferred.

[0316] There is no particular limitation on the number of carbon atoms in the arylene group, but 4 to 20 is preferred, and 6 to 12 is more preferred. For example, phenylene can be cited as an arylene group.

[0317] There is no particular limitation on the number of carbon atoms in the heteroaryl group, but 3 to 10 is preferred, and 3 to 5 is more preferred. Examples of heteroatoms contained in the heteroaryl group include oxygen, nitrogen, and sulfur atoms.

[0318] R B12 and R B13 Each of the following can be independently represented: a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or a heteroaryl group that may have substituents. Among these, considering at least one aspect of superior adhesion and orientation, a hydrogen atom or an alkyl group that may have substituents is preferred, and a hydrogen atom is more preferred.

[0319] There is no particular limitation on the number of carbon atoms in the alkyl group, but 1 to 10 is preferred, and 1 to 5 is more preferred. Examples of alkyl groups include methyl, ethyl, and propyl.

[0320] There is no particular limitation on the number of carbon atoms in the aryl group, but 4 to 20 is preferred, and 6 to 12 is more preferred. For example, phenyl can be cited as an aryl group.

[0321] There is no particular limitation on the number of carbon atoms in the heteroaryl group, but 3 to 10 is preferred, and 3 to 5 is more preferred. Examples of heteroatoms contained in the heteroaryl group include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0322] R B12 and R B13 They can bond with each other to form a ring, such as an aliphatic hydrocarbon ring containing boron atoms.

[0323] Considering at least one superior aspect of fit and orientation, the compound represented by formula (B-1) is preferably the compound represented by formula (B-2).

[0324] [Chemical Formula 21]

[0325]

[0326] In equation (B-2), R B21 It represents a hydrogen atom or a methyl group.

[0327] L B2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R). B25 The divalent group (hereinafter also referred to as "divalent linker B2") is substituted by at least one group (hereinafter also referred to as "specific group B2") in the group consisting of )-. Among them, the divalent linker B2 is preferred from the viewpoint of superior orientation and tightness.

[0328] R B25 The symbol represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. There is no particular limitation on the number of carbon atoms in an alkyl group, but 1 to 3 are preferred, and 1 is particularly preferred.

[0329] L B2 The divalent aliphatic hydrocarbon group, the divalent linker B2, and the specific group B2 in formula (B-1) are respectively associated with L B1 The divalent aliphatic hydrocarbon group, the divalent linker B1, and the specific group B1 are the same, so their descriptions are omitted.

[0330] R B22 and R B23 Each of the following can be independently represented: a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or a heteroaryl group that may have substituents. Among these, considering at least one aspect of superior adhesion and orientation, a hydrogen atom or an alkyl group that may have substituents is preferred, and a hydrogen atom is more preferred.

[0331] R B22 The groups in the formula (B-1) are similar to the R group in the formula (B-1). B12 The groups in the text are identical, therefore their descriptions are omitted.

[0332] R B23 The groups in the formula (B-1) are similar to the R group in the formula (B-1). B13 The groups in the text are identical, therefore their descriptions are omitted.

[0333] R B22 and R B23 They can bond with each other to form a ring, such as an aliphatic hydrocarbon ring containing boron atoms.

[0334] R B24 This indicates a monovalent substituent. Specific examples of monovalent substituents are described below. Alkyl, halogen, alkoxy, or aryl substituents are preferred as monovalent substituents.

[0335] nb represents an integer from 0 to 4. Among them, considering at least one aspect of better fit and orientation, 0 or 1 is preferred, and 0 is more preferred.

[0336] When nb is 2 or higher, multiple R B24 They can be the same or different.

[0337] In the compounds represented by formula (B-2), -B(OR) B22 (OR) B23 The position of the group represented by ) is not particularly limited, but considering at least one aspect of better adhesion and orientation, it is preferred to be relative to L. B2 The bonding positions are configured at interpositions or parallel positions.

[0338] The following are specific examples of compounds represented by formula (B-1), but are not limited to them. Additionally, in the formula, Me refers to a methyl group.

[0339] [Chemical Formula 22]

[0340]

[0341] [Chemical Formula 23]

[0342]

[0343] In equation (BX-1), R BX11 Represents a hydrogen atom or a methyl group. Multiple RBs X11 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0344] L BX1The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. BX14 The divalent group (hereinafter also referred to as "divalent linker BX1") is substituted by at least one group (hereinafter also referred to as "specific group BX1") in the group L-. Among these, the divalent linker BX1 is preferred from the viewpoint of superior orientation and tightness. Multiple L BX1 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0345] R BX14 The symbol represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and particularly 1 is preferred. In the presence of multiple R groups... BX14 In the case of multiple R BX14 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0346] L BX1 The divalent aliphatic hydrocarbon group, the divalent linker BX1, and the specific group BX1 in formula (B-1) are respectively associated with L B1 The divalent aliphatic hydrocarbon group, the divalent linker B1, and the specific group B1 are the same, so their descriptions are omitted.

[0347] A BC1 This refers to an arylene group that may have substituents or a heteroarylene group that may have substituents. Among these, considering at least one aspect of superiority in terms of tightness and orientation, an arylene group that may have substituents is preferred, and an arylene group (i.e., an arylene group without substituents) is particularly preferred.

[0348] Multiple A's BX1 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0349] There is no particular limitation on the number of carbon atoms in the arylene group, but 4 to 20 is preferred, and 6 to 12 is more preferred. Examples of arylene groups include phenylene and naphthyl groups.

[0350] There is no particular limitation on the number of carbon atoms in the heteroaryl group, but 3 to 10 is preferred, and 3 to 5 is more preferred. Examples of heteroatoms contained in the heteroaryl group include oxygen, nitrogen, and sulfur atoms.

[0351] Considering at least one superior aspect of fit and orientation, the compound represented by formula (BX-1) is preferably the compound represented by formula (BX-2).

[0352] [Chemical Formula 24]

[0353]

[0354] In equation (BX-2), R BX21 Represents a hydrogen atom or a methyl group. Multiple R's BX21 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0355] L Bx2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. BX25 The divalent group (hereinafter also referred to as "divalent linker BX2") substituted by at least one group (hereinafter also referred to as "specific group BX2") from the group consisting of )-. Among these, the divalent linker BX2 is preferred from the viewpoint of superior orientation and tightness. Multiple L BX2 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0356] R BX25 The symbol represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and particularly 1 is preferred. In the presence of multiple R groups... BX25 In the case of multiple R BX25 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0357] L BX2 The divalent aliphatic hydrocarbon group, the divalent linker BX2, and the specific group BX2 in formula (B-1) are respectively associated with L B1 The divalent aliphatic hydrocarbon group, the divalent linker B1, and the specific group B1 are the same, so their descriptions are omitted.

[0358] R BX24 This represents a substituent with a monovalent valence. In the presence of multiple R... BX24 In the case of multiple R BX24 They can be the same or different, but considering at least one aspect of superior fit and orientation, they are preferred to be the same.

[0359] As R BX24 Specific examples of monovalent substituents are described below. Alkyl, halogen, alkoxy, or aryl groups are preferred as monovalent substituents.

[0360] nc represents an integer from 0 to 4. Preferably, 0 or 1 is preferred, and more preferably 0, considering at least one superior aspect of fit and orientation. Multiple nc values ​​may be the same or different, but preferably the same, considering at least one superior aspect of fit and orientation.

