Dichroic dye composition, liquid crystal element, retardation plate and polarizer

Abstract

To provide a novel dichroic dye composition useful for various optical elements, and an optical element using the same.SOLUTION: A dichroic dye composition comprises a squarylium pigment containing a heteroatom and a liquid crystal compound transmitting visible light.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dichroic dye composition, a liquid crystal device, a retardation plate, a polarizer, and the like. [Background technology]

[0002] In liquid crystal display devices, polarizers are used to control the optical rotation and birefringence in display, and in recent years, organic dyes have been considered as dichroic materials to be used in polarizers. For example, polarizers using guest-host type liquid crystal compositions containing a liquid crystal material as a host and a dichroic dye as a guest have been proposed (Patent Document 1, Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5923941 [Patent Document 2] Patent No. 6343866 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above Patent Documents 1 and 2 do not disclose the use of squarylium dyes as dichroic dyes. An object of the present invention is to provide a novel dichroic dye composition useful for various optical elements such as polarizers, and a liquid crystal element, a retardation plate, a polarizer, etc., which utilizes the same. [Means for solving the problem]

[0005] The present invention relates to the following dichroic dye composition. [1] A dichroic dye composition comprising a squarylium dye containing a heteroatom and a liquid crystal compound that transmits visible light. Effect of the Invention

[0006] According to the present invention, it is possible to provide a novel dichroic dye composition useful for various optical elements such as liquid crystal elements, retardation plates and polarizers, and liquid crystal elements, retardation plates and polarizers using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Hereinafter, an embodiment of the present invention will be described. In this specification, the compound represented by formula (A1) is referred to as compound (A1). The same applies to compounds represented by other formulas. The NIR dye made of compound (A1) is also referred to as NIR dye (A1), and the same applies to other dyes. In addition, for example, the group represented by formula (1a) is also referred to as group (1a), and the same applies to groups represented by other formulas. In this specification, the term "to" indicating a numerical range includes the upper and lower limits.

[0008] In this specification, unless otherwise specified, the alkyl group may be linear, branched, or cyclic, or may be a combination of these structures. Unless otherwise specified, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., with a fluorine atom being preferred. In this specification, unless otherwise specified, an aryl group refers to a group that bonds via a carbon atom constituting an aromatic ring of an aromatic compound, such as a benzene ring, a naphthalene ring, a biphenyl ring, etc., and a heteroaryl group refers to a group that bonds via a carbon atom or a hetero atom constituting an aromatic ring of an aromatic compound having a hetero atom, such as a furan ring, a thiophene ring, a pyrrole ring, etc.

[0009] In the present specification, a squarylium compound refers to a compound having a squarylium skeleton represented by the following formula (S1) which can have a resonance structure represented by the following formula (S2) in the structural formula. In the present specification, the squarylium skeleton is represented by either formula (S1) or formula (S2).

[0010] [ka]

[0011] <Dichroic dye composition> The dichroic dye composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains a squarylium dye containing a heteroatom and a liquid crystal compound that transmits visible light. In the present invention, the squarylium dye functions as a dichroic dye. The dichroic dye means a dye having different absorbance in the long axis direction and the short axis direction of the molecule. When the composition of the present invention contains the dichroic dye, the obtained optical element can function as a polarizer. The squarylium dye is also a near-infrared absorbing dye that transmits visible light and has a maximum absorption wavelength in the wavelength region of 700 nm or more. When the dichroic dye is a near-infrared absorbing dye, an optical element capable of absorbing polarized light in the near-infrared and infrared regions can be obtained.

[0012] <Squarylium dye> The squarylium dye contained in the composition of the present invention contains a heteroatom. This increases the absorption coefficient and the visible light transmittance. The heteroatom is distinguished from the oxygen atom in the squarylium skeleton. That is, the squarylium dye of the present invention contains a heteroatom in the structure other than the squarylium skeleton. Examples of the heteroatom include a nitrogen atom, a sulfur atom, and an oxygen atom.

[0013] The squarylium dye is preferably a compound represented by the following formula (X).

[0014] [ka]

[0015] The symbols in formula (X) are as follows. Ar is a monocyclic, condensed or linked ring having 5 to 14 carbon atoms and having aromaticity. R 1 and R 2 , R 1 and R 2At least one of the carbon atoms constituting Ar and the nitrogen atom may be bonded to each other to form a heterocycle having 3 to 10 members.

[0016] R 1 and R 2 does not form a heterocycle, R 1 and R 2 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a hetero atom or a ring structure. The monovalent hydrocarbon group may be branched, straight-chain, or cyclic, but is preferably straight-chain from the viewpoint that the squarylium dye is likely to have a straight-chain structure, that is, to exhibit dichroism. The monovalent hydrocarbon group more preferably has 1 to 8 carbon atoms.

[0017] R 1 and R 2 When forms a heterocycle, R 1 and R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a hetero atom or a ring structure.

[0018] R 1 and R 2 Examples of the substituent in include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 19 carbon atoms. In addition, R 1 and R 2 When R has a substituent, the number of carbon atoms of the substituent is 1 and R 2 is included in the carbon number.

[0019] R 1 and R 2Further examples of the substituent in include a cyclic alkyl group or an aryl group. The aryl group is preferably a phenyl group which may have 1 to 5 substituents, or a naphthyl group which may have 1 to 7 substituents. Examples of the substituent which may substitute a hydrogen atom in the phenyl group or naphthyl group include an alkyl group having 1 to 12 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 12 carbon atoms). The phenyl group and naphthyl group are preferably unsubstituted or substituted with 1 to 3 hydrogen atoms, and examples of the substituent include a methyl group, a t-butyl group, a dimethylamino group, a methoxy group, and the like.

[0020] R 1 and R 2 The heteroatom in is preferably an oxygen atom or a nitrogen atom.

[0021] R 1 and R 2 However, when the main chain or side chain contains an alicyclic ring or an aromatic ring, the number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0022] R 1 and R 2 From the viewpoint of improving the reliability of the optical element, the substituent in is preferably a polymerizable group.

[0023] R 1 and R 2 When they are linked to each other to form a heterocycle together with the nitrogen atom, the number of members of such a heterocycle is preferably 4 to 6 from the viewpoint that the squarylium dye is likely to have a linear shape, that is, is likely to exhibit dichroism. In such a heterocycle, one of the hydrogen atoms bonded to the carbon atom farthest from the nitrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 3 to 8 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms. In addition, in such a heterocycle, the carbon atom farthest from the nitrogen atom may be replaced with a nitrogen atom, and the hydrogen atom bonded to the nitrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 3 to 8 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms. The alkyl group may be branched, linear, or cyclic, but is preferably linear from the viewpoint that the squarylium dye is likely to exhibit dichroism. In addition, some or all of the hydrogen atoms in the heterocycle may be substituted with halogen atoms, and in this case, it is preferred that some or all of the hydrogen atoms bonded to the carbon atom not adjacent to the nitrogen atom are substituted with halogen atoms.

[0024] R 1 and R 2 When at least one of the carbon atoms constituting Ar is linked to each other to form a heterocycle together with the nitrogen atom, the number of members of the heterocycle is preferably 5 to 7. In the heterocycle, one of the hydrogen atoms bonded to the carbon atom adjacent to the nitrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8, more preferably 3 to 8 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms, and some or all of the remaining hydrogen atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms. The alkyl group may be branched, straight-chained, or cyclic, but is preferably straight-chained from the viewpoint that the squarylium dye is likely to exhibit dichroism. In addition, some or all of the hydrogen atoms in the heterocycle may be substituted with halogen atoms, and in that case, it is preferable that some or all of the hydrogen atoms bonded to the carbon atom not adjacent to the nitrogen atom are substituted with halogen atoms.

[0025] In addition, the two R 1 Although R may be different on the left and right sides of the squarylium skeleton, it is preferable that R is the same on the left and right sides from the viewpoint of ease of production. 2 The same applies to Ar. The same applies to the subsequent symbols. That is, the two symbols in the chemical formula may be different on the left and right of the squarylium skeleton, but from the viewpoint of ease of production, it is preferable that the two symbols are the same on the left and right.

[0026] Ar may have one or more substituents. Here, from the viewpoint that the squarylium dye is more likely to exhibit dichroism when the ratio (aspect ratio) of the molecular length in the minor axis direction to the molecular length in the major axis direction is larger, the substituents are halogen atoms, hydroxyl groups, or monovalent organic groups R having 1 to 9 carbon atoms which may have a substituent. Ar It is preferable that R Ar The number of carbon atoms and R Ar The number of carbon atoms of the substituents of is not included in the number of carbon atoms of Ar. Examples of the halogen atom include a chlorine atom, a fluorine atom, an iodine atom, and a bromine atom. Monovalent organic group R Ar Examples of the group include an alkyl group, an alkoxy group, an acyloxy group, an araryl group, an amino group, an alkenyl group, an alkynyl group, an imino group, a cyano group, a carbonyl group, an aryl group, and a heteroaryl group. R Ar may have a substituent. The number of carbon atoms of the substituent is Ar is included in the carbon number.

[0027] The squarylium dye is preferably a compound represented by any one of the following formulas (I) to (VI): The squarylium dye may contain one or more compounds.

[0028] <Squarylium dyes (I)>

[0029] [ka]

[0030] Here, the symbols in the above formula are as follows:

[0031] R 11 and R 21each independently represents a hydrogen atom, an alkyl group or alkoxy group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond or a heteroatom between the carbon atoms, an acyloxy group having 1 to 19 carbon atoms, an aryl group having 6 to 11 carbon atoms, or an araryl group having 7 to 18 carbon atoms which may have a substituent and which may contain an oxygen atom between the carbon atoms. The alkyl group is preferably linear from the viewpoint that the squarylium dye is likely to exhibit dichroism.

[0032] R 31 and R 51 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an acyloxy group having 1 to 8 carbon atoms, an aryl group having 6 to 9 carbon atoms, an aryl group having 7 to 9 carbon atoms which may have a substituent and which may have an oxygen atom between the carbon atoms, -NR 31a R 31b (R 31a and R 31b are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -C(=O)-R 31c (R 31c represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, an oxygen atom, or a saturated or unsaturated ring structure), -NHR 31d , or -SO 2 -R 31d (R 31d represents a hydrocarbon group having 1 to 8 carbon atoms, each of which may have one or more hydrogen atoms substituted with a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, or a cyano group, and which may contain an unsaturated bond, an oxygen atom, or a saturated or unsaturated ring structure between the carbon atoms), or a group represented by the following formula (S) (R 31e , R 31f each independently represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 3 carbon atoms. k is 2 or 3.

[0033] [ka]

[0034] R 41 and R 61 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an acyloxy group having 1 to 8 carbon atoms, an aryl group having 6 to 9 carbon atoms, or an araryl group having 7 to 9 carbon atoms which may have a substituent and which may have an oxygen atom between the carbon atoms.

[0035] R 11 and R 21 , R 11 and R 41 , and R 21 and R 61 may be linked together with the nitrogen atom to form a 4- to 6-membered heterocycle A1, a 5- to 7-membered heterocycle B1, and a 5- to 7-membered heterocycle C1, respectively.

[0036] R when heterocycle A1 is formed 11 and R 21 are the divalent groups -Q 1 - represents an alkylene group having 3 to 5 carbon atoms or an alkyleneoxy group having 2 to 4 carbon atoms. 1 In the heterocycle, one of the hydrogen atoms bonded to the carbon atom farthest from the nitrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms. The alkyl group is preferably linear from the viewpoint that the squarylium dye is likely to exhibit dichroism. In addition, some or all of the hydrogen atoms in the heterocycle may be substituted with halogen atoms, and in this case, it is preferable that some or all of the hydrogen atoms bonded to the carbon atom not adjacent to the nitrogen atom are substituted with halogen atoms.

[0037] R when heterocycle B1 is formed 11 and R 41 and R when the heterocycle C1 is formed. 21 and R 61 are the divalent groups -X 1 -Y 1-and-X 2 -Y 2 - (The side that is bonded to nitrogen is X 1 and X 2 ) as X 1 and X 2 are groups represented by the following formula (1x) or (2x), and Y 1 and Y 2 Each of X is a group selected from the following formulas (1y) to (5y). 1 and X 2 are groups represented by the following formula (2x), Y 1 and Y 2 may each be a single bond, in which case there may be an oxygen atom between the carbon atoms.

[0038] [ka]

[0039] In formula (1x), each of the four Z's is independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or -Nx 38 x 39 (x 38 and x 39 Each of x independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 31 ~x 36 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms; 37 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. R 31a , R 31b , R 31c , x 31 ~x 37 , R when not forming a heterocycle 11 , R 21 , R 41 and R 61 may be bonded to any other of these to form a 5- or 6-membered ring. 31 and x 36 , x 31 and x37 may be directly bonded.

[0040] R 11 and R 21 Examples of the substituent in include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 19 carbon atoms.