[0361] The following are specific examples of compounds represented by formula (BX-1), but are not limited to them. Additionally, in the formula, Me refers to a methyl group.

[0362] [Chemical Formula 25]

[0363]

[0364]

[0365] [Chemical Formula 26]

[0366]

[0367] [Chemical Formula 27]

[0368]

[0369] [Chemical Formula 28]

[0370]

[0371] [Chemical Formula 29]

[0372]

[0373] The content of the polymeric boric acid compound relative to the total solid content of the liquid crystal composition 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. When the content of the polymeric boric acid compound is above the lower limit, the adhesion of the light-absorbing anisotropic film is more excellent. When the content of the polymeric boric acid compound is below the upper limit, the orientation of the light-absorbing anisotropic film is more excellent.

[0374] Polymerizable boric acid compounds can be used alone or in combination of two or more. When two or more polymerizable boric acid compounds are included, it is preferable that their total amount is within the range described above.

[0375] The content of polymeric boric acid compound in the light-absorbing anisotropic film is preferably the same as the content of polymeric boric acid compound relative to the total solid content of the liquid crystal composition described above.

[0376] In terms of excellent storage stability of the liquid crystal composition, the liquid crystal composition preferably contains both a compound represented by formula (B-1) (preferably a compound represented by formula (B-2)) and a compound represented by formula (BX-1) (preferably a compound represented by formula (BX-2)).

[0377] In this case, from the perspective of better 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 compound represented by formula (B-1) / content of compound represented by formula (BX-1)) is preferably 0.1 to 2000, more preferably 1 to 1000, and even more preferably 5 to 500.

[0378] Solvent

[0379] From the viewpoint of operability, liquid crystal compositions preferably contain a solvent.

[0380] 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 cyclopentylmethyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), carbon halogens (e.g., dichloromethane, chloroform, dichloroethane, dichlorobenzene, and chlorotoluene), and esters (e.g., ethyl acetate). Organic solvents such as methyl esters, ethyl acetate, butyl acetate, diethyl carbonate, etc., alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosols (e.g., methyl cellosol, ethyl cellosol, and 1,2-dimethoxyethane, etc.), cellosol acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide and dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolium ketone, etc.), and heterocyclic compounds (e.g., pyridine, etc.) and water can be used. These solvents can be used individually or in combination of two or more.

[0381] Of these solvents, organic solvents are preferred for the sake of superior performance of the present invention, and halogenated carbons or ketones are more preferred.

[0382] When the liquid crystal composition contains a solvent, the solvent content relative to the total mass of the liquid crystal composition is preferably 80 to 99% by mass, more preferably 83 to 97% by mass, and particularly preferably 85 to 95% by mass.

[0383] A single solvent may be used, or two or more solvents may be used in combination. When two or more solvents are used, it is preferable that their total amount is within the range described above.

[0384] <Surface Modifier>

[0385] The liquid crystal composition preferably contains a surface modifier (hereinafter also referred to as "surfactant"). By containing a surface modifier, the smoothness of the coated surface is improved, the orientation degree is improved or depressions and unevenness are suppressed, and it is expected to improve the in-plane uniformity.

[0386] As a surface modifier, it is preferable to horizontally align the liquid crystal compound, and compounds (horizontal alignment agents) described in paragraphs

[0253] to

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

[0018] to

[0043] of Japanese Patent Application Publication No. 2007-272185 can also be used. Other compounds can also be used as surface modifiers.

[0387] When the liquid crystal composition contains a surface modifier, the content of the surface modifier in the liquid crystal composition is preferably 0.1 to 2.0% by mass relative to the total solid content of the liquid crystal composition, more preferably 0.1 to 1.0% by mass.

[0388] A single surface modifier or two or more can be used. When two or more surface modifiers are used, it is preferable that their total amount is within the range described above.

[0389] When the light-absorbing anisotropic film contains a surface modifier, the content of the surface modifier relative to the total mass of the light-absorbing anisotropic film is preferably the same as the content of the surface modifier relative to the total solid content of the liquid crystal composition.

[0390] <Polymerization initiator>

[0391] The liquid crystal composition preferably contains a polymerization initiator.

[0392] Preferably, the polymerization initiator used is a photopolymerization initiator that can initiate a polymerization reaction by ultraviolet irradiation.

[0393] Examples of photopolymerization initiators include α-carbonyl compounds (described in U.S. Patent Nos. 2,367,661 and 2,367,670), azobin ethers (described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic azobin compounds (described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (described in U.S. Patent Nos. 3,046,127 and 2,951,758), triarylimidazolium dimers, and p-aminophenyl ketones. Combinations (described in U.S. Patent No. 3,549,367), acridine and phenazine compounds (described in Japanese Patent Application Publication No. 60-105,667 and U.S. Patent No. 4,239,850), oxadiazole compounds (described in U.S. Patent No. 4,212,970), acylphosphine oxide compounds (described in Japanese Patent Application Publication No. 63-40,799, Japanese Patent Application Publication No. 5-29,234, Japanese Patent Application Publication No. 10-95,788 and Japanese Patent Application Publication No. 10-29,997), etc.

[0394] Furthermore, in this invention, the polymerization initiator is preferably an oxime-type polymerization initiator. As a specific example, the initiator described in paragraphs

[0049] to

[0052] of International Publication No. 2017 / 170443 can be cited.

[0395] When the liquid crystal composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, relative to the total of 100 parts by mass of the dichroic substance and the liquid crystal compound in the liquid crystal composition. When the content of the polymerization initiator is 0.01 parts by mass or more, the durability of the light-absorbing anisotropic film becomes better; when the content of the polymerization initiator is 30 parts by mass or less, the orientation degree of the light-absorbing anisotropic film becomes better.

[0396] A single polymerization initiator may be used, or two or more may be used in combination. When two or more polymerization initiators are used, it is preferable that their total amount is within the range described above.

[0397] <Substituent>

[0398] Unless otherwise specified, substituents in this specification refer to the following groups.