[0041] R 11 and R 21 Further examples of the substituent in include a cyclic alkyl group or an aryl group. The aryl group is preferably a phenyl group which may have 1 to 5 substituents, or a naphthyl group which may have 1 to 7 substituents. Examples of the substituent which may substitute a hydrogen atom in the phenyl group or naphthyl group include an alkyl group having 1 to 12 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 12 carbon atoms). The phenyl group and naphthyl group are preferably unsubstituted or substituted with 1 to 3 hydrogen atoms, and examples of the substituent include a methyl group, a t-butyl group, a dimethylamino group, a methoxy group, and the like.

[0042] R 11 and R 21 However, when the main chain or side chain contains an alicyclic ring or an aromatic ring, the number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0043] R 11 and R 21 From the viewpoint of improving the reliability of the optical element, the substituent in is preferably a polymerizable group.

[0044] Examples of compound (I) include compounds represented by any of formulas (I-1) to (I-4).

[0045] [ka]

[0046] The symbols in formulae (I-1) to (I-4) have the same definitions as those in formula (I), and preferred embodiments are also the same unless otherwise specified.

[0047] In compound (I-1), X 1 As the group (2x), the group (2x) is preferable. 1 is preferably a single bond or a group (1y). That is, -Y 1 -X 1 -C(x 31 )(x 32 )-C(x 33 )(x 34 )-or-C(x 35 )(x 36 )-C(x 31 )(x 32 )-C(x 33 )(x 34 )- is preferred. In this case, x 31 , x 32 , x 35 , x 36 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 33 , x 34 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8, and more preferably 3 to 8. When one linear alkyl group is bonded to a carbon atom adjacent to a nitrogen atom, dichroism is easily exhibited, so that x 33 , x 34 It is particularly preferable that one of these groups is a hydrogen atom and the other is a linear alkyl group having 3 to 8 carbon atoms.

[0048] In addition, -Y 1 -X 1 Specific examples of - include divalent organic groups represented by the following formulas (11-1) to (11-4) and (12-1) to (12-3). -C(CH 3 ) 2 -CH(CH 3 )- …(11-1) -C(CH3 ) 2 -CH 2 - ... (11-2) -C(CH 3 ) 2 -CH(nC k H 2k+1 )- …(11-3)(k=2~6) -C(CH 3 ) 2 -C(CH 3 )(nC k H 2k+1 )- …(11-4)(k=3~6) -C(CH 3 ) 2 -CH 2 -CH 2 - ...(12-1) -C(CH 3 ) 2 -CH 2 -CH(CH 3 )- …(12-2) -C(CH 3 ) 2 -CH(CH 3 )-CH 2 - ... (12-3)

[0049] In addition, in compound (I-1), R 11 From the viewpoint of improving the dichroic ratio, each of the groups is more preferably a methyl group.

[0050] In compound (I-4), R 51 is preferably a hydrogen atom or a hydroxyl group.

[0051] <Squarylium dye (II)>

[0052] [ka]

[0053] Here, the symbols in the above formula are as follows: Each ring Z2 is independently a 5- or 6-membered ring having 0 to 3 heteroatoms in the ring, and the hydrogen atom in ring Z2 may be substituted. R 12 and R 22 each independently represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an unsaturated bond between carbon atoms, a heteroatom, or a saturated or unsaturated ring structure, and which may have a substituent. R 32 and R 42 each independently represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 8 carbon atoms which may contain a heteroatom between the carbon atoms and which may have a substituent. R 12 and R 22 , R 12 and R 42 , and R 22 and the carbon atoms or heteroatoms constituting ring Z2 may be bonded to each other and, together with the nitrogen atom, form a 4- to 6-membered heterocycle A2, a 5- to 7-membered heterocycle B2, and a 5- to 7-membered heterocycle C2, respectively, in which case the hydrogen atoms in heterocycle A2, heterocycle B2, and heterocycle C2 are optionally substituted.

[0054] R 12 and R 22 Examples of the substituent in include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 19 carbon atoms.

[0055] R 12 and R 22Further examples of the substituent in include a cyclic alkyl group or an aryl group. The aryl group is preferably a phenyl group which may have 1 to 5 substituents, or a naphthyl group which may have 1 to 7 substituents. Examples of the substituent which may substitute a hydrogen atom in the phenyl group or naphthyl group include an alkyl group having 1 to 12 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 12 carbon atoms). The phenyl group and naphthyl group are preferably unsubstituted or substituted with 1 to 3 hydrogen atoms, and examples of the substituent include a methyl group, a t-butyl group, a dimethylamino group, a methoxy group, and the like.

[0056] R 12 and R 22 However, when the main chain or side chain contains an alicyclic ring or an aromatic ring, the number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0057] R 12 and R 22 From the viewpoint of improving the reliability of the optical element, the substituent in is preferably a polymerizable group.

[0058] Examples of compound (II) include compounds represented by any one of formulas (II-1) to (II-3). From the viewpoint of durability, the compounds represented by formula (II-1) and formula (II-3) are particularly preferred.

[0059] [ka]

[0060] In formula (II-1) and formula (II-2), R 12 and R 22 R each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may have an unsaturated bond or a heteroatom between the carbon atoms. 32 , R 42 , R 52 , R 62each independently represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms. An example of the substituent in the alkyl group is a halogen atom.

[0061] In formula (II-3), R 12 R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may have an unsaturated bond or a hetero atom between the carbon atoms. 92a ~R 92d each independently represents a hydrogen atom, a halogen atom, or an alkyl group having one or more carbon atoms which may have a substituent and which may have an unsaturated bond or a hetero atom between carbon atoms, and -CR 92a R 92b -CR 92c R 92d -The total number of carbon atoms is 20 or less. 32 , R 72 and R 82 each independently represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms. An example of the substituent in the alkyl group is a halogen atom.

[0062] R in compound (II-1) and compound (II-2) 12 and R 22 From the viewpoint of the degree of orientation, R is preferably a linear alkyl group having 1 to 20 carbon atoms, which may have a substituent and may have an unsaturated bond or a heteroatom between the carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms. 12 and R 22 It is preferable that the carbon atoms constituting the heterocyclic ring are linked to each other to form a heterocyclic ring, and it is particularly preferable that the heterocyclic ring is a 4- to 6-membered ring.

[0063] R in compound (II-3) 12 From the viewpoint of the degree of orientation, a linear alkyl group having 1 to 8 carbon atoms is preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

[0064] R 32 and R42 are each independently preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom, from the viewpoint of the degree of orientation.

[0065] R 72 and R 82 are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, and more preferably a hydrogen atom, a halogen atom, or a methyl group.

[0066] R 92a is more preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom and which may have an unsaturated bond or a hetero atom between the carbon atoms. 92a is particularly preferably a linear alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom. R 92b ~R 92d are preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom. -CR 92a R 92b -CR 92c R 92d Examples of - include divalent organic groups represented by the following groups (13-1) to (13-9). -CH(CH 3 )-C(CH 3 ) 2 - ... (13-1) -C(CH 3 ) 2 -CH(CH 3 )- …(13-2) -C(CH 3 ) 2 -CH 2 - …(13-3) -C(CH 3 ) 2 -CH(C 2 H 5 )- …(13-4) -CH(CH 3 )-C(CH3 )(CH 2 -CH(CH 3 ) 2 )-…(13-5) -CH(CH 2 CH(CH 3 ) 2 )-C(CH 3 ) 2 -…(13-6) -CH(C n H 2n+1 )-C(CH 3 ) 2 - …(13-7)(n=1~12) -CH(C n H 2n+1 )-CH 2 - …(13-8)(n=1~12) -C(CH 3 )(C n H 2n+1 )-C(CH 3 ) 2 - …(13-9)(n=1~12)

[0067] More specifically, examples of compound (II-1) include the compounds shown in the following table. In the compounds shown in the following table, the symbols on the left and right of the squarylium skeleton have the same meaning.

[0068] [Table 1]

[0069] More specifically, examples of compound (II-3) include the compounds shown in the following table. In the compounds shown in the following table, the symbols on the left and right of the squarylium skeleton have the same meaning.

[0070] [Table 2]

[0071] Compounds (I) to (II) can be produced by known methods. Compound (I) can be produced by the methods described in U.S. Pat. No. 5,543,086, U.S. Patent Application Publication No. 2014 / 0061505, and WO 2014 / 088063. Compound (II) can be produced by the methods described in WO 2017 / 135359.

[0072] <Squarylium dye (III)>

[0073] [ka]

[0074] Here, the symbols in the above formula are as follows: R 13 and R 23 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a heteroatom, an alicyclic ring, or an aromatic ring.

[0075] R 13 is R 23 , R 33 , X 31 , X 32 , or X 33 may be linked to form a ring. R 23 is R 13 , R 33 , X 31 , X 32 , or X 33 may be linked to form a ring. The ring is preferably an alicyclic or aromatic ring having 3 to 6 members, and the ring may have a substituent.

[0076] R 13 and R 23Examples of the substituent in include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 19 carbon atoms.

[0077] R 13 and R 23 Further examples of the substituent in include a cyclic alkyl group or an aryl group. The aryl group is preferably a phenyl group which may have 1 to 5 substituents, or a naphthyl group which may have 1 to 7 substituents. Examples of the substituent which may substitute a hydrogen atom in the phenyl group or naphthyl group include an alkyl group having 1 to 12 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 12 carbon atoms). The phenyl group and naphthyl group are preferably unsubstituted or substituted with 1 to 3 hydrogen atoms, and examples of the substituent include a methyl group, a t-butyl group, a dimethylamino group, a methoxy group, and the like.

[0078] R 13 and R 23 However, when the main chain or side chain contains an alicyclic ring or an aromatic ring, the number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0079] R 13 and R 23 From the viewpoint of improving the reliability of the optical element, the substituent in is preferably a polymerizable group.

[0080] R 13 and R 23 The carbon number of R may be 1 to 20. 13 and R 23 In the case of a linear structure, the number of carbon atoms in R is preferably 2 to 20, more preferably 3 to 16, and further preferably 4 to 12. 13 and R 23 In the case of a branched chain, the number of carbon atoms is preferably 3 to 20, more preferably 4 to 16, and further preferably 8 to 10. R 13 and R 23 has a substituent, or contains an alicyclic or aromatic ring in the main chain or side chain, the number of carbon atoms in the above includes the number of carbon atoms in the substituent, alicyclic or aromatic ring.

[0081] R 13 and R 23 may be the same or different, but is preferably the same from the viewpoint of ease of production.

[0082] R 13 and R 23 From the viewpoint of the degree of orientation, it is preferable that the polymer has a linear shape.

[0083] R 13 and R 23 is more preferably a group selected from groups (1b) to (5b) and groups (1c) to (2c), for example. -CH(C n H 2n+1 ) 2 …(1b) -C(C n H 2n+1 ) 3 …(1c) -CH 2 -CH(C n H 2n+1 ) 2 …(2b) -CH 2 -C(C n H 2n+1 ) 3 …(2c) -(CH 2 ) 2 -CH(C n H 2n+1 ) 2 …(3b) -(CH 2 ) 3 -CH(C n H 2n+1 ) 2 …(4b) -(CH 2 ) m -CH 3 …(5b)

[0084] In the formulae (1b) to (4b) and (1c) to (2c), n is an integer of 1 to 10, preferably 2 to 8, and more preferably 2 to 4. However, the number of carbon atoms in the groups (1b) to (4b) and the groups (1c) to (2c) is within the range of 1 to 20. n H 2n+1 , three C in formulas (1c) to (2c) n H 2n+1 may be linear or branched, and may be the same or different. In formula (5b), m is an integer of 0 to 19, preferably 1 to 19, more preferably 2 to 15, and further preferably 3 to 11. Furthermore, groups (1b) to (5b) and groups (1c) to (2c) may have an oxygen atom between carbon atoms.

[0085] Also, R 13 and R 23 When R 13 and R 23 A divalent group -Q 3 - represents an alkylene group having 3 to 5 carbon atoms or an alkyleneoxy group having 2 to 4 carbon atoms. 3 In the heterocycle, one of the hydrogen atoms bonded to the carbon atom farthest from the nitrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms. The alkyl group is preferably linear, from the viewpoint that the squarylium dye is likely to exhibit dichroism. In addition, some or all of the hydrogen atoms in the heterocycle may be substituted with halogen atoms, and in this case, it is preferable that some or all of the hydrogen atoms bonded to the carbon atom not adjacent to the nitrogen atom are substituted with halogen atoms.

[0086] R 33 is an organic group R that does not necessarily have an unsaturated bond. 33A Or an organic group R that requires an unsaturated bond 33B It is. Organic group R that does not necessarily have an unsaturated bond 33Ais a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group, an alkoxy group, an aryl group, or an araryl group which may have a substituent and which may contain an unsaturated bond or an oxygen atom between carbon atoms. Organic group R that requires an unsaturated bond 33B is an alkenyl group having 2 or more carbon atoms which may have a substituent, an alkynyl group having 2 or more carbon atoms which may have a substituent, an imino group having 1 or more carbon atoms which may have a substituent, a cyano group, an organic group having 1 or more carbon atoms which contains a carbonyl structure and may have a substituent, an aryl group having 6 to 9 carbon atoms which may have a substituent, or a heteroaryl group having 3 to 9 carbon atoms which may have a substituent. R 33 X 31 , X 32 , or X 33 and may be linked to form a ring. The ring is preferably a ring having 5 to 7 members. The ring may have a substituent.