[0399] Examples of substituents include alkyl groups (preferably with 1 to 20 carbon atoms, more preferably with 1 to 12 carbon atoms, and especially preferably with 1 to 8 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl), alkenyl groups (preferably with 2 to 20 carbon atoms, more preferably with 2 to 12 carbon atoms, and especially preferably with 2 to 8 carbon atoms, such as vinyl, aryl, 2-butenyl, and 3-pentenyl), alkynyl groups (preferably with 2 to 20 carbon atoms, more preferably with 2 to 12 carbon atoms, and especially preferably with 2 to 8 carbon atoms, such as propynyl and 3-pentynyl), and aryl groups (preferably...). The group consists of aryl groups with 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl, 2,6-diethylphenyl, 3,5-ditrifluoromethylphenyl, styryl, naphthyl, and biphenyl, etc.; substituted or unsubstituted amino groups (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, such as unsubstituted amino, methylamino, dimethylamino, diethylamino, and aniline, etc.); alkoxy groups (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as methoxy, ethoxy, and butoxy, etc.); and oxycarbonyl groups (preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, etc.). Preferably, the carbon number is 2 to 15, more preferably 2 to 10, for example, methoxycarbonyl, ethoxycarbonyl and phenoxycarbonyl, etc.); acyloxy (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6, for example, acetoxy, benzoyloxy, acryloyl and methacryloyl, etc.); amide (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, acetamino and benzoylamino, etc.); alkoxycarbonylamino (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino, etc.); aryloxycarbonyl Amino groups (preferably with 7 to 20 carbon atoms, more preferably with 7 to 16 carbon atoms, and especially preferably with 7 to 12 carbon atoms, such as phenoxycarbonylamino), sulfonylamino (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, and especially preferably with 1 to 6 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), aminosulfonyl (preferably with 0 to 20 carbon atoms, more preferably with 0 to 10 carbon atoms, and especially preferably with 0 to 6 carbon atoms, such as aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, and phenylaminosulfonyl), and carbamoyl (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, and especially preferably with 1 to 6 carbon atoms).Examples of examples include unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl groups; alkylthio groups (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, and especially preferably with 1 to 6 carbon atoms, such as methylthio and ethylthio groups); arylthio groups (preferably with 6 to 20 carbon atoms, more preferably with 6 to 16 carbon atoms, and especially preferably with 6 to 12 carbon atoms, such as phenylthio groups); and sulfonyl groups (preferably with 1 to 20 carbon atoms). More preferably, the carbon number is 1 to 10, especially preferably 1 to 6, for example, methanesulfonyl and toluenesulfonyl, etc.); thionyl (preferably 1 to 20 carbon atoms, more preferably 1 to 10, especially preferably 1 to 6, for example, methanethionyl and phenylthionyl, etc.); urea (preferably 1 to 20 carbon atoms, more preferably 1 to 10, especially preferably 1 to 6, for example, unsubstituted urea, methylurea and phenyl, etc.). Urea group, etc.), phosphoramide group (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, especially preferably with 1 to 6 carbon atoms, such as diethylphosphatamide group and phenylphosphatamide group, etc.), hydroxyl group, mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom and iodine atom), cyano group, nitro group, oxime group, sulfinyl group, hydrazine group, imino group, azo group, heterocyclic group (preferably with 1 to 30 carbon atoms, more preferably with 1 to 12 carbon atoms, such as nitrogen atom). Heterocyclic groups containing heteroatoms such as oxygen and sulfur atoms, including, for example, epoxy, oxacyclobutyl, imidazolyl, pyridinyl, quinolinyl, furanyl, piperidinyl, morpholino, maleimide, benzoxazolyl, benzimidazolyl, and benzothiazolyl, etc.; silyl groups (preferably with 3 to 40 carbon atoms, more preferably with 3 to 30 carbon atoms, and especially preferably with 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl, etc.); carboxyl groups, sulfonic acid groups, and phosphate groups, etc.

[0400] [Horizontal orientation]

[0401] As described above, in the anisotropic light-absorbing film of the present invention, the liquid crystal compound is horizontally oriented. Furthermore, in the anisotropic light-absorbing film of the present invention, the dichroic material is preferably also horizontally oriented along the liquid crystal compound.

[0402] Here, horizontal alignment means that the molecular axis of the liquid crystal compound (e.g., the long axis in the case of rod-shaped liquid crystal compounds) is parallel to the main surface of the light-absorbing anisotropic film, but strict parallelism is not required. It means that the tilt angle between the average molecular axis of the liquid crystal compound in the light-absorbing anisotropic film and the main surface of the light-absorbing anisotropic film is less than ±10 degrees. Furthermore, the above tilt angle can be measured using an AxoScan OPMF-1 (manufactured by Opto Science, Inc.).

[0403] Specifically, using an AxoScan OPMF-1 (manufactured by Opto Science, Inc.), the Mueller matrix of the anisotropic film with light absorption at wavelength λ was measured at polar angles every 10 degrees between -50°C and 50°C. After removing the influence of surface reflection, the matrix was fitted with the theoretical formula considering Snell and Fresnel forms to calculate the extinction coefficients ko[λ] (in-plane direction) and ke[λ] (thickness direction). Unless otherwise specified, the wavelength λ was set to 550 nm.

[0404] k = -log(T) × λ / (4πd)

[0405] Here, T represents transmittance, and d represents the thickness of the polarizer.

[0406] Based on the calculated ko[λ] and ke[λ], the absorbance and dichroism ratio in the in-plane and thickness directions can be calculated, thereby confirming whether the orientation is horizontal.

[0407] [Method for manufacturing anisotropic light-absorbing films]

[0408] There are no particular limitations on the method for manufacturing the light-absorbing anisotropic film of the present invention. However, considering that the degree of orientation of the obtained light-absorbing anisotropic film is higher, it is preferable to include the following steps in sequence (hereinafter also referred to as "the manufacturing method of the present invention"): a step of coating the above-mentioned liquid crystal composition onto an alignment film to form a coating film (hereinafter also referred to as "coating film forming step"); and a step of aligning the liquid crystal components contained in the above-mentioned coating film (hereinafter also referred to as "alignment step").

[0409] In addition, liquid crystal components refer to components that not only contain the aforementioned liquid crystal compounds but also contain dichroic substances with liquid crystal properties.

[0410] The following is a description of each process.

[0411] <Coating film formation process>

[0412] The coating film formation process involves coating the aforementioned liquid crystal composition onto an alignment film to form a coating film. The liquid crystal compound in the coating film is horizontally aligned through the interaction between the alignment film and (in the case where the liquid crystal composition contains a surface modifier) ​​the surface modifier.

[0413] By using a liquid crystal composition containing the aforementioned solvent or by using a substance that forms a liquid liquid such as a melt by heating, the liquid crystal composition can be easily coated onto an alignment film.

[0414] Commonly known methods for coating liquid crystal compositions include roller coating, gravure printing, spin coating, wire-wound coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0415] (Orientation film)

[0416] The alignment film can be any film as long as it is a film that horizontally aligns the liquid crystal compounds contained in the liquid crystal composition.

[0417] Alignment films can be formed by methods such as triboelectric treatment of the film surface of organic compounds (preferably polymers), tilted evaporation of inorganic compounds, formation of layers with microgrooves, or accumulation of organic compounds (e.g., ω-trisanoic acid, dioctadecylmethylammonium chloride, methyl stearate) based on the Langmuir Blodgett process (LB film). Alignment films that generate alignment functions by imparting an electric field, a magnetic field, or light irradiation are also known. In this invention, from the perspective of easily controlling the pretilt angle of the alignment film, an alignment film formed by triboelectric treatment is preferred; from the perspective of alignment uniformity, a photo-alignment film formed by light irradiation is also preferred.

[0418] (1) Friction-treated orientation film

[0419] Polymer materials used in alignment films formed by friction processing have been described in numerous documents, and many commercially available products are readily available. In this invention, polyvinyl alcohol or polyimide and its derivatives are preferably used. Regarding the alignment film, reference can be made to the description on page 43, line 24 to page 49, line 8 of International Publication No. 2001 / 88574A1. The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm.

[0420] (2) Photoalignment film

[0421] Photoalignment materials for alignment films formed by light irradiation have been described in numerous documents. In this invention, preferred examples include, for instance, the azo dyes described in Japanese Patent Application Publication Nos. 2006-285197, 2007-76839, 2007-138138, 2007-94071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, Japanese Patent Nos. 3883848, and 4151746. Compounds, aromatic ester compounds described in Japanese Patent Application Publication No. 2002-229039, maleimides having photo-orientation units and / or alkenyl-substituted nadicimide compounds described in Japanese Patent Application Publication No. 2002-265541 and No. 2002-317013, photocrosslinkable silane derivatives described in Japanese Patent Nos. 4205195 and 4205198, photocrosslinkable polyimides, polyamides, or esters described in Japanese Patent Application Publication Nos. 2003-520878, 2004-529220, or 4162850. More preferably, azo compounds, photocrosslinkable polyimides, polyamides, or esters.

[0422] The photo-alignment film is manufactured by irradiating the photo-alignment film formed from the above materials with linearly polarized light or unpolarized light.

[0423] In this specification, "linearly polarized light irradiation" and "unpolarized light irradiation" refer to operations used to induce a photoreaction in a photo-alignment material. The wavelength of the light used varies depending on the photo-alignment material used, and is not particularly limited as long as it is the wavelength required for the photoreaction. The peak wavelength of the light used in the irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light with a peak wavelength of 400 nm or less.

[0424] Light sources used in illumination can include commonly used light sources such as 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.

[0425] Methods for obtaining linearly polarized light include using polarizers (e.g., iodine polarizers, dichroic material polarizers, and wire-grid polarizers), using prism-like elements (e.g., Glan-Thomson prisms), using Brewster angle reflective polarizers, or using light emitted from a laser source with polarization. Furthermore, filters or wavelength conversion elements can be used to selectively illuminate only the desired wavelength of light.

[0426] When the irradiated light is linearly polarized, a method is used to irradiate the alignment film from the top surface or from the back surface, either perpendicularly or obliquely. The incident angle of the light varies depending on the photoalignment material, preferably 0–90° (perpendicular), and more preferably 40–90°.

[0427] In the case of unpolarized light, unpolarized light is irradiated at an angle towards the alignment film. The incident angle is preferably 10 to 80°, more preferably 20 to 60°, and particularly preferably 30 to 50°.

[0428] The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

[0429] When patterning is required, the method of applying light through a photomask to create the pattern the required number of times can be used, or the pattern can be written by laser scanning.

[0430] <Orientation Process>

[0431] The alignment process is a process of orienting the dichroic material contained in the coated film. This allows the light-absorbing anisotropic film of the present invention to be obtained. It is understood that in the alignment process, the dichroic material is aligned along the liquid crystal compound oriented through the alignment film.

[0432] The orientation process may include a drying process. This drying process removes components such as solvents from the coated film. The drying process can be performed by placing the coated film at room temperature for a specified time (e.g., natural drying), or by heating and / or air supply.

[0433] Here, the dichroic substances contained in the liquid crystal composition are sometimes oriented through the above-described coating film formation process or drying treatment. For example, sometimes in the process of preparing the liquid crystal composition into a coating liquid containing a solvent, the solvent is removed from the coating film by drying the coating film, and the dichroic substances contained in the coating film are oriented to obtain the light absorption anisotropic film of the present invention.

[0434] The orientation process preferably includes heat treatment. As a result, the dichroic substances contained in the coated film are further oriented, and the degree of orientation of the obtained light-absorbing anisotropic film becomes higher.

[0435] From the perspective of manufacturing applicability, the heat treatment is preferably 10–250°C, more preferably 25–190°C. Furthermore, the heating time is preferably 1–300 seconds, more preferably 1–60 seconds.

[0436] The orientation process can include a cooling process performed after the heat treatment. The cooling process involves cooling the heated coated film to approximately room temperature (20–25°C). This further fixes the orientation of the dichroic substances contained in the coated film, and the degree of orientation of the resulting anisotropic light-absorbing film becomes higher. There are no particular limitations on the cooling method; it can be implemented using known methods.

[0437] Through the above processes, the light absorption anisotropic film of the present invention can be obtained.

[0438] [Other processes]

[0439] This manufacturing method may include a step (hereinafter also referred to as the "curing step") after the above-mentioned orientation step, in which the light-absorbing anisotropic film is cured.

[0440] The curing process is carried out, for example, by heating and / or light irradiation (exposure). Preferably, the curing process is carried out by light irradiation.

[0441] The light source used for curing can be various light sources such as infrared, visible light, or ultraviolet light, but ultraviolet light is preferred. Furthermore, ultraviolet light can be irradiated while heating is being performed during curing, or ultraviolet light can be irradiated through a filter that allows only specific wavelengths to pass through.

[0442] Furthermore, exposure can be performed under a nitrogen atmosphere. In the case of curing anisotropic films with light absorption via free radical polymerization, the polymerization hindrance caused by oxygen can be reduced, therefore exposure under a nitrogen atmosphere is preferred.

[0443] [Liquid Crystal Composition]

[0444] The liquid crystal composition of the present invention contains a liquid crystal compound, a dichroic substance, and a boric acid compound having polymerizable groups, wherein the aforementioned boric acid compound having polymerizable groups is a compound represented by formula (B-2).

[0445] The components contained in the liquid crystal composition of the present invention and the components that may be contained therein are the same as those contained in the liquid crystal composition used in the formation of the light absorption anisotropic film of the present invention and the preferred manner therein are also the same, therefore their description is omitted.

[0446] The liquid crystal composition of the present invention is preferably used for the formation of the above-mentioned light-absorbing anisotropic film.

[0447] [Layered Body]

[0448] The laminate of the present invention has the light-absorbing anisotropic film of the present invention described above and a layer configured to be in contact with the light-absorbing anisotropic film and containing a polyvinyl alcohol resin.

[0449] Furthermore, the laminate of the present invention may have a λ / 4 plate on the side of the light-absorbing anisotropic film opposite to the layer containing polyvinyl alcohol resin. Additionally, the laminate of the present invention may have a barrier layer between the light-absorbing anisotropic film and the λ / 4 plate.

[0450] Furthermore, the laminate of the present invention may have a substrate on the side opposite to the light-absorbing anisotropic film containing the polyvinyl alcohol resin layer.

[0451] The layers constituting the laminate of the present invention will be described below.

[0452] [Substrate]

[0453] The substrate can be appropriately selected, for example, glass and polymer films. The light transmittance of the substrate is preferably 80% or higher.

[0454] When using a polymer film as the substrate, an optically isotropic polymer film is preferred. Specific examples and preferred embodiments of the polymer are described in paragraph

[0013] of Japanese Patent Application Publication No. 2002-22942. Furthermore, even polymers that readily exhibit birefringence, such as polycarbonate or polysulfone, which are known in the past, can be used, as described in International Publication No. 2000 / 26705, which reduce the visibility of birefringence through molecular modification.

[0455] [Layer containing polyvinyl alcohol resin]

[0456] The layer containing polyvinyl alcohol resin is preferably an oriented film. As described above, the explanation of the oriented film is omitted.

[0457] Polyvinyl alcohol resins are resins containing repeating units of -CH2-CHOH-, such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers.

[0458] Polyvinyl alcohol resins are obtained, for example, by saponifying polyvinyl acetate resins. Examples of polyvinyl acetate resins include homopolymers of vinyl acetate, i.e., polyvinyl acetate, as well as copolymers with other monomers capable of copolymerizing with vinyl acetate.