[0087] R 33A Examples of the substituent in R include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 8 carbon atoms. 33A When is an aryl group or an araryl group, the substituent is a hydrogen atom bonded to the aromatic ring or a group substituting a hydrogen atom of an alkyl group contained therein, and further includes an aryl group in addition to the above-mentioned substituents.

[0088] R 33A When R is an alkyl group or an alkoxy group, it preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms. 33A When R is an aryl group, the number of carbon atoms is preferably 6 to 9. 33A When the aryl group is an aryl group, it preferably has 7 to 9 carbon atoms. R 33A When R has a substituent, 33A The number of carbon atoms of the substituent is included in the number of carbon atoms of the group.

[0089] R 33AFrom the viewpoint of photostability, is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom.

[0090] Organic group R that requires an unsaturated bond 33B Examples of the substituent in include a halogen atom, a hydroxyl group, a carbonyl structure-containing monovalent organic group, a phosphate group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a thiol group, a sulfide group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, a heteroaryl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, a silyl group, and a halogenated alkyl group having 1 to 8 carbon atoms. R 33B When R has a substituent, 33B The number of carbon atoms of the substituent is included in the number of carbon atoms of the group.

[0091] R 33B When it is an alkenyl group, it has 2 or more carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms. The alkenyl group is preferably a group represented by the following formula (3-1).

[0092] [ka]

[0093] R 3a , R 3b , R 3care each independently a hydrogen atom, a halogen atom, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 7 carbon atoms, an alkyl group having 1 to 7 carbon atoms, an aralkyl group having 6 to 7 carbon atoms, an aryl group having 6 to 7 carbon atoms which may have a substituent, a heteroaryl group having 3 to 7 carbon atoms which may have a substituent, an alkenyl group having 2 to 7 carbon atoms which may have a substituent, an alkynyl group having 2 to 7 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 7 carbon atoms (such as a trimethylsilyl group, a triphenylsilyl group, or a t-butyldiphenylsilyl group), a trialkoxysilyl group having 3 to 7 carbon atoms (such as a trimethoxysilyl group or a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 7 carbon atoms. 3b is R 3a or R 3c may be linked to form a 3- to 6-membered ring which may contain a heteroatom, in which case the ring may have a substituent.

[0094] Aryl group, heteroaryl group, alkenyl group, alkynyl group, R 3b R 3a or R 3c Examples of the substituent in the ring formed by linking with the above include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a triorganosilyl group having 3 to 6 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 6 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 6 carbon atoms.

[0095] Preferred examples of the group (3-1) include the following structures.

[0096] [ka]

[0097] R 33B When it is an alkynyl group, it has 2 or more carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms. The alkynyl group is preferably a group represented by the following formula (3-2).

[0098] [ka]

[0099] R 3d is a hydrogen atom, a halogen atom, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 7 carbon atoms, an alkyl group having 1 to 7 carbon atoms, an aralkyl group having 6 to 7 carbon atoms, an aryl group having 6 to 7 carbon atoms which may have a substituent, a heteroaryl group having 3 to 7 carbon atoms which may have a substituent, an alkenyl group having 2 to 7 carbon atoms which may have a substituent, an alkynyl group having 2 to 7 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 7 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 7 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 7 carbon atoms.

[0100] Examples of the substituent in the aryl group, heteroaryl group, alkenyl group, and alkynyl group include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 5 carbon atoms, a triorganosilyl group having 3 to 5 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 5 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 5 carbon atoms.

[0101] Preferred examples of the group (3-2) include the following structures.

[0102] [ka]

[0103] R 33B When it is an imino group, it has 1 or more carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. The imino group is preferably a group represented by the following formula (3-3).

[0104] [ka]

[0105] R 3e , R 3f are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 6 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms which may have a substituent, a heteroaryl group having 3 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 8 carbon atoms (trimethylsilyl group, etc.), a trialkoxysilyl group having 3 to 8 carbon atoms (trimethoxysilyl group, dimethoxyethoxysilyl group, etc.), or a halogenated alkyl group having 1 to 8 carbon atoms. R 3e and R 3f may be linked to form a 3- to 6-membered ring which may contain a heteroatom, in which case the ring may have a substituent.

[0106] Aryl group, heteroaryl group, alkenyl group, alkynyl group, R 3e and R 3fExamples of the substituent in the ring formed by linking the groups include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a triorganosilyl group having 3 to 6 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 6 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 6 carbon atoms.

[0107] Preferred examples of the group (3-3) include the following structures.

[0108] [ka]

[0109] R 33B When is a cyano group, it is a group represented by the following formula (3-4).

[0110] [ka]

[0111] R 33B When is an organic group having 1 or more carbon atoms which contains a carbonyl structure and may have a substituent, the number of carbon atoms is 1 or more, preferably 1 to 8, more preferably 1 to 6, and further preferably 1 to 4. Such an organic group is preferably a group represented by the following formula (3-5).

[0112] [ka]

[0113] R 3gis a hydrogen atom, a hydroxyl group, a cyano group, an amino group, an N-substituted amino group, an alkoxycarbonyl group, a sulfide group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 6 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms which may have a substituent, a heteroaryl group having 3 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 8 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 8 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 8 carbon atoms.

[0114] Examples of the substituent in the aryl group, heteroaryl group, alkenyl group, and alkynyl group include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a triorganosilyl group having 3 to 6 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 6 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 6 carbon atoms.

[0115] Preferred examples of the group (3-5) include the following structures.

[0116] [ka]

[0117] R 33B When it is an aryl group, it has 6 to 9 carbon atoms.

[0118] The aryl group is preferably a group represented by the following formula (3-6).

[0119] [ka]

[0120] R 3h , R 3i , R 3j , R 3k , R 3l are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms which may have a substituent, an alkynyl group having 2 to 3 carbon atoms which may have a substituent, a trimethylsilyl group, a trimethoxysilyl group, or a halogenated alkyl group having 1 to 3 carbon atoms. R 3h and R 3i , R 3i and R 3j , R 3j and R 3k , R 3k and R 3l may be linked to each other to form a 3-6 membered ring which may contain a heteroatom.

[0121] Substituents in the alkenyl group and alkynyl group include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, a methoxy group, a methyl group, or a halogenated methyl group.

[0122] Preferred examples of the group (3-6) include the following structures.

[0123] [ka]

[0124] R 33B When is a heteroaryl group, it has 3 to 9 carbon atoms.

[0125] The heteroaryl group is preferably a group represented by any one of the following formulas (3-7) to (3-9).

[0126] [ka]

[0127] X 3a , X 3b , X 3c , X 3d , X 3e are each independently N or CR 3m and at least one is N. 3m is a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a heteroaryl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, an alkynyl group having 2 to 6 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 6 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 6 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 6 carbon atoms. X 3a , X 3b , X 3c , X 3d , X 3e CR 3m If so, the adjacent X 3a ~X 3e are linked together to form a 3-6-membered ring Ar 30 , Ar 31 , Ar 32 , Ar 33 In this case, the ring may have a substituent. Heteroaryl group, alkenyl group, alkynyl group, ring Ar 30 , Ar 31 , Ar 32 , Ar 33Examples of the substituent in include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, a trimethylsilyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.

[0128] Preferred examples of the group (3-7) include the following structures.

[0129] [ka]

[0130] [ka]

[0131] X 3f , X 3g , X 3h are each independently N or CR 3n Y 3a is S, O or NR 3o It is. R 3n and R 3o are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a heteroaryl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, an alkynyl group having 2 to 6 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 6 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 6 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 6 carbon atoms. X 3f , X 3g , X 3h CR3n and Y 3a NR 3o If so, the adjacent X 3f , X 3g , X 3h , Y 3a are linked together to form a 3-6-membered ring Ar 34 , Ar 35 , Ar 36 In this case, the ring may have a substituent. Heteroaryl group, alkenyl group, alkynyl group, ring Ar 34 , Ar 35 , Ar 36 Examples of the substituent in include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, a trimethylsilyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.

[0132] Preferred examples of the group (3-8) include the following structures.

[0133] [ka]

[0134] [ka]

[0135] X 3i , X 3j , X 3k are each independently N or CR 3p Y 3b is S, O or NR 3q R 3p and R 3qare each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a heteroaryl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, an alkynyl group having 2 to 6 carbon atoms which may have a substituent, a triorganosilyl group having 3 to 6 carbon atoms (e.g., a trimethylsilyl group), a trialkoxysilyl group having 3 to 6 carbon atoms (e.g., a trimethoxysilyl group, a dimethoxyethoxysilyl group), or a halogenated alkyl group having 1 to 6 carbon atoms. X 3i , X 3j , X 3k CR 3p and Y 3b NR 3q If so, the adjacent X 3i , X 3j , X 3k , Y 3b are linked together to form a 3-6-membered ring Ar 37 , Ar 38 , Ar 39 In this case, the ring may have a substituent. Aryl group, heteroaryl group, alkenyl group, alkynyl group, ring Ar 37 , Ar 38 , Ar 39 Examples of the substituent in include a halogen atom, a formyl group, a carboxy group, a sulfo group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a sulfide group, a trimethylsilyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.

[0136] Preferred examples of the group (3-9) include the following structures:

[0137] [ka]

[0138] In formula (III), X 31 is CR 43 Or N. X 32 S, NR 53 , or O. X 33 S, NR 63 , or O.

[0139] R 43 is a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a monovalent organic group containing a carbonyl structure, a phosphate group, a silyl group, a thiol group, a sulfide group, a monovalent organic group containing an amide structure, a sulfonamide group, a urea group, a monovalent organic group containing a urethane structure, an alkyl group having 1 to 9 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, an alkynyl group having 2 to 9 carbon atoms which may have a substituent, an aryl group having 6 to 9 carbon atoms which may have a substituent, a heteroaryl group having 3 to 9 carbon atoms which may have a substituent, an alkoxy group having 1 to 9 carbon atoms which may have a substituent, an acyloxy group having 2 to 9 carbon atoms which may have a substituent, or —N(R 43g ) 2 (R 43g is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.

[0140] R 43 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an acyloxy group, or —N(R 43g ) 2 If R 43 is R 13 ~R 33 may be linked to each other to form a ring having 3 to 6 members. In addition, the ring may have a substituent.

[0141] R 43Examples of the substituent in include a halogen atom, a hydroxyl group, a carbonyl structure-containing monovalent organic group, a phosphate group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, a thiol group, a sulfide group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, a heteroaryl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, a silyl group, and a halogenated alkyl group having 1 to 8 carbon atoms. R 43 When R has a substituent, 43 The number of carbon atoms of the substituent is included in the number of carbon atoms of the group.

[0142] R 43 The halogen atom in is preferably a fluorine atom.

[0143] R 43 The carbonyl structure-containing monovalent organic group in is -C(=O)-R 43a is preferred. 43a represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an alkoxy group having 1 to 8 carbon atoms which may have a substituent, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an isopropyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, an isopropoxy group, an isobutoxy group, or a 2-ethylhexyloxy group.

[0144] R 43 The silyl group in is -Si(R 43b ) 3 is preferred. 43b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. 43b may be the same or different.

[0145] R 43 The sulfide group in is -SR 43cis preferred. 43c represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a substituent, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an isopropyl group, a t-butyl group, or a 2-ethylhexyl group.

[0146] R 43 The amide structure-containing monovalent organic group in is -C(=O)-NH-R 43d is preferred. 43d represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an isopropyl group, a t-butyl group, or a 2-ethylhexyl group.

[0147] R 43 The sulfonamide group in the 2 -N(R 43e ) 2 is preferred. 43e is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a t-butyl group. 43e may be the same or different.

[0148] R 43 The urethane structure-containing monovalent organic group in the formula is -NH-C(=O)OR 43f is preferred. 43f represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an isopropyl group, a t-butyl group, or a 2-ethylhexyl group.

[0149] R 43 In the above formula, the alkyl group having 1 to 9 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an isopropyl group, an isobutyl group, a t-butyl group, or a 2-ethylhexyl group.

[0150] R 43In the above formula, the alkenyl group having 2 to 9 carbon atoms is preferably a vinyl group, a 1-propenyl group, an isobutenyl group, a styryl group, a 2-fluorovinyl group, a 2,2-difluorovinyl group, or a 3,3,3-trifluoropropenyl group.

[0151] R 43 In the above formula, the alkynyl group having 2 to 9 carbon atoms is preferably an acetylenyl group, a 1-propynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylsilylethynyl group, or a t-butyldimethylsilylethynyl group.