[0459] Other monomers that can copolymerize with vinyl acetate include, for example, unsaturated carboxylic acids, alkenes, vinyl ethers, unsaturated sulfonic acids, and acrylamides with ammonium groups.

[0460] At least one hydroxyl group in a polyvinyl alcohol resin can be modified by functional groups such as acetylacetyl, sulfonic acid, carboxyl, and alkylene oxide. That is, polyvinyl alcohol resins can be so-called modified polyvinyl alcohol resins.

[0461] Furthermore, as a modified polyvinyl alcohol resin, polyvinyl alcohol resins having polymerizable groups (e.g., (meth)acryloyl, vinyl) can also be cited.

[0462] Therefore, polyvinyl alcohol resins include unmodified polyvinyl alcohol resins and modified polyvinyl alcohol resins.

[0463] There is no particular limitation on the content of polyvinyl alcohol resin in the alignment film, but it is preferred that polyvinyl alcohol resin is included as a main component in the alignment film. A main component refers to a polyvinyl alcohol resin content of 50% by mass or more relative to the total mass of the alignment film. Preferably, the polyvinyl alcohol resin content is 90% by mass or more relative to the total mass of the alignment film. There is no particular upper limit, but it is usually below 99.9% by mass.

[0464] [Anisotropic light absorption film]

[0465] Regarding the light-absorbing anisotropic film (light-absorbing anisotropic layer) of the present invention, as described above, its description is therefore omitted. In the present invention, the light-absorbing anisotropic film is sometimes referred to as a polarizer.

[0466] [λ / 4 board]

[0467] "λ / 4 plate" refers to a plate with λ / 4 function, specifically, a plate that can convert linearly polarized light of a certain wavelength into circularly polarized light (or convert circularly polarized light into linearly polarized light).

[0468] For example, as a single-layer structure of the λ / 4 plate, examples include extended polymer films or phase retardation films with λ / 4 function light absorption anisotropy films disposed on a support. As a multi-layer structure of the λ / 4 plate, examples include broadband λ / 4 plates formed by stacking λ / 4 plates and λ / 2 plates.

[0469] The λ / 4 plate and the polarizer of the present invention can be disposed in contact, or other layers can be disposed between the λ / 4 plate and the light-absorbing anisotropic film of the present invention. Examples of such layers include adhesive layers or bonding layers and barrier layers for ensuring adhesion.

[0470] [Blocking layer]

[0471] When the laminate of the present invention includes a barrier layer, the barrier layer is disposed between the polarizer and the λ / 4 plate of the present invention. Alternatively, when the polarizer and the λ / 4 plate of the present invention have other layers besides the barrier layer (e.g., an adhesive layer or bonding layer), the barrier layer can be disposed, for example, between the light-absorbing anisotropic film of the present invention and other layers.

[0472] The barrier layer, also known as the gas barrier layer (oxygen barrier layer), has the function of protecting the light absorption anisotropic film of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers.

[0473] Regarding the barrier layer, for example, reference can be made to paragraphs

[0014] to

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

[0042] to

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

[0045] to

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

[0010] to

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

[0021] to

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

[0474] 〔use〕

[0475] The laminate of the present invention can be used, for example, as a polarizing element (polarizer), such as as a linear polarizer or a circular polarizer.

[0476] In the absence of an optically anisotropic layer such as the λ / 4 plate described above, the laminate of the present invention can be used as a linear polarizer.

[0477] On the other hand, when the laminate of the present invention has the above-mentioned λ / 4 plate, the laminate can be used as a circular polarizer.

[0478] [Image display device]

[0479] The image display device of the present invention has the light absorption anisotropic film of the present invention described above or the laminate of the present invention described above.

[0480] The display element used in the image display device of the present invention is not particularly limited, and examples include liquid crystal cells, organic electroluminescent (hereinafter referred to as "EL") display panels and plasma display panels.

[0481] Among these, liquid crystal cells or organic EL display panels are preferred, and liquid crystal cells are more preferred. That is, as the image display device of the present invention, a liquid crystal display device that uses a liquid crystal cell as a display element, an organic EL display device that uses an organic EL display panel as a display element, and a liquid crystal display device are more preferred.

[0482] [Liquid Crystal Display Device]

[0483] As an example of the image display device of the present invention, a liquid crystal display device is preferably provided that has the light absorption anisotropic film and liquid crystal cell of the present invention as described above. More preferably, a liquid crystal display device is provided that has the laminate (however, excluding the λ / 4 plate) and liquid crystal cell of the present invention as described above.

[0484] Furthermore, in this invention, among the polarizing elements disposed on both sides of the liquid crystal cell, it is preferable to use the laminate of this invention as the front polarizing element, and more preferably to use the laminate of this invention as both the front and rear polarizing elements.

[0485] The liquid crystal unit that constitutes a liquid crystal display device will be described in detail below.

[0486] <Liquid Crystal Unit>

[0487] The liquid crystal cells used in the liquid crystal display device 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.

[0488] In TN mode liquid crystal cells, the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and then twisted to an orientation of 60–120°. TN mode liquid crystal cells are most commonly used in color TFT (Thin Film Transistor) liquid crystal display devices, and are documented in several publications.

[0489] In a VA-mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In a VA-mode liquid crystal cell, in addition to the narrow definition of a VA-mode liquid crystal cell which has rod-shaped liquid crystal molecules substantially vertically oriented when no voltage is applied and substantially horizontally oriented when a voltage is applied (as described in Japanese Patent Application Publication No. 2-176625), there are also (2) a liquid crystal cell in which the VA mode is multi-domainized (MVA mode) in order to expand the viewing angle (as described in SID97, Digest of Tech. Papers 28 (1997) 845), (3) a liquid crystal cell in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted into multi-domain orientation when a voltage is applied (n-ASM mode) (as described in the proceedings of the Japan Liquid Crystal Conference 58-59 (1998)), and (4) a SURVIVAL mode liquid crystal cell (published in LCD International 98). Furthermore, it can be any of the following: PVA (Patterned Vertical Alignment), Optical Alignment, and PSA (Polymer-Sustained Alignment). Detailed information about these modes can be found in Japanese Patent Application Publication Nos. 2006-215326 and 2008-538819.

[0490] In IPS-mode liquid crystal cells, rod-shaped liquid crystal molecules are substantially parallel to the substrate. By applying an electric field parallel to the substrate surface, the liquid crystal molecules exhibit planar response. Regarding the IPS mode, black is displayed without an applied electric field, and the absorption axes of the upper and lower polarizers are orthogonal to each other. Methods for reducing light leakage and improving viewing angle when displaying black in an oblique direction using optical compensation sheets are disclosed in Japanese Patent Application Publications Nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0491] [Organic EL display device]

[0492] As an example of the image display device of the present invention, an organic EL display device may preferably be provided in a manner in which the light absorption anisotropic film, λ / 4 plate and organic EL display panel of the present invention are sequentially arranged from the visual recognition side.

[0493] More preferably, the laminate of the present invention, including the λ / 4 plate, and the organic EL display panel are arranged sequentially from the visual recognition side. In this case, the laminate is arranged sequentially from the visual recognition side as needed, including a substrate, an alignment film (a layer containing polyvinyl alcohol resin), the light-absorbing anisotropic film of the present invention, a blocking layer, and the λ / 4 plate.