[0152] R 43 In the above formula, the aryl group having 6 to 9 carbon atoms is preferably a phenyl group, a 4-methoxyphenyl group, a 3,4,5-trifluorophenyl group, a 4-trifluoromethylphenyl group, a 2,5-dimethylphenyl group, or a 3-nitrophenyl group.

[0153] R 43 In the above, the heteroaryl group having 3 to 9 carbon atoms is preferably a pyridyl group, a pyrimidyl group, a quinolyl group, a furyl group, a thienyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a benzoxazolyl group, a benzimidazolyl group or a benzthiazolyl group.

[0154] R 43 In the above formula, the alkoxy group having 1 to 9 carbon atoms is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, an isopropoxy group, an isobutoxy group, or a 2-ethylhexyloxy group.

[0155] R 43 In the above formula, the acyloxy group having 2 to 9 carbon atoms is preferably an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, or a benzoyloxy group.

[0156] R 43 In -N(R 43g ) 2 In two R 43g may be the same or different. Also, two R43g They may be linked together to form a ring. 43g ) 2 As the amino group, a dimethylamino group, a diethylamino group, an ethylisopropylamino group, and a morpholino group are preferable.

[0157] X 32 S, NR 53 , or O. R 53 represents a hydrogen atom, a carbonyl structure-containing monovalent organic group, a sulfo group, or an alkyl group having 1 to 9 carbon atoms which may have a substituent, and is preferably a hydrogen atom, a methyl group, an ethyl group, an isobutyl group, a 2-ethylhexyl group, a benzyl group, a t-butoxycarbonyl group, a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a 2,2,2-triethoxycarbonyl group, or a 2-nitrobenzenesulfonyl group. The substituent is R 43 The substituents are the same as those in the above.

[0158] R 53 is an alkyl group having 1 to 9 carbon atoms which may have a substituent, R 53 is R 13 ~R 33 may be linked to any one of the following to form a 3-6 membered ring.

[0159] X 33 is S, NR 63 , or O. R 63 represents a hydrogen atom, a carbonyl structure-containing monovalent organic group, a sulfo group, or an alkyl group having 1 to 9 carbon atoms which may have a substituent, and is preferably a hydrogen atom, a methyl group, an ethyl group, an isobutyl group, a 2-ethylhexyl group, a benzyl group, a t-butoxycarbonyl group, a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a 2,2,2-triethoxycarbonyl group, or a 2-nitrobenzenesulfonyl group. The substituent is R 43 The substituents are the same as those in the above.

[0160] R 63 When R is an alkyl group, 63 is R 43 may be linked to form a 3-6 membered ring.

[0161] In formula (III), X 31 ,X 32 ,X 33 The following combinations are included:

[0162] [Table 3]

[0163] From the viewpoint of ease of synthesis, the preferred combination is (X 31 ,X 32 ,X 33 )=(CR 43 ,S,S), (CR 43 ,S,O), (CR 43 ,O,S), (CR 43 ,O,O), (CR 43 ,NR 53 ,S), (CR 43 ,NR 53 , O), and more preferred combinations are (X 31 ,X 32 ,X 33 )=(CR 43 ,S,S), (CR 43 ,S,O), (CR 43 ,NR 53 ,S), (CR 43 ,NR 53 ,O).

[0164] As the squarylium compound represented by formula (III), from the viewpoints of ease of synthesis and increased molecular linearity, squarylium compounds represented by the following formula (III-1) and squarylium compounds represented by the following formula (III-2) are preferred.

[0165] [ka]

[0166] R 13 , R 23 , R 33A , R 33B , R 43 is R in formula (III) 13 , R 23 , R 33A , R 33B , R 43 and preferred embodiments are the same as those mentioned above.

[0167] More specifically, examples of compound (III-1) include the compounds shown in the following table. In the compounds shown in the following table, the symbols on the left and right of the squarylium skeleton have the same meaning.

[0168] [Table 4]

[0169] More specifically, examples of compound (III-2) include the compounds shown in the following table. In the compounds shown in the following table, the symbols on the left and right of the squarylium skeleton have the same meaning.

[0170] [Table 5]

[0171] [Table 6]

[0172] [Table 7]

[0173] [Table 8]

[0174] The squarylium compound (III) can be synthesized by a known production method or a production method described below.

[0175] The squarylium compound (III-1) can be produced, for example, by the method described in WO 2019 / 230570.

[0176] R in squarylium compounds (III) 33 R 33B A method for obtaining the squarylium compound (III-B) is shown in Scheme (FB).

[0177] [ka]

[0178] Step (A) is a reaction for converting a carboxylic acid into a dialkylamine, and the details are shown in the following scheme. In the following scheme, HetAr means heteroaryl. Azide is preferably diphenylphosphoryl azide. N alkylation is S using an alkyl halide and a base. N 2 reaction or a reductive amination reaction using an aldehyde and a reducing agent is preferred.

[0179] [ka]

[0180] Step B is a reaction for converting halogen into various substituents, and may utilize, but is not limited to, a cross-coupling reaction, a Heck reaction, formylation, a Wittig reaction of an aldehyde obtained by formylation, a Knevenagel reaction, a Henry reaction, a nucleophilic addition reaction of an alkyl metal reactant, and the like.

[0181] The starting material (a2-1) in scheme (FB) can be obtained, for example, from a known compound by the following synthesis method.

[0182] In the starting material (a2-1), X 31 , X 32 , R is as follows, a method for synthesizing a compound: Compound (a2-1-1): (X 31 , X 32 , R) = (-CH, S, -CH 2 CH 3 ) Compound (a2-1-2): (X 31 , X 32 , R) = (-CH, S, H) Compound (a2-1-3): (X 31 , X 32 , R) = (-CH, O, -CH 2 CH 3 ) Compound (a2-1-4): (X 31 , X 32 , R) = (-CH, O, H)

[0183]

Chemical formula

[0184] In the starting material (a2-1), X 31 , X 32 , (X 33 ), R is as follows, a method for synthesizing a compound: Compound (a2-1-5): (X 31 , X 32 , R) = (-CH, -NH, -CH 2 CH 3 ) Compound (a2-1-6): (X 31 , X 32 , R) = (-CH, -NH, H) Compound (a2-1-7): (X 31 , X 32 , X 33 , R) = (-CH, -NH, -NH, -CH 2 CH 3 ) Compound (a2-1-8): (X 31 , X 32 , X 33 , R) = (-CH, -NH, -NH, H)

[0185] [ka]

[0186] In the starting material (a2-1), X 31 , X 32 and R is: Compound (a2-1-9):(X 31 , X 32 , R)=(N, O, -CH 2 CH 3 ) Compound (a2-1-10):(X 31 , X 32 , R)=(N, O, H)

[0187] [ka]

[0188] In the starting material (a2-1), X 31 , X 32 and R is: Compound (a2-1-11):(X 31 , X 32 , R)=(N, -NH, -CH 2 CH 3 ) Compound (a2-1-12):(X 31 , X 32 , R)=(N, -NH, H)

[0189] [ka]

[0190] In the starting material (a2-1), X 31 , X 32 and R is: Compound (a2-1-13):(X 31 , X 32 , R)=(N, S, -CH 2 CH3 ) Compound (a2-1-14):(X 31 , X 32 , R)=(N, S, H)

[0191] [ka]

[0192] <Squarylium dyes (IV)>

[0193] [ka]

[0194] Here, the symbols in the above formula are as follows: R 14 and R 24 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a heteroatom, an alicyclic ring, or an aromatic ring.

[0195] R 14 is R 24 , R 54 or R 74 may be linked to form a ring. R 24 is R 14 , R 54 or R 74 may be linked to form a ring. The ring is preferably an alicyclic or aromatic ring having 3 to 6 members, and the ring may have a substituent.

[0196] R 14 and R 24 The carbon number of R may be 1 to 20. 14 and R 24 In the case of a linear structure, the number of carbon atoms in R is preferably 2 to 12, more preferably 3 to 10, and further preferably 4 to 8. 14 and R 24 In the case of a branched chain, the number of carbon atoms is preferably 3 to 12, and more preferably 4 to 8.

[0197] R 14 and R 24 The substituents in the squarylium dye (III) include R 13 and R 23 The substituents are the same as those in the above.

[0198] R 14 and R 24 However, when the main chain or side chain contains an alicyclic ring or an aromatic ring, the number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0199] R 14 and R 24 has a substituent, or contains an alicyclic or aromatic ring in the main chain or side chain, the number of carbon atoms in the above includes the number of carbon atoms in the substituent, alicyclic or aromatic ring.

[0200] R 14 and R 24 may be the same or different, but is preferably the same from the viewpoint of ease of production.

[0201] R 14 and R 24 From the viewpoint of the degree of orientation, it is preferable that the polymer has a linear shape.

[0202] R 14 and R 24 is, for example, R in the above squarylium dye (III). 13 and R 23 In the above formula, a group selected from the groups (1b) to (5b) and the groups (1c) to (2c) is more preferable.

[0203] Also, R 14 and R 24 When R 14 and R 24 A divalent group -Q 4 - is a divalent group -Q in the above squarylium dye (III). 3 Groups similar to - are preferred.

[0204] R 34 is an organic group R that does not necessarily have an unsaturated bond. 34A Or an organic group R that requires an unsaturated bond 34B It is. Organic group R that does not necessarily have an unsaturated bond 34A is a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group, an alkoxy group, an aryl group, or an araryl group which may have a substituent and which may contain an unsaturated bond or an oxygen atom between carbon atoms. Organic group R that requires an unsaturated bond 34B is an alkenyl group having 2 or more carbon atoms which may have a substituent, an alkynyl group having 2 or more carbon atoms which may have a substituent, an imino group having 1 or more carbon atoms which may have a substituent, a cyano group, an organic group having 1 or more carbon atoms which contains a carbonyl structure and may have a substituent, an aryl group having 6 to 9 carbon atoms which may have a substituent, or a heteroaryl group having 3 to 9 carbon atoms which may have a substituent.

[0205] R 34A The substituents in the above-mentioned squarylium dye (III) include R 33A The substituents are the same as those in the above.

[0206] R 34A When R is an alkyl group or an alkoxy group, it preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms. 34A When R is an aryl group, the number of carbon atoms is preferably 6 to 9. 34A When the aryl group is an aryl group, it preferably has 7 to 9 carbon atoms. R 34A When R has a substituent, 34A The number of carbon atoms of the substituent is included in the number of carbon atoms of the group.

[0207] R 34A From the viewpoint of photostability, is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom.

[0208] Organic group R that requires an unsaturated bond 34BThe substituents in the above-mentioned squarylium dye (III) include R 33B The substituents are the same as those in the above. R 34B When R has a substituent, 34B The number of carbon atoms of the substituent is included in the number of carbon atoms of the group.

[0209] R 34B When it is an alkenyl group, it has 2 or more carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms. The alkenyl group is R in the above squarylium dye (III). 33B Similarly, the group represented by the above formula (3-1) is preferred.

[0210] R 34B When it is an alkynyl group, it has 2 or more carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms. The alkynyl group is R 33B Similarly, the group represented by the above formula (3-2) is preferred.

[0211] R 34B When it is an imino group, it has 1 or more carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. The imino group is R in the above-mentioned squarylium dye (III). 33B Similarly, the group represented by the above formula (3-3) is preferred.

[0212] R 34B When R is a cyano group, R in the above squarylium dye (III) 33B Similarly, it is a group represented by the above formula (3-4).

[0213] R 34B When is an organic group having 1 or more carbon atoms which contains a carbonyl structure and may have a substituent, the number of carbon atoms is 1 or more, preferably 1 to 8, more preferably 1 to 6, and further preferably 1 to 4. Such an organic group is R in the above-mentioned squarylium dye (III). 33B Similarly, the group represented by the above formula (3-5) is preferred.

[0214] R 34B When it is an aryl group, it has 6 to 9 carbon atoms. The aryl group is R in the squarylium dye (III) described above. 33B Similarly, the group represented by the above formula (3-6) is preferred.

[0215] R 34B When is a heteroaryl group, it has 3 to 9 carbon atoms. As the heteroaryl group, R in the squarylium dye (III) described above can be used. 33B Similarly, a group represented by any one of the above formulas (3-7) to (3-9) is preferred.

[0216] R 44 , R 54 , R 64 , R 74 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 9 carbon atoms.

[0217] Examples of the halogen atom include a chlorine atom, a fluorine atom, an iodine atom, and a bromine atom. Examples of the monovalent organic group include an alkyl group, an alkoxy group, an acyloxy group, an araryl group, an amino group, an alkenyl group, an alkynyl group, an imino group, a cyano group, a carbonyl group, an aryl group, and a heteroaryl group.

[0218] In formula (IV), X 41 is CR 43 Or N. X 42 S, NR 53 , or O. X 43 S, NR 63 , or O. 43 , R 53 , R 63 is R in the above squarylium dye (III). 43 , R 53 , R 63The same applies including definitions and preferred embodiments.

[0219] More specifically, compound (IV) includes the compounds shown in the following table. In the compounds shown in the following table, the symbols on the left and right of the squarylium skeleton have the same meaning.

[0220] [Table 9]

[0221] [Table 10]

[0222] Compound (IV) has an R 14 and R 24 4-aminobenzeneboronic acid bound to X 41 and X 42 It can be produced by coupling a fused heterocyclic compound in which halogen atoms are bonded to the carbon atoms between the rings, and then reacting it with squaric acid.

[0223] [ka]

[0224] <Squarylium dyes (V)>

[0225] [ka]

[0226] Here, the symbols in the above formula are as follows: R 35 , R 45 , R 55 , R 65are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aryl group having 4 to 9 carbon atoms which may have a substituent, or an aryl group having 5 to 9 carbon atoms which may have a substituent.

[0227] R 35 , R 45 , R 55 , R 65 In the above, the alkyl group, the aryl group or the araryl group may have a substituent. In addition, the alkyl group, aryl group, or araryl group may contain an unsaturated bond, an oxygen atom, an ester bond, an amide bond, or a thioamide bond between carbon atoms. Furthermore, the alkyl group, aryl group, or araryl group may have an oxygen atom, an ester bond, an amide bond, or a thioamide bond at the end bonding to the thiophene ring.

[0228] R 35 , R 45 , R 55 , R 65 Examples of the substituent in R include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 8 carbon atoms. 35 , R 45 , R 55 , R 65 When is an aryl group or an araryl group, the substituent is a hydrogen atom bonded to the aromatic ring or a group substituting a hydrogen atom of an alkyl group contained therein, and further includes an aryl group in addition to the above-mentioned substituents.

[0229] R 35 , R 45 , R 55 , R 65 When the group is an alkyl group, it has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms. R 35 , R 45 , R 55 , R 65When the group is an aryl group, it has 4 to 9 carbon atoms, and preferably 4 to 6 carbon atoms. R 35 , R 45 , R 55 , R 65 When the aryl group is an araryl group, it has 5 to 9 carbon atoms, and preferably 5 to 7 carbon atoms.

[0230] R 35 , R 45 , R 55 , R 65 When the group has a substituent, the number of carbon atoms included in the number of carbon atoms of the substituent.

[0231] R 35 and R 45 , R 45 and R 55 , and R 55 and R 65 may be linked to each other to form a monocycle or a polycycle having 2 to 4 condensed rings, in which case a hydrogen atom bonded to the ring may be substituted with a substituent.

[0232] R 35 and R 45 , and R 55 and R 65 The ring formed by linking may be an alicyclic ring or an aromatic ring, a hydrocarbon ring or a heterocyclic ring. An aromatic ring is preferable. An example of the monocyclic ring is a benzene ring, and an example of the polycyclic ring is a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, etc.

[0233] R 45 and R 55 When these are linked, the dye (V) contains a structure in which a ring is formed between two thiophene rings to form at least three condensed rings.

[0234] R 35 and R 45 , R 45 and R 55 , and R 55 and R 65 A hydrogen atom bonded to the ring formed by linking may be substituted with a substituent. The substituents on these connecting rings include R 35 , R 45 , R 55 , R 65 and a phenyl group which may have a substituent.

[0235] R 15 and R 25 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms.

[0236] R 15 and R 25 may have a substituent and may contain an unsaturated bond or a heteroatom between carbon atoms. R 15 and R 25 Examples of the substituent in include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 19 carbon atoms. In addition, R 1 and R 2 When R has a substituent, the number of carbon atoms of the substituent is 1 and R 2 is included in the carbon number.

[0237] R 15 and R 25 Further examples of the substituent in include a cyclic alkyl group or an aryl group. The aryl group is preferably a phenyl group which may have 1 to 5 substituents, or a naphthyl group which may have 1 to 7 substituents. Examples of the substituent which may substitute a hydrogen atom in the phenyl group or naphthyl group include an alkyl group having 1 to 12 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 12 carbon atoms). The phenyl group and naphthyl group are preferably unsubstituted or substituted with 1 to 3 hydrogen atoms, and examples of the substituent include a methyl group, a t-butyl group, a dimethylamino group, a methoxy group, and the like.

[0238] R 15 and R 25 However, when the main chain or side chain contains an alicyclic ring or an aromatic ring, the number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0239] R 15 and R 25 From the viewpoint of improving the reliability of the optical element, the substituent in is preferably a polymerizable group.

[0240] R 15 and R 25 When R is an alkyl group, it has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms. 15 and R 25 From the viewpoint of improving visible light transmittance and dichroic ratio, R is preferably a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms, which may contain a heteroatom between carbon atoms. The number of carbon atoms in the alkyl group is more preferably 3 to 12 in the case of a linear alkyl group, more preferably 3 to 10 in the case of a branched alkyl group, and more preferably 5 to 10 in the case of a cyclic alkyl group. 15 and R 25 When the group has a substituent, the number of carbon atoms included in the number of carbon atoms of the substituent.

[0241] R 15 and R 25 is, for example, more preferably a group selected from groups (1a) to (15a), and particularly preferably group (3a).

[0242] [ka]

[0243] R 15 and R 25may be linked together to form a heterocycle having 4 to 10 members together with the nitrogen atom, and from the viewpoint that the squarylium dye is likely to be linear, i.e., to easily exhibit dichroism, the number of members is particularly preferably 4 to 6. In such a heterocycle, one of the hydrogen atoms bonded to the carbon atom furthest from the nitrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, which may have an unsaturated bond or a heteroatom between the carbon atoms. The alkyl group may be branched, linear, or cyclic, but from the viewpoint that the squarylium dye is likely to exhibit dichroism, a linear alkyl group is preferred. In addition, some or all of the hydrogen atoms in such a heterocycle may be substituted with halogen atoms, and in this case, it is preferred that some or all of the hydrogen atoms bonded to the carbon atom not adjacent to the nitrogen atom are substituted with halogen atoms.

[0244] R 15 and R 25 A divalent group to which is bonded is called -Q 5 -Q 5 Specific examples of - include the following groups (11) to (15).

[0245] -(CH 2 ) 4 - (11) -(CH 2 ) 5 - (12) -C(CH 3 ) 2 (CH 2 ) 2 C(CH 3 ) 2 - (13) -C(CH 3 ) 2 (CH 2 ) 3 C(CH 3 ) 2 - (14) -CH 2 -CH(nC 8 H 17 )-(CH 2 ) 2 - (15)

[0246] As the squarylium compound (V), for example, a compound represented by the following formula (V-1) or a compound represented by the following formula (V-2) is preferable. The squarylium compound (V-1) is a squarylium compound (V) in which R 45 and R 55 are linked to form a cyclopentadithiophene ring. The squarylium compound (V-2) is a squarylium compound (V) in which R 45 and R 55 is not linked, but is a compound that contains a structure in which two thiophene rings are bonded together.

[0247] [ka]

[0248] R 15 , R 25 , R 35 and R 65 The definition of R in formula (V) 15 , R 25 , R 35 and R 65 The same applies to the definitions and preferred embodiments of the above. R 45b and R 55b The definition of R in formula (V) applies, except that they are not linked together to form a ring. 45 and R 55 The same applies to the definitions and preferred embodiments of the above.

[0249] R 45a and R 55a From the viewpoint of visible light transmittance, light resistance, and improvement of the dichroic ratio, R is preferably a straight-chain, branched-chain, or cyclic alkyl group having 1 to 9 carbon atoms, which may contain an unsaturated bond or an oxygen atom between carbon atoms. The number of carbon atoms in the alkyl group is 1 to 9 in the case of a straight-chain, preferably 3 to 9 in the case of a branched-chain, and more preferably 5 to 9 in the case of a cyclic group. 45a and R 55a is, for example, a methyl group and the above-mentioned R 15 and R 25More preferred are groups selected from groups (1a) to (13a) shown as specific examples of the above, with a methyl group, group (1a), group (3a) or group (9a) being particularly preferred.

[0250] R 45a and R 55a From the viewpoints of heat resistance, light resistance, and control of NIR absorption wavelength, a phenyl group which may have a substituent or a cyclic alkyl group having 5 to 9 carbon atoms is preferable. Examples of the substituent of the phenyl group include an alkyl group having 1 to 3 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 3 carbon atoms), and in particular, a methyl group, a dimethylamino group, a methoxy group, etc. are preferable. The phenyl group is preferably unsubstituted or substituted with 1 to 3 hydrogen atoms.

[0251] Specific examples of the phenyl group which may have a substituent include groups (P1) to (P6).

[0252] [ka]

[0253] More specifically, examples of compound (V-1) include the compounds shown in the following table. In addition, in the compounds shown in the following table, the meanings of the symbols on the left and right of the squarylium skeleton are the same.

[0254] [Table 11]

[0255] [Table 12]

[0256] [Table 13]

[0257] [Table 14]

[0258] Of these, compound (V-1-59) and the like are preferred as compound (V-1) from the viewpoint of improving the dichroic ratio.

[0259] More specifically, examples of compound (V-2) include the compounds shown in the following table. In addition, in the compounds shown in the following table, the meanings of the symbols on the left and right of the squarylium skeleton are the same.

[0260] [Table 15]

[0261] [Table 16]

[0262] [Table 17]

[0263] Of these, compound (V-2) is preferably compound (V-2-36) or the like from the viewpoint of improving the dichroic ratio.

[0264] Compound (V) can be produced by a known method, for example, the method described in WO 2019 / 230660.

[0265] <Squarylium dyes (VI)>

[0266] [ka]

[0267] Here, the symbols in the above formula are as follows:

[0268] R 16 and R26 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a heteroatom, an alicyclic ring, or an aromatic ring.

[0269] R 16 and R 26 Examples of the substituent in include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an amino group, an N-substituted amino group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an N-substituted carbamoyl group, an imido group, and an alkoxy group having 1 to 19 carbon atoms.

[0270] R 16 and R 26 Further examples of the substituent in include a cyclic alkyl group or an aryl group. The aryl group is preferably a phenyl group which may have a substituent or a naphthyl group which may have a substituent. Examples of the substituent which may replace the hydrogen atom of the phenyl group and the naphthyl group include an alkyl group having 1 to 9 carbon atoms, which may contain an unsaturated bond or an oxygen atom between the carbon atoms, an alkoxy group, or an alkylamino group (the alkyl group has 1 to 9 carbon atoms). The phenyl group and the naphthyl group are preferably unsubstituted or substituted with 1 to 3 hydrogen atoms, and examples of the substituent include a methyl group, a t-butyl group, a dimethylamino group, a methoxy group, etc.

[0271] R 16 and R 26 From the viewpoint of improving the reliability of the optical element, the substituent in is preferably a polymerizable group.

[0272] R 16 and R 26 However, when the main chain or side chain contains an alicyclic or aromatic ring, this is preferable in terms of heat resistance and control of the NIR absorption wavelength. 16 and R 26 However, when the main chain or side chain does not have an alicyclic ring or an aromatic ring, it is preferable in terms of light resistance, ease of production, and improvement of the dichroic ratio. The number of carbon atoms in the alicyclic ring is preferably 3 to 10. The number of carbon atoms in the aromatic ring is preferably 4 to 14.

[0273] R 16 and R 26 The carbon number of R may be 1 to 20. 16 and R 26 In the case of a linear structure, the number of carbon atoms in R is preferably 2 to 20, more preferably 3 to 16, and further preferably 4 to 12. 16 and R 26 In the case of a branched chain, the number of carbon atoms is preferably 3 to 20, more preferably 4 to 16, and further preferably 4 to 8.

[0274] R 16 and R 26 has a substituent, or contains an alicyclic or aromatic ring in the main chain or side chain, the number of carbon atoms in the above includes the number of carbon atoms in the substituent, alicyclic or aromatic ring.

[0275] R 16 and R 26 may be the same or different, but is preferably the same from the viewpoint of ease of production. 16 and R 26 From the viewpoint of the degree of orientation, the linear chain is preferable to the branched chain, and the carbon number is more preferably 1 to 8, and further preferably 1 or 2.

[0276] R 16 and R 26 When the alkyl group is branched, the number of branches is not particularly limited. The number of branches is preferably 1 to 5, more preferably 1 to 3. From the viewpoints of both solubility in liquid crystal and solvent and ease of production, the branch position is preferably the β position. Also, one carbon atom may be branched into two or three.