[0494] Furthermore, the organic EL display panel is a display panel made of organic EL elements formed by sandwiching an organic light-emitting layer (organic electroluminescent layer) between electrodes (between the cathode and the anode). There are no particular restrictions on the structure of the organic EL display panel, and a known structure can be used.

[0495] Example

[0496] The present invention will now be described in further detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0497] [Example 1]

[0498] The laminate A of Example 1 was manufactured as follows.

[0499] [Preparation of cellulose acylated membrane 1]

[0500] Cellulose acylated membrane 1 was prepared as follows.

[0501] <Preparation of Core Cellulose Acid Compound Concentrate>

[0502] The following composition was added to a mixing tank and stirred to dissolve the components, thus preparing a cellulose acetate solution for use as a core layer cellulose acylate concentrate.

[0503]

[0504]

[0505] Compound F

[0506] [Chemical Formula 30]

[0507]

[0508] <Preparation of concentrated outer cellulose acylate>

[0509] Ten parts by mass of the following matting agent solution were added to 90 parts by mass of the above-mentioned core layer cellulose acylate concentrate to prepare a cellulose acetate solution for use as an outer layer cellulose acylate concentrate.

[0510]

[0511] <Preparation of Cellulose Acid Membrane 1>

[0512] After filtering the core cellulose acylate concentrate and the outer cellulose acylate concentrate using filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm, the three layers of the core cellulose acylate concentrate and the outer cellulose acylate concentrate on both sides are simultaneously cast from the casting port onto a roller at 20°C (ring tape casting machine).

[0513] Next, the film was peeled off with a solvent content of approximately 20% by mass, and the two ends of the film in the width direction were fixed with a tenter frame clamp. The film was then dried while being stretched laterally at an elongation ratio of 1.1.

[0514] The film was then further dried by conveying it between rollers in a heat treatment apparatus, resulting in an optical film with a thickness of 40 μm, which was designated as cellulose acylated film 1. The in-plane retardation of the obtained cellulose acylated film 1 was 0 nm.

[0515] (Creation of Layer A)

[0516] A laminate A is fabricated as follows, comprising the cellulose acylated film 1, the light-oriented layer PA1, the light-absorbing anisotropic layer P1, and the oxygen barrier layer B1 arranged sequentially adjacent to each other.

[0517] Fabrication of TAC film with light alignment layer

[0518] The cellulose acylated membrane 1 described later is continuously coated onto the oriented layer forming coating solution PA1 using a winding bar. The support with the coating is dried with warm air at 140°C for 120 seconds, followed by polarized ultraviolet irradiation (10 mJ / cm²). 2 A photo-alignment layer PA1 was formed using an ultra-high pressure mercury lamp, thereby obtaining a TAC film with a photo-alignment layer.

[0519]

[0520] Polymer A1

[0521] [Chemical Formula 31]

[0522]

[0523] [Chemical Formula 32]

[0524]

[0525] [Chemical Formula 33]

[0526]

[0527] <Formation of the light-absorbing anisotropic layer P1>

[0528] The following liquid crystal composition P1 is continuously coated onto the photoalignment layer PA1 of the obtained TAC film with photoalignment layer by means of a wire rod, thus forming the coating layer P1.

[0529] Next, the coating layer P1 was heated at 140°C for 30 seconds and then cooled to room temperature (23°C).

[0530] Next, heat at 80°C for 60 seconds, and then cool again to room temperature.

[0531] Then, an LED (Light Emitting Diode) lamp (center wavelength 365nm) was used to illuminate the material for 2 seconds under an illumination of 200mW / cm², thereby forming a light-absorbing anisotropic layer P1 (light-absorbing anisotropic film) on the light-alignment layer PA1. The thickness of the light-absorbing anisotropic layer P1 is 2.0μm.

[0532]

[0533]

[0534] B1

[0535] [Chemical Formula 34]

[0536]

[0537] L1

[0538] [Chemical Formula 35]

[0539]

[0540] LM1

[0541] [Chemical Formula 36]

[0542]

[0543] Y1

[0544] [Chemical Formula 37]

[0545]

[0546] M1

[0547] [Chemical Formula 38]

[0548]

[0549] C1

[0550] [Chemical Formula 39]

[0551]

[0552] Surfactant F1

[0553] [Chemical Formula 40]

[0554]

[0555] <Formation of Oxygen Barrier Layer B1>

[0556] The coating solution with the following composition was continuously coated onto the formed light-absorbing anisotropic layer P1 using a wire rod. Then, it was dried in warm air at 100°C for 2 minutes, thereby forming a 1.1 μm thick polyvinyl alcohol (PVA) oriented layer (oxygen barrier layer B1) on the light-absorbing anisotropic layer P1.

[0557]

[0558] Modified polyvinyl alcohol

[0559] [Chemical Formula 41]

[0560]

[0561] Thus, a laminate A of Example 1 was obtained, which sequentially comprises a cellulose acylated membrane 1, a light-oriented layer PA1, a light-absorbing anisotropic layer P1, and an oxygen-barrier layer B1.

[0562] [Examples 2-13, Comparative Examples 1-6]

[0563] The liquid crystal composition was changed to the liquid crystal composition described in Table 1 below. Otherwise, each of the laminates of Examples 2 to 9 and Comparative Examples 1 to 5 was produced by the same method as laminate A of Example 1.

[0564] The liquid crystal composition was changed to the liquid crystal composition described in Table 2 below. Otherwise, the laminates of Examples 10 to 13 and Comparative Example 6 were prepared by the same method as laminate A of Example 1.

[0565] The following is a summary of the components contained in the liquid crystal compositions used in the fabrication of the laminates of Examples 2-13 and Comparative Examples 1-6.

[0566] Polymerizable boric acid compounds (structures described below)

[0567] [Chemical Formula 42]

[0568]

[0569] Compounds other than polymerizable borate compounds (i.e., compounds that do not have polymerizable groups but have borate or borate groups, or compounds that have polymerizable groups but do not have borate or borate groups)

[0570] [Chemical Formula 43]

[0571]

[0572] Liquid crystal compounds (structures described below)

[0573] [Chemical Formula 44]

[0574]

[0575]

[0576] Dichroic substances (structures described below)

[0577] [Chemical Formula 45]

[0578]

[0579] Surfactants (structures described below)

[0580] [Chemical Formula 46]

[0581]

[0582] Polymerization initiator I1: IRGACUREOXE-02, manufactured by BASF

[0583] Tetrahydrofuran (solvent)

[0584] Cyclopentanone (solvent)

[0585] (Synthesis of polymeric boric acid compound B1)

[0586] The polymeric boric acid compound B1 described above was synthesized as follows. Additionally, in the following formula, Et represents the ethyl group.

[0587] [Chemical Formula 47]

[0588]

[0589] 30.0 g of m-hydroxymethylphenylboronic acid (refer to formula (B1A) above), 0.308 g of 2,2,6,6-tetramethylpiperidine 1-oxo radical (TEMPO, manufactured by Wako Pure Chemical, Ltd.), 65 mL of DMAc (N,N-dimethylacetoamide, manufactured by Wako Pure Chemical, Ltd.), and 100 mL of methyl isobutyl ketone were added to a three-necked flask. 50.13 g of 3-chloropropionyl chloride was then added dropwise to the solution at an internal temperature not exceeding 30°C. The mixture was then stirred at an internal temperature of 30–40°C for 4 hours. The reaction solution was then washed sequentially with 100 g of 5% saline solution at an internal temperature of 30–35°C, followed by 120 g of 5% saline solution.