[0277] R 16 and R 26 is, for example, R in squarylium dye (III) 13 and R 23 More preferred are groups selected from groups (1b) to (5b), (1c) and (2c) described as more preferred embodiments of the above. -CH(C n H 2n+1 )2 …(1b) -C(C n H 2n+1 ) 3 …(1c) -CH 2 -CH(C n H 2n+1 ) 2 …(2b) -CH 2 -C(C n H 2n+1 ) 3 …(2c) -(CH 2 ) 2 -CH(C n H 2n+1 ) 2 …(3b) -(CH 2 ) 3 -CH(C n H 2n+1 ) 2 …(4b) -(CH 2 ) m -CH 3 …(5b)

[0278] In the formulae (1b) to (4b), (1c) and (2c), n is an integer of 1 to 10, preferably 2 to 8, and more preferably 2 to 4. However, the number of carbon atoms in the groups (1b) to (4b) and the groups (1c) to (2c) is within the range of 1 to 20. n H 2n+1 , three C in formulas (1c) to (2c) n H 2n+1 may be linear or branched, and may be the same or different. In formula (5b), m is an integer of 0 to 19, preferably 1 to 19, more preferably 2 to 15, and further preferably 3 to 11. Furthermore, groups (1b) to (5b), (1c), and (2c) may have a heteroatom between carbon and carbon atoms.

[0279] R 36is a monovalent organic group having 9 or less carbon atoms and containing an atom having an unshared electron pair. By bonding a group having an unshared electron pair to the carbon atom closest to the squarylium skeleton, the electron density of the unsaturated carbon ring increases, and an atom having an unshared electron pair is required for the production of the dye (reaction with squaric acid). From this perspective, R 36 The atom with the lone pair in is R 36 is preferably bonded directly to a carbon atom of the unsaturated carbocyclic ring to which it is attached. The atom having an unshared electron pair is preferably N, S or O.

[0280] R 36 As for NH-Y 36a -R 36a , SH, or OH are preferred. NH-Y 36a -R 36a In this case, Y 36a is a single bond or a divalent organic group having 0 to 3 carbon atoms, preferably -CO-, -COO-, -CONH-, or -SO 2 -It is. R 36 As for NH-R 36a , NH-CO-R 36a , NH-COO-R 36a , NH-CONH-R 36a , NH-SO 2 -R 36a , SH, or OH are preferred.

[0281] NH-Y 36a -R 36a In R 36a is an alkyl group having 1 to 9 carbon atoms, which may have a substituent and may contain an unsaturated bond between carbon atoms, an oxygen atom, an alicyclic ring, or an aromatic ring. 36a and R 36a The total number of carbon atoms is limited to 9.

[0282] R 36a The carbon number of is preferably 1 to 9, more preferably 1 to 4, and particularly preferably 1 or 2, when it is linear, and is preferably 3 to 9, and particularly preferably 3 or 4, when it is branched.

[0283] R 36a The substituents in 16 and R 26 The substituents are the same as those in the above. R 36a has a substituent, or contains an alicyclic or aromatic ring in the main chain or side chain, the number of carbon atoms in the above includes the number of carbon atoms in the substituent, alicyclic or aromatic ring.

[0284] R 36a From the viewpoint of improving the dichroic ratio, it is preferable that the compound has a linear structure.

[0285] R 36a As the group, a group selected from the groups (11b) to (15b), (11c) and (12c) is more preferable. -CH(C n H 2n+1 ) 2 …(11b) -C(C l H 2l+1 ) 3 …(11c) -CH 2 -CH(C n H 2n+1 ) 2 …(12b) -CH 2 -C(C l H 2l+1 ) 3 …(12c) -(CH 2 ) 2 -CH(C n H 2n+1 ) 2 …(13b) -(CH 2 ) 3 -CH(C n H 2n+1 ) 2 …(14b) -(CH 2 ) m -CH 3 …(15b)

[0286] In the formulae (11b) to (14b), n is an integer of 1 to 3, preferably 2 to 3. In the formulae (11c) and (12c), l is an integer of 1 to 2. n H 2n+1 Or 3 C's l H 2l+1 may be linear or branched, and may be the same or different. In formula (15b), m is an integer of 0 to 8, preferably 0 to 8, more preferably 0 to 3, and further preferably 0 to 1. Furthermore, the groups (11b) to (15b), (11c), and (12c) may have an oxygen atom between carbon and carbon atoms.

[0287] R 46 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0288] The alkyl group preferably has 1 to 8 carbon atoms, and more preferably has 1 to 4 carbon atoms. The alkyl group may be linear or branched, but is preferably linear from the viewpoint of improving the dichroic ratio.

[0289] R 46 When R is an alkyl group having 1 to 9 carbon atoms, 36a More preferred are groups selected from groups (11b) to (15b), (11c) and (12c) described as preferred embodiments in the above.

[0290] From the viewpoint of steric hindrance, R 46 is preferably a hydrogen atom.

[0291] R 56 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. From the viewpoint of steric hindrance, R 56 is preferably a hydrogen atom.

[0292] R 16 and R 26 , R 16 and R 46 , R 36 and R 46may be linked to each other to form a ring. As a ring, R 16 and R 26 , R 16 and R 46 is an alicyclic ring having 3 to 6 ring members, R 36 and R 46 is preferably an alicyclic or aromatic ring having 3 to 6 members. The ring may have a substituent. Examples of the substituent include R 16 and R 26 The substituents are the same as those in the above.

[0293] X 61 is C=O, C=S, or SO 2 It is.

[0294] The squarylium compound (VI) is preferably a squarylium compound represented by the following formula (VI-1).

[0295] [ka]

[0296] R 16 ~R 46 is R in formula (VI) 16 ~R 46 The same applies including preferred embodiments.

[0297] The squarylium compound (VI) is R 36 NH-CO-R 36a The following squarylium compound (VI-11), R 36 NH-SO 2 -R 36a The following squarylium compound (VI-12), R 36 NH-CONH-R 36a The following squarylium compound (VI-13), R 36 NH-COO-R 36a The following squarylium compound (VI-14), R 36 is OH, the following squarylium compound (VI-15) is preferred.

[0298] [ka]

[0299] [ka]

[0300] More specifically, the squarylium compounds (VI-11) to (VI-15) include R 16 , R 26 , R 36a , R 46 The following compounds are shown in the table (the abbreviations of the squarylium compounds (VI-11) to (VI-15) are also shown in the table). In the table, R 16 , R 26 , R 36a , R 46 In all compounds shown in the table, R 16 , R 26 , R 36a , R 46 are all identical on both sides of the equation.

[0301] [Table 18]

[0302] [Table 19]

[0303] [Table 20]

[0304] [Table 21]

[0305] <Method for producing compound (VI)> The production method of the squarylium compound (VI) will be explained using the production method of the squarylium compound (VI-11), but the production method of the squarylium compound (VI) is not limited thereto. A method for obtaining the squarylium compound (VI-11) is shown in Scheme (F-A11).

[0306] [ka]

[0307] (1) The starting material (pA11-1), which is a known compound, was treated with diisopropylethylamine (CH 3 CH 2 N(CH(CH 3 ) 2 ) 2 ) is reacted with acetic anhydride to obtain a compound (pA11-2) with a protected amino group. (2) Compound (pA11-3) is obtained by nitration reaction. (3) The compound (pA11-4) is obtained by deprotection of the amino group. (4) N alkylation (S using alkyl halides and bases) N 2 reaction, or reductive amination reaction using an aldehyde and a reducing agent) to obtain compound (pA11-5). (5) The compound (pA11-6) is obtained by reduction of the nitro group. (6) Compound (pA11-6) and alkanoyl chloride (R 36a —C(═O)—Cl) to obtain compound (pA11-7). (7) The compound (pA11-8) is obtained by deprotection of the methoxy group. (8) Compound (pA11-8) is reacted with squaric acid to obtain compound (VI-11).

[0308] The squarylium compound (VI-12) can be prepared by reacting the alkanoyl chloride (R 36a -C(=O)-Cl) to R 36a SO 2It can be produced by changing it to Cl. The squarylium compound (VI-13) can be prepared by reacting it with carbonyldiimidazole in the above step (6) and then reacting it with R 36a NH 2 It can be produced by reacting The squarylium compound (VI-14) can be prepared by reacting the alkanoyl chloride (R 36a -C(=O)-Cl) to R 36a It can be produced by changing OC(=O)-Cl.

[0309] The content of the squarylium dye in the dichroic dye composition of the present invention is preferably 0.1 mmol or more, more preferably 0.3 mmol or more, per 100 parts by mass of the liquid crystal compound from the viewpoint of sufficient absorbance, and is preferably 10 mmol or less, more preferably 5 mmol or less, per 100 parts by mass of the liquid crystal compound from the viewpoint of expressing a stable liquid crystal phase over a wide temperature range. Two or more kinds of dyes may be used in combination, in which case the total content is within the above range.

[0310] <Liquid crystal compounds> The dichroic dye composition of the present invention contains, in addition to the dye, a liquid crystal compound that transmits visible light.

[0311] The types of liquid crystal compounds include non-polymerizable liquid crystal compounds exhibiting a nematic phase, polymerizable liquid crystal compounds exhibiting a nematic phase, polymerizable liquid crystal compounds exhibiting a smectic phase, etc. The liquid crystal compounds may be synthesized by a known method, or commercially available products may be used.

[0312] The content of the liquid crystal compound in the dichroic dye composition of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, from the viewpoint of expressing a stable liquid crystal phase over a wide temperature range, and is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less, from the viewpoint of sufficient absorbance.

[0313] <Other ingredients> A compound that does not exhibit liquid crystallinity may be added to the dichroic dye composition of the present invention for the purpose of changing the physical properties of the host liquid crystal to a desired range (for example, to set the temperature range of the liquid crystal phase to a desired range). In addition, compounds such as chiral compounds, ultraviolet absorbers, antioxidants, and polymerization initiators may be contained. Examples of such additives include the chiral agents for TN and STN described on pages 199 to 202 of "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989). The dichroic dye composition of the present invention may contain an optically active compound, such as cholesteryl nonanoate, which may or may not exhibit a liquid crystal phase, and may also contain various additives, such as an ultraviolet absorber and an antioxidant.

[0314] In addition, when the liquid crystal compound is a non-polymerizable liquid crystal compound exhibiting a nematic phase, a liquid crystal curable compound having a polymerizable functional group or a non-liquid crystal curable compound having a polymerizable functional group may be added to the dichroic dye composition of the present invention. From the viewpoint of producing a polymer-dispersed liquid crystal element (PDLC) having a high-quality transmission-scattering type operation mode, it is preferable that the content of the non-liquid crystal curable compound is greater than the content of the liquid crystal curable compound in the dichroic dye composition, and the total amount of the liquid crystal curable compound and the non-liquid crystal curable compound is 8% by mass or more and less than 20% by mass of the total.

[0315] In addition, PDLC shows a scattering state when no voltage is applied, but also includes elements that show a transparent state when no voltage is applied. An element that shows a transparent state when no voltage is applied contains a structure made of a curable compound having an orientation similar to that of liquid crystal molecules in the composition, and the liquid crystal molecules are oriented so as to have the same orientation axis as the structure, thereby ensuring transparency. In the present invention, the curable compound includes both those that have liquid crystallinity and those that do not have liquid crystallinity, and it is preferable that the content of the curable compound is 5% by mass or more and less than 20% by mass of the entire composition.

[0316] <Refractive index anisotropic film, optical absorption anisotropic film> In the present invention, the squarylium dye, which is a dichroic dye, transmits visible light and absorbs near-infrared light, so that the film formed from the dichroic dye composition of the present invention has both properties of refractive index anisotropy and light absorption anisotropy. Therefore, it functions as a retardation film in the visible light region and functions as a polarizing film in the near-infrared light region. The retardation film is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or conversely, to convert circularly polarized light or elliptically polarized light into linearly polarized light. Polarizing films are used to split unpolarized incident light into two orthogonal polarized components, transmit one polarized component, and absorb the other. The axial direction of the transmitted polarized component is called the transmission axis, and the axial direction of the absorbed polarized component is called the absorption axis.

[0317] <Optical elements> The dichroic dye composition of the present invention, which has both liquid crystallinity and dichroism, is useful as a material for various optical elements such as retardation plates, polarizers, liquid crystal elements, etc. Since the dichroic dye of the present invention has a property of absorbing near-infrared light, it is possible to prepare a retardation film for visible light that absorbs near-infrared light, or a near-infrared-absorbing polarizing film that transmits visible light. Each optical element will be described below.

[0318] <Retardation plate, polarizer> The present invention also relates to a retardation plate having a substrate and the refractive index anisotropic film of the present invention on the substrate or between a pair of substrates. The present invention also relates to a polarizer having a substrate and the optically absorptive anisotropic film of the present invention on the substrate or between a pair of substrates. The substrate may be a substrate made of glass or plastic. Examples of plastic substrates include acrylic resin, polycarbonate resin, and epoxy resin. The substrate may be, for example, one described on pages 218 to 231 of "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989).

[0319] It is preferable to form an alignment layer (alignment film) on the surface of the substrate that contacts the refractive index anisotropic film or the light absorption anisotropic film. Examples of the alignment treatment include a method of applying a quaternary ammonium salt and aligning it, a method of applying a polyimide and aligning it by rubbing, a method of evaporating SiOx from an oblique direction and aligning it, and an alignment method by light irradiation utilizing photoisomerization. As the alignment film, for example, the one described on pages 240 to 256 of "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989) is used.