[0590] After adding 0.154 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical (TEMPO, manufactured by Wako PureChemical, Ltd.) to the cleaned organic layer, 40.00 g of triethylamine (manufactured by Wako PureChemical, Ltd.) was added dropwise at an internal temperature not exceeding 50°C, and then stirred at an internal temperature of 60°C for 1 hour.

[0591] Subsequently, the reaction solution was washed twice at an internal temperature of 30-35℃ with 120g of 10% saline solution, followed by a mixture of 5mL concentrated hydrochloric acid and 85mL water, 120g of 5% sodium acetate aqueous solution, and 120g of water.

[0592] 0.52 g of p-methoxyphenol, 90 mL of water, and 75 mL of heptane were added to the obtained organic layer at an internal temperature of 30–35 °C. After cooling the solution to 0–5 °C for 1 hour, 150 mL of heptane was added dropwise while maintaining the internal temperature at 0–5 °C, resulting in crystal precipitation. The mixture was stirred for 1 hour while maintaining the internal temperature at 0–5 °C, and the crystals were filtered off and washed sequentially with 150 mL of cooled heptane and 150 mL of water containing 0.23 g of p-methoxyphenol.

[0593] The obtained crystals were air-dried at room temperature (23°C) to obtain a white solid polymeric boric acid compound B1 (29.6 g, yield: 72%).

[0594] (Synthesis of polymeric borate compound BX1)

[0595] The polymeric boric acid compound BX1 was synthesized as follows. In the following formula, Et represents ethyl.

[0596] [Chemical Formula 48]

[0597]

[0598] 30.0 g of m-hydroxymethylphenylboronic acid (refer to formula (B1A) above), 0.308 g of 2,2,6,6-tetramethylpiperidine 1-oxo radical (TEMPO, manufactured by Wako Pure Chemical, Ltd.), 65 mL of DMAc (N,N-dimethylacetoamide, manufactured by Wako Pure Chemical, Ltd.), and 100 mL of methyl isobutyl ketone were added to a three-necked flask. 50.13 g of 3-chloropropionyl chloride was then added dropwise to the solution at an internal temperature not exceeding 30°C. The mixture was then stirred at an internal temperature of 30–40°C for 4 hours. The reaction solution was then washed sequentially with 100 g of 5% saline solution at an internal temperature of 30–35°C, followed by 120 g of 5% saline solution.

[0599] After adding 0.154 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical (TEMPO, manufactured by Wako PureChemical, Ltd.) to the cleaned organic layer, 40.00 g of triethylamine (manufactured by Wako PureChemical, Ltd.) was added dropwise at an internal temperature not exceeding 50°C, and then stirred at an internal temperature of 60°C for 1 hour.

[0600] Subsequently, the reaction solution was washed twice at an internal temperature of 30-35℃ with 120g of 10% saline solution, followed by a mixture of 5mL concentrated hydrochloric acid and 85mL water, 120g of 5% sodium acetate aqueous solution, and 120g of water.

[0601] 0.52 g of p-methoxyphenol, 90 mL of water, and 75 mL of heptane were added to the obtained organic layer at an internal temperature of 30–35 °C. After cooling the solution to 0–5 °C for 1 hour, 150 mL of heptane was added dropwise while maintaining the internal temperature at 0–5 °C, resulting in crystal precipitation. The mixture was stirred for 1 hour while maintaining the internal temperature at 0–5 °C, and the crystals were filtered off and washed sequentially with 150 mL of cooled heptane and 150 mL of water containing 0.23 g of p-methoxyphenol.

[0602] The obtained crystals were air-dried at 55°C for 48 hours and subjected to a dehydration condensation reaction to obtain a white solid polymeric boric acid compound BX1 (25.5 g, yield: 68%).

[0603] [Evaluation Test]

[0604] The following evaluation was performed using the laminates of the embodiments and comparative examples obtained as described above.

[0605] Furthermore, the light-absorbing anisotropic layer contained in the laminate of each embodiment was evaluated according to the above-described evaluation method for horizontal orientation. As a result, the polymer liquid crystal compound and the dichroic material in the light-absorbing anisotropic layer contained in the laminate of each embodiment are both horizontally oriented.

[0606] [Orientation Degree]

[0607] With a linear polarizer inserted at the light source side of an optical microscope (Nikon Corporation, product name "ECLIPSE E600POL"), the laminates of the examples and comparative examples were assembled 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 region of 380 nm to 780 nm was measured at 1 nm intervals. The orientation degree in the range of 400 nm to 700 nm was calculated using the following formula. Based on the obtained orientation degree, the orientation degree was evaluated according to the following evaluation criteria.

[0608] Orientation degree: S=((Az0 / Ay0)-1) / ((Az0 / Ay0)+2)

[0609] In the above formula, "Az0" represents the absorbance of the anisotropic layer relative to the absorption axis direction of polarized light, and "Ay0" represents the absorbance of the anisotropic layer relative to the transmission axis direction of polarized light.

[0610] A: Orientation degree is 0.93 or higher.

[0611] B: Orientation degree is 0.90 or higher and less than 0.93.

[0612] C: Orientation degree less than 0.90

[0613] [Seamless]

[0614] Cellophane tape was applied to the oxygen barrier layer side of the laminates obtained in the examples and comparative examples. The cellophane tape was then peeled off in a vertical direction, and the peeling condition of the laminates was visually observed. The following evaluation was conducted. For the test specimens that showed peeling, cross-sectional observation was performed using an optical microscope. The results confirmed that peeling occurred at the interface between the light absorption anisotropic layer and the oxygen barrier layer.

[0615] A: The oxygen barrier layer was peeled off in the area less than half of the section where cellophane tape was applied.

[0616] B: The oxygen barrier layer was peeled off in an area exceeding half of the area covered by cellophane tape, but a portion of the oxygen barrier layer was not peeled off.

[0617] C: The oxygen barrier layer was completely peeled off from the entire surface of the area where cellophane tape was applied.

[0618] [Liquid stability]

[0619] Liquid crystal compositions used in Examples 10-13 and Comparative Example 6 were evaluated for liquid stability. 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.

[0620] A: No precipitate was observed visually.

[0621] B: Very little precipitate was observed under visual inspection.

[0622] C: Precipitates were observed visually as a whole.

[0623] The results of the above evaluation tests are shown in Tables 1 and 2 below.

[0624] In Table 1, the "mass percentage (mass%) relative to total solids" in the column for polymeric boric acid compounds refers to the content (mass%) of polymeric boric acid compounds relative to the mass of the total solids in the liquid crystal composition. Furthermore, the "mass percentage (mass%) relative to total solids" in the column for compounds other than polymeric boric acid compounds refers to the content (mass%) of compounds other than polymeric boric acid compounds relative to the mass of the total solids in the liquid crystal composition.

[0625] In Table 2, the "mass percentage (mass%)" in the columns for polymeric borate compound 1 and polymeric borate compound 2 refers to the content (mass%) of polymeric borate compound 1 or polymeric borate compound 2 relative to the total solids content of the liquid crystal composition. Furthermore, the "mass percentage (mass%)" in the columns for compounds other than polymeric borate compounds refers to the content (mass%) of compounds other than polymeric borate compounds relative to the total solids content of the liquid crystal composition.