[0320] When a refractive index anisotropic film or an optical absorption anisotropic film is formed between a pair of substrates, for example, a pair of substrates are placed facing each other at an interval of 1 to 50 μm via a spacer or the like, the dichroic dye composition of the present invention is injected into the space formed between the substrates, and photopolymerization is performed by irradiating light of a predetermined wavelength as necessary. As the spacer, for example, those described on pages 257 to 262 of "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989) can be used.

[0321] <Liquid crystal element> The present invention also relates to a liquid crystal element comprising a pair of electrode substrates and a liquid crystal layer formed between the electrode substrates. The liquid crystal layer is formed from the dichroic dye composition of the present invention. The electrode layer formed on the substrate is preferably a transparent electrode layer, and can be formed from, for example, indium oxide, indium tin oxide (ITO), tin oxide, or the like. As for the transparent electrode, for example, one described on pages 232 to 239 of "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989) is used. The liquid crystal element of the present invention also functions as a retardation plate in the visible light region, and also functions as a polarizer in the near infrared light region.

[0322] The optical element of the present invention can be mounted in various instruments described below.

[0323] <Imaging device> The imaging device of the present invention includes, for example, a solid-state imaging element, an imaging lens, and the optical element of the present invention, and can provide a good image with high color reproducibility.

[0324] <Lightwave ranging device> The optical distance measuring device of the present invention includes, for example, a laser diode, a scanning unit such as a beam splitter or a MEMS mirror, a photodiode, and the optical element of the present invention. This suppresses the return light noise to the laser diode and the stray light in the optical distance measuring device, improves the detection accuracy, and reduces false detections.

[0325] <Solar radiation control components> The solar radiation control member of the present invention includes, for example, the optical element of the present invention, which can switch between transmitting and absorbing near-infrared light without impairing the transmittance of visible light.

[0326] <Virtual reality device> The virtual reality device of the present invention includes a display unit such as an LCD, OLED, or μLED, a lens unit, an optical element of the present invention between the display unit and the lens unit, and a camera equipped with near-infrared lighting capable of photographing the user's eyes. The lens unit can include a retardation plate and a reflective polarizer, and the retardation plate can be the retardation plate of the present invention. As an optical element between the display unit and the lens unit, the retardation plate or polarizer of the present invention can be used. The above configuration suppresses stray near-infrared light within the virtual reality device, improves gaze tracking accuracy, and reduces false detections. EXAMPLES

[0327] Next, the present invention will be described more specifically with reference to examples.

[0328] The dyes used in each example are as follows: Compounds 1 to 4: Synthesized based on WO 2017 / 135359. Compound 5: Pyrrolidone and TMS-Cl are reacted to produce N-TMS pyrrolidone, which is then treated with LDA and reacted with n-octane iodide. Water is added to produce 5-octylpyrrolidone, which is then reacted with LiAlH 4 The corresponding amine (3-octylpyrrolidine) was synthesized by reduction with , and the rest was synthesized according to WO 2017 / 135359. Compounds 6-7: Synthesized based on WO 2017 / 135359. Compound 8: Synthesized based on WO 2019 / 230570.

[0329] Compound 9: Synthesized according to the reaction pathway shown below.

[0330] [ka]

[0331] <Step 1> Lithium diisopropylamide (THF / hexane solution, 1.08M, 200mL, 216mmol) was placed in a nitrogen-purged 1L four-neck flask and cooled to -78°C. 3,4-dibromothiophene (50.11g, 207mmol) diluted with THF (200mL) was added over 10 minutes using a dropping funnel and then stirred for 30 minutes. The temperature was raised to 0°C and stirred for 10 minutes, after which DMF (19.2mL, 248mmol) was added and stirred at 30°C for 2.5 hours. After the reaction was completed, the mixture was cooled to 0°C and saturated ammonium chloride water (200mL) was added. The mixture was extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a crude product (60.8g) of intermediate a1-1. The crude product was used as it was in the next reaction. 1 H NMR (CDCl 3 ,300MHz)δ9.95(1H,s),7.76(1H,s).

[0332] <Step 2> Potassium carbonate (42.86 g, 310 mmol), the above intermediate a1-1 crude product (60.82 g), DMF (200 mL), ethyl mercaptoacetate (25 mL, 229 mmol), and 18-crown-6-ether (2.742 g, 10.4 mmol) were added to a nitrogen-purged 500 mL four-neck flask, and the mixture was heated and stirred overnight at 60° C. After cooling to room temperature, the solid was removed by filtration, water was added, and the mixture was extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate, concentrated under reduced pressure, and washed with hexane to obtain intermediate a1-2 (42.6 g, 71% yield for two steps). 1 H NMR (CDCl 3 , 300MHz) δ8.01(1H,s),7.47(1H,s),4.39(2H,q,J=7.1Hz),1.40(3H,t,J=7.2Hz).

[0333] <Step 3> In a nitrogen-substituted eggplant flask (500 mL), intermediate a1-2 (29.31 g, 100.6 mmol), potassium vinyl trifluoroborate (15.52 g, 110.1 mmol), palladium (II) chloride (374.6 mg, 2.007 mmol), triphenylphosphine (1.571 g, 5.990 mmol), cesium carbonate (97.72 g, 299.9 mmol), and THF / water (9 / 1) (200 mL) were added and heated and stirred at 85 ° C for 3 days. After the reaction was completed, water was added, extracted with dichloromethane, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a crude product of intermediate a1-3 (27.09 g). The crude product was used in the next reaction as it was. 1 H NMR (CDCl 3 ,300MHz)δ8.00(1H,s),7.47(1H,s),6.83(1H,dd,J=17.7,11.0Hz),5.73(1H,d, J=17.6Hz), 5.48(1H,d,J=10.9Hz),4.40(2H,q,J=7.1Hz),1.41(3H,t,J=7.1Hz).

[0334] <Step 4> The crude product, lithium hydroxide monohydrate (4.617 g, 110.0 mmol), tetrabutylammonium iodide (1.848 g, 5.003 mmol), water (33 mL), methanol (20 mL), and THF (67 mL) were added to a nitrogen-substituted eggplant flask (300 mL) and heated and stirred at 80° C. for 3 hours. After the reaction was completed, hexane was added, extracted with water, and acidified with 6N hydrochloric acid. The mixture was extracted with ethyl acetate, dried with magnesium sulfate, concentrated under reduced pressure, and washed with dichloromethane to obtain intermediate a1-4 (18.69 g, 88% yield for two steps). 1 H NMR (DMSO-d 6 ,300MHz)δ8.04(1H,s),7.72(1H,s),6.91(1H,dd,J=17.6,11.1Hz),5.69(1H,d,J=17.8Hz),5.47(1H,d,J=11.1Hz).

[0335] <Step 5> In a nitrogen-purged two-necked eggplant flask (300 mL), intermediate a1-4 (7.489 g, 35.61 mmol), diphenylphosphoryl azide (11.3 mL, 52.0 mmol), triethylamine (7.3 mL, 52 mmol), and THF (140 mL) were added, and the mixture was heated to reflux at 80° C. for 2.5 hours. After cooling to room temperature, the mixture was poured into a silica gel (500 cm 3 ) was added, the mixture was filtered, concentrated under reduced pressure, and purified by silica gel column chromatography (hexane:ethyl acetate=95:5) to obtain intermediate a1-5 (6.938 g, 94% yield). 1 H NMR (CDCl 3 ,300MHz)δ8.04(1H,s),7.55(1H,s),6.83(1H,dd,J=17.8,11.1Hz),5.73(1H,d,J=17.6Hz),5.51(1H,d,J=11.1Hz).

[0336] <Step 6> Intermediate a1-5 (724.4 mg, 3.495 mmol), THF (8.0 mL), and water (8.0 mL) were added to a nitrogen-substituted microwave test tube, and the mixture was heated and stirred at 150° C. for 5 minutes under microwave irradiation. This was repeated 7 batches, and a total of 4.926 g of intermediate a1-5 was used for the reaction. After the reaction was completed, the 7 batches were combined, extracted with ethyl acetate, concentrated, and then subjected to silica gel column chromatography (hexane:ethyl acetate=80:20) to obtain intermediate a1-6 (2.223 g, 52% yield). 1 H NMR (CDCl 3 ,300MHz)δ7.02(1H,s),6.76(1H,dd,J=17.7,11.0Hz),6.43(1H,s),5.53(1H,d,J=17.6Hz),5.35(1H,d,J=10.9Hz),3.91(2H,brs).

[0337] <Step 7> In a nitrogen-purged two-neck flask (200 mL), intermediate a1-6 (3.008 g, 16.59 mmol), 2-ethylhexanal (9.297 g, 72.51 mmol), sodium triacetoxyborohydride (15.38 g, 72.58 mmol), and 1,2-dichloroethane (82.5 mL) were added and stirred at room temperature for 7.5 hours. After adding saturated sodium bicarbonate water, the mixture was extracted with dichloromethane, dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography (hexane 100%) to obtain intermediate a2-7 (369.1 mg, 6% yield). 1 H NMR (CDCl 3 ,400MHz)δ6.91(1H,s),6.76(1H,dd,J=17.6,11.0Hz),6.05(1H,s),5.57(1H,d,J=17.6Hz),5.33(1 H,d,J=11.0Hz),3.14(4H,d,J=9.8Hz),1.88-1.77(2H,m),1.44-1.21(16H,m),0.93-0.85(12H,m).

[0338] <Step 8> Intermediate a2-7 (249.9 mg, 0.6160 mmol), 3,4-dihydroxy-3-cyclobutene-1,2-dione (37.8 mg, 0.331 mmol), trimethyl orthoformate (0.33 mL, 3.0 mmol), and 1-propanol (30 mL) were added to a nitrogen-substituted recovery flask (100 mL), and the mixture was heated to reflux at 80° C. for 2 hours. After completion of the reaction, the solvent was removed, and compound (9) (39.7 mg, 14% yield) was obtained by silica gel chromatography (hexane:ethyl acetate=80:20). 1 H NMR (CDCl 3 ,300MHz)δ8.59(2H,dd,J=17.6,11.1Hz),6.09(2H,s),5.73(2H,d,J=17.3Hz),5.72(2H,d,J =11.4Hz),3.33(8H,d,J=7.3Hz),2.00-1.87(4H,m),1.45-1.21(32H,m),0.99-0.85(24H,m).

[0339] Compound 10: Synthesized according to the reaction pathway shown below.

[0340] [ka]

[0341] <Steps 1-2> Intermediate a1-2 was obtained by steps similar to steps 1 and 2 of the production method of compound (9).

[0342] <Step 3> Intermediate a1-2 (83.66 g, 272.9 mmol), THF (175 mL), ethanol (175 mL), and aqueous sodium hydroxide solution (1.0 M, 430 mL, 430 mmol) were added to a nitrogen-substituted eggplant flask (2 L), and the mixture was heated and stirred at 40 ° C for 1 hour. After the reaction was completed, hydrochloric acid (1.0 M, 450 mL) was added at 0 ° C to acidify the mixture, and the organic solvent was removed under reduced pressure, followed by filtration using a hydrophilic membrane filter. The residue was washed with water, then with a mixed solvent of water:methanol (= 1: 1), and the solvent was removed by azeotropic distillation with toluene, followed by vacuum drying to obtain intermediate a4-3 (79.4 g, > 99% yield). 1 H NMR (DMSO-d 6 ,300MHz)δ13.51(1H,brs),8.23(1H,s),8.08(1H,s).

[0343] <Step 4> Intermediate A4-3 (26.53 g, 100.8 mmol), toluene (200 mL), triethylamine (21.0 mL, 151 mmol), and diphenylphosphoryl azide (30.62 g, 111.3 mmol) were added to a nitrogen-substituted eggplant flask (300 mL), and the mixture was heated and stirred at 60° C. for 30 minutes. After the reaction was completed, saturated sodium bicarbonate water and ethyl acetate were added at 0° C. and the mixture was separated. The resulting organic layer was washed with saturated sodium bicarbonate water, water, and saturated saline, dried over sodium sulfate, concentrated, washed with hexane, and then vacuum dried to obtain intermediate A4-4 (25.24 g, 96% yield). 1 H NMR (CDCl 3 ,400MHz)δ8.05(1H,s),7.55(1H,s).

[0344] <Step 5> Intermediate A4-4 (12.01 g, 46.19 mmol), t-butyl alcohol (100 mL), and toluene (100 mL) were added to a nitrogen-substituted recovery flask (500 mL), and the mixture was heated and stirred at 80° C. for 15 hours. After the reaction was completed, the mixture was concentrated, dissolved in dichloromethane, filtered with silica gel, the solvent was removed, and the mixture was dried in vacuum to obtain intermediate A4-5 (12.21 g, 79% yield). 1 H NMR (DMSO-d6 ,300MHz)δ10.80(1H,s),7.50(1H,s),6.92(1H,s),1.49(9H,s).