[0626]

[0627]

[0628] As shown in Tables 1 and 2, it was found that liquid crystal compositions containing liquid crystal compounds, dichroic substances, and boric acid compounds with polymerizable groups were formed, and the light-absorbing anisotropic films with horizontally oriented liquid crystal compounds exhibited excellent adhesion to other layers and a high degree of orientation (Examples 1-13).

[0629] A comparison of Examples 1-6 with Example 7 shows that if the compound represented by the above formula (B-2) (Examples 1-6) is used as the polymeric boric acid compound, an anisotropic film with better orientation can be obtained.

[0630] The comparison between Example 1 and Example 8 shows that as long as a polymeric liquid crystal compound (Example 1) is used, anisotropic light absorption films with better orientation and adhesion can be obtained.

[0631] The comparison between Examples 10 and 11 and Examples 12 and 13 shows that, in the case of polymeric boric acid compounds and compounds represented by the above formula (B-1) and compounds represented by the above formula (BX-1) (Examples 10 and 11), the liquid crystal compositions exhibit excellent liquid stability.

[0632] In contrast, as shown in Tables 1 and 2, when anisotropic light-absorbing films are fabricated without using polymeric boric acid compounds, at least one of the orientation and adhesion is worse (Comparative Examples 1-6).

Claims

1. A light-absorbing anisotropic film formed from a liquid crystal composition, said liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a boric acid compound having polymerizable groups. The liquid crystal compound is horizontally oriented. The boric acid compound having polymerizable groups comprises at least one of the compounds represented by formula (B-1) and the compounds represented by formula (BX-1). In equation (B-1), R B11 Indicates a hydrogen atom or a methyl group. L B1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. B14 A divalent group formed by substituting at least one group from the group consisting of R. B14 Indicates a hydrogen atom or an alkyl group. A B1 represents an arylene group with or without substituents or a heteroarylene group with or without substituents, R B12 and R B13 Each of the following independently represents a hydrogen atom, an alkyl group with or without substituents, an aryl group with or without substituents, or a heteroaryl group with or without substituents, R B12 and R B13 This indicates that the bonds between the elements form a ring or that they are not bonded. In formula (BX-1), R BX11 Represents a hydrogen atom or a methyl group, multiple R BX11 Whether they are the same or different, L BX1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. BX14 A divalent group formed by substituting at least one group from the group consisting of multiple L groups. BX1 Whether they are the same or different, R BX14 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX14 In the case of multiple R BX14 Whether they are the same or different, A BX1 This indicates an arylene group with or without substituents, or a heteroarylene group with or without substituents, and multiple A's. BX1 They are the same or different.

2. The light-absorbing anisotropic film according to claim 1, wherein, The boric acid compound having polymerizable groups comprises at least one of the compounds represented by formula (B-2) and the compounds represented by formula (BX-2). In equation (B-2), R B21 Indicates a hydrogen atom or a methyl group. L B2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. B25 A divalent group formed by substituting at least one group from the group consisting of R. B25 Indicates a hydrogen atom or an alkyl group. R B22 and R B23 Each of the following independently represents a hydrogen atom, an alkyl group with or without substituents, an aryl group with or without substituents, or a heteroaryl group with or without substituents, R B22 and R B23 This indicates that the bonds between the elements form a ring or that they are not bonded. R B24 Indicates a substituent with a 1 valence. nb represents an integer from 0 to 4. When nb is greater than 2, multiple R... B24 Whether they are the same or different, In formula (BX-2), R BX21 Represents a hydrogen atom or a methyl group, multiple R BX21 Whether they are the same or different, L BX2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. BX25 A divalent group formed by substituting at least one group from the group consisting of multiple L groups. BX2 Whether they are the same or different, R BX25 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX25 In the case of multiple R BX25 Whether they are the same or different, R BX24 Describing a substituent with a valence of 1, in the presence of multiple R... BX24 In the case of multiple R BX24 Whether they are the same or different, nc represents an integer from 0 to 4, and multiple nc values ​​may be the same or different.

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

4. The light-absorbing anisotropic film according to claim 1 or 2, wherein, The boric acid compound having polymerizable groups includes the compound represented by formula (B-1) and the compound represented by formula (BX-1). 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 light-absorbing anisotropic film according to claim 2, wherein, The boric acid compound having polymerizable groups includes the compound represented by formula (B-2) and the compound represented by formula (BX-2). 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 claim 1 or 2, wherein, The liquid crystal compound includes a high molecular weight liquid crystal compound.

7. A laminated body having: The light-absorbing anisotropic film according to any one of claims 1 to 6; and A layer containing polyvinyl alcohol resin configured in contact with the light-absorbing anisotropic film.

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

10. A liquid crystal composition comprising a liquid crystal compound, a dichroic substance, and a boric acid compound having polymerizable groups. The boric acid compound having polymerizable groups comprises at least one of the compounds represented by formula (B-2) and the compound represented by formula (BX-1). In equation (B-2), R B21 Indicates a hydrogen atom or a methyl group. L B2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. B25 A divalent group formed by substituting at least one group from the group consisting of R. B25 Indicates a hydrogen atom or an alkyl group. R B22 and R B23 Each of the following independently represents a hydrogen atom, an alkyl group with or without substituents, an aryl group with or without substituents, or a heteroaryl group with or without substituents, R B22 and R B23 This indicates that the bonds between the elements form a ring or that they are not bonded. R B24 Indicates a substituent with a 1 valence. nb represents an integer from 0 to 4. When nb is greater than 2, multiple R... B24 Whether they are the same or different, In formula (BX-1), R BX11 Represents a hydrogen atom or a methyl group, multiple R BX11 Whether they are the same or different, L BX1 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. BX14 A divalent group formed by substituting at least one group from the group consisting of multiple L groups. BX1 Whether they are the same or different, R BX14 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX14 In the case of multiple R BX14 Whether they are the same or different, A BX1 This indicates an arylene group with or without substituents, or a heteroarylene group with or without substituents, and multiple A's. BX1 They are the same or different.

11. The liquid crystal composition according to claim 10, wherein, The compound represented by formula (BX-1) is the same as the compound represented by formula (BX-2). In formula (BX-2), R BX21 Represents a hydrogen atom or a methyl group, multiple R BX21 Whether they are the same or different, L BX2 The -CH2- group representing a single bond, a divalent aliphatic hydrocarbon group, or one or more -CH2- groups constituting a divalent aliphatic hydrocarbon group are selected from -O-, -C(=O)-, and -N(R)-. BX25 A divalent group formed by substituting at least one group from the group consisting of multiple L groups. BX2 Whether they are the same or different, R BX25 Represents a hydrogen atom or an alkyl group, in the presence of multiple R atoms. BX25 In the case of multiple R BX25 Whether they are the same or different, R BX24 Describing a substituent with a valence of 1, in the presence of multiple R... BX24 In the case of multiple R BX24 Whether they are the same or different, nc represents an integer from 0 to 4, and multiple nc values ​​may be the same or different.

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

13. The liquid crystal composition according to claim 10 or 11, wherein, The boric acid compound having polymerizable groups includes the compound represented by formula (B-2) and the compound represented by formula (BX-1). 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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