[0345] <Steps 6-7> In a nitrogen-substituted eggplant flask (1L), intermediate a4-5 (12.20 g, 36.49 mmol), sodium iodide (11.00 g, 73.40 mmol), and acetonitrile (370 mL) were added, and chlorotrimethylsilane (7.776 g, 71.58 mmol) was added at 40°C. After heating and stirring for 16.5 hours, saturated sodium bicarbonate water and ethyl acetate were added at room temperature and the mixture was separated, and the organic layer was washed with saturated sodium bicarbonate water, water, and saturated saline. 2-Ethylhexanal (7.021 g, 54.76 mmol) and sodium sulfate were added to the obtained organic layer, and the mixture was left to stand for 15 minutes, filtered, and the solvent was distilled off. The resulting material was transferred to a four-neck flask (1 L), and methanol (270 mL), acetic acid (37 mL), and 2-ethylhexanal (14.05 g, 109.6 mmol) were added. The mixture was stirred at -10°C under a nitrogen atmosphere, and a solution of 2-picoline borane (7.900 g, 71.65 mmol) in methanol (100 mL) was added dropwise over 10 minutes. After stirring for 19 hours, saturated aqueous sodium bicarbonate, hexane, and ethyl acetate were added and the mixture was separated. The resulting organic layer was washed with saturated aqueous sodium bicarbonate, water, and saturated saline, dried over sodium sulfate, and concentrated to obtain a crude product. The raw aldehyde was converted to NH 2 After removal by silica gel filtration, intermediate a4-7 (12.01 g, 72% yield) was obtained by silica gel column chromatography (100% hexane). 1 H NMR (CDCl 3 ,300MHz)δ6.98(1H,s),6.14(1H,s),3.13(4H,d,J=7.5Hz),1.91-1.75(2H,m),1.45-1.21(16H,m),1.00-0.82(12H,m).

[0346] <Step 8> In a nitrogen-substituted two-neck flask (50 mL), intermediate a4-7 (1.994 g, 4.349 mmol), methyl acrylate (560.4 mg, 6.509 mmol), triethylamine (1.300 g, 12.84 mmol), palladium (II) acetate (49.9 mg, 0.222 mmol), tri-orthotolylphosphine (132.8 mg, 0.4363 mmol), and DMF (25.0 mL) were added, and the mixture was heated and stirred at 85 ° C for 3 hours. After the reaction was completed, a saturated aqueous ammonium chloride solution was added at 0 ° C, extracted with hexane / ethyl acetate, washed with water and saturated saline, dried over magnesium sulfate, concentrated, and intermediate a9-8 (461.9 mg, 23% yield) was obtained by silica gel column chromatography (hexane: ethyl acetate = 20: 1). 1 H NMR (CDCl 3 ,300MHz)δ7.71(1H,d,J=16.1Hz),7.24(1H,s),6.23(1H,d,J=15.8Hz),6.04(1H ,s),3.82(3H,s),3.15(4H,d,J=7.3Hz),1.47-1.21(16H,m),0.96-0.83(12H,m).

[0347] <Step 9> In a nitrogen-substituted eggplant flask (100 mL), intermediate a9-8 (461.9 mg, 0.996 mmol), 3,4-dihydroxy-3-cyclobutene-1,2-dione (172.2 mg, 1.509 mmol), trimethyl orthoformate (1.279 g, 12.05 mmol), and 1-propanol (50 mL) were added and heated and stirred at 80 ° C for 1.5 hours. After the reaction was completed, the mixture was concentrated to about half the volume, and hexane, ethyl acetate, and saturated sodium bicarbonate water were added to separate the mixture. The resulting organic layer was washed with water, dried over sodium sulfate, concentrated, and washed with hexane. The obtained solid was purified by silica gel column chromatography (dichloromethane: ethyl acetate = 30: 1) to obtain compound (10) (345.5 mg, 69% yield). 1 H NMR (CDCl 3,300MHz)δ9.57(2H,d,J=14.3Hz),6.32(2H,d,J=16.1Hz),6.13(2H,s),3.94(6H,s) ,3.35(8H,d,J=7.1Hz),2.00-1.87(4H,m),1.48-1.23(32H,m),1.01-0.85(24H,m).

[0348] Compound 11: Synthesized based on WO 2019 / 230660.

[0349] Compound 12: Synthesized based on the following reaction pathway:

[0350] [ka]

[0351] (Step 1): Compound (1x) (3-amino-2-methoxypyridine, manufactured by Tokyo Chemical Industry Co., Ltd.) (2.5 g) was dissolved in dichloromethane (60 ml), and diisopropylethylamine (2.8 g) and acetic anhydride (2.25 g) were added and stirred at room temperature for 3 hours. The product was purified by silica gel column chromatography to obtain compound (2x) (yield 94%). (Step 2): To compound (2x) (2.5 g), trifluoroacetic anhydride (7.5 ml) was added at 0° C. and stirred for 30 minutes, after which a mixed solution of 1.1 equivalents of nitric acid (1.1 g) and trifluoroacetic anhydride (12 g) was added dropwise at 0° C. After stirring at room temperature for 12 hours, the mixture was neutralized with an aqueous sodium hydroxide solution, and 2.4 g of the resulting solid compound (3x) was collected (yield 76%). (Step 3): Compound (3x) (1.9 g) was dissolved in methanol (50 ml), and 1 M hydrochloric acid (18 ml) was added and stirred for 12 hours at 60° C. After removing the methanol, the mixture was neutralized and 1.47 g of compound (4x) was filtered off as a solid (yield 96%). (Step 4): Compound (4x) (5.1 g) was dissolved in dichloromethane (80 ml), 2-ethylhexylaldehyde (42 ml) (20 equivalents), triacetoxyborohydride (25 g) (4 equivalents), and acetic acid (0.2 ml) were added, and the mixture was stirred at room temperature for 4 hours. After adding an alkali until the pH reached 7, the mixture was separated into dichloromethane and water, and the concentrated organic layer was purified by silica gel chromatography to obtain compound (5x) (5.9 g) (yield 78%). (Step 5): Compound (5x) (5.9 g) was dissolved in methanol, palladium on carbon (3 g) was added, and the mixture was stirred under a hydrogen atmosphere for 5 hours. Water was added, and the palladium was removed by filtration through Celite. After removing the methanol, the mixture was separated with ethyl acetate / water to obtain the desired compound (6) (3.7 g) (yield 71%). (Step 6): Compound (6x) (3.7 g) was dissolved in dichloromethane (50 ml) and diisopropylethylamine (2.36 g) was added. The solution was cooled to 0°C, isobutyl chloroformate (2.7 g) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the mixture was separated into dichloromethane and water, and the organic layer was concentrated and then purified by column chromatography to obtain the target compound (7x) (yield 88%). (Step 7): Compound (7x) (5.8 g) was dissolved in 150 ml of acetonitrile, and 3 equivalents each of TMS-Cl (5.4 g) and sodium iodide (7.5 g) were added. After reacting at 80°C for 3 hours, the mixture was concentrated and purified by column chromatography to obtain the desired compound (8x) (2 g) (yield 35%). (Step 8): Compound (8x) and 0.6 equivalents of 3,4-dihydroxy-3-cyclobutene-1,2-dione were added and reacted in 1-butanol at 110° C. for 16 hours. After the reaction was completed, the solvent was completely removed, and the product was purified using a column and extracted with an acetic acid / methanol solution to obtain squarylium compound (12) in a 35% yield.

[0352] Compounds 13 to 15: Synthesized based on WO 2017 / 135359. In Compounds 13 to 15, indoline was synthesized according to the following method. In compound 13, 2,3,3-trimethylindolenine was reacted with an excess of sodium borohydride in acetic acid solvent, and then reacted with isobutyraldehyde to synthesize N-isobutyl-2,3,3-trimethylindoline. In the case of compound 14, isobutyronitrile was reacted with isobutylmagnesium and then with phenylhydrazine to synthesize indolenine, which was then reacted with an excess of sodium borohydride in acetic acid solvent and then with propionaldehyde to synthesize N-propyl-2-isobutyl-3,3-dimethylindoline. In the case of compound 15, 2,3-dimethylindole was reacted with ethylmagnesium bromide and then with methallyl chloride to synthesize indolenine. In acetic acid, this indolenine was reacted with an excess of sodium borohydride and then with acetaldehyde to synthesize N-ethyl-3-isobutyl-2,3-dimethylindoline.

[0353] Compound 16: Synthesized based on the method described in Dyes and pigments 73 (2007) 344-352.

[0354] As the liquid crystal compound, the following non-polymerizable nematic liquid crystal compound (ZLI-1132 manufactured by LCC Corporation) was used.

[0355] [Table 22]

[0356] <Production and evaluation of dichroic dye compositions> (Example 1) The squarylium dye of Compound 1 below and the above liquid crystal compound were mixed to obtain a dichroic dye composition of Example 1 having a squarylium dye content of 0.19 mass % (0.34 mmol relative to 100 parts by mass of the liquid crystal compound). The obtained dichroic dye composition was injected into a horizontal alignment cell with a gap of 5 μm manufactured by EHC Corporation, and polarized light parallel to the rubbing direction and polarized light perpendicular to the rubbing direction were irradiated. The respective absorption spectra (A|| and A⊥) were measured using a visible absorption spectrometer (manufactured by Shimadzu Corporation) to determine the dichroic ratio.

[0357] [ka]

[0358] (Example 2) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 2 below was used as the squarylium dye and the squarylium dye content was 0.24 mass % (0.30 mmol per 100 parts by mass of the liquid crystal compound).

[0359] [ka]

[0360] (Example 3) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 3 below was used as the squarylium dye and the squarylium dye content was 0.21 mass % (0.34 mmol per 100 parts by mass of the liquid crystal compound).

[0361] [ka]

[0362] (Example 4) The dichroic ratio was measured in the same manner as in Example 1, except that Compound 4 below was used as the squarylium dye and the squarylium dye content was 0.10% by mass (0.22 mmol relative to 100 parts by mass of the liquid crystal compound).

[0363] [ka]

[0364] (Example 5) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 5 below was used as the squarylium dye and the squarylium dye content was 0.18 mass % (0.27 mmol per 100 parts by mass of the liquid crystal compound).

[0365] [ka]

[0366] (Example 6) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 6 below was used as the squarylium dye and the squarylium dye content was 0.16 mass % (0.33 mmol per 100 parts by mass of the liquid crystal compound).

[0367] [ka]

[0368] (Example 7) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 7 below was used as the squarylium dye and the squarylium dye content was 0.16 mass % (0.33 mmol per 100 parts by mass of the liquid crystal compound).

[0369] [ka]

[0370] (Example 8) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 8 below was used as the squarylium dye and the squarylium dye content was 0.25% by mass (0.30 mmol per 100 parts by mass of the liquid crystal compound).

[0371] [ka]

[0372] (Example 9) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 9 below was used as the squarylium dye and the squarylium dye content was 0.20% by mass (0.22 mmol per 100 parts by mass of the liquid crystal compound).

[0373] [ka]

[0374] (Example 10) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that Compound 10 below was used as the squarylium dye and the squarylium dye content was 0.50 mass % (0.50 mmol per 100 parts by mass of the liquid crystal compound).

[0375] [ka]

[0376] (Example 11) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that the following compound 11 was used as the squarylium dye and the squarylium dye content was 0.31% by mass (0.33 mmol per 100 parts by mass of the liquid crystal compound).

[0377] [ka]

[0378] (Example 12) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that the following compound 12 was used as the squarylium dye and the squarylium dye content was 0.20 mass % (0.20 mmol per 100 parts by mass of the liquid crystal compound).

[0379] [ka]

[0380] (Example 13) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that the following compound 13 was used as the squarylium dye and the squarylium dye content was 0.16 mass % (0.27 mmol per 100 parts by mass of the liquid crystal compound).

[0381] [ka]

[0382] (Example 14) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that the following compound 14 was used as the squarylium dye and the squarylium dye content was 0.17% by mass (0.26 mmol per 100 parts by mass of the liquid crystal compound).

[0383] [ka]

[0384] (Example 15) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that the following compound 15 was used as the squarylium dye and the squarylium dye content was 0.19% by mass (0.30 mmol per 100 parts by mass of the liquid crystal compound).

[0385] [ka]

[0386] (Example 16) A dichroic dye composition was prepared and the dichroic ratio was measured in the same manner as in Example 1, except that the squarylium dye was replaced with the cyanine dye, Compound 16 below, and the cyanine dye content was 0.25% by mass (0.32 mmol per 100 parts by mass of the liquid crystal compound).

[0387] [ka]

[0388] The dichroic ratios of the above dichroic dye compositions are shown in the table below. Examples 1 to 15 are working examples, and Example 16 is a comparative example.

[0389] [Table 23]

[0390] [Table 24]

[0391] As can be seen from the above results, all of the dichroic dye compositions of the Examples exhibited excellent dichroic properties. [Industrial Applicability]

[0392] The dichroic dye composition of the present invention is useful as a material for optical elements such as liquid crystal elements, polarizers, retardation plates, etc. In addition, since the dichroic dye composition of the present invention has near-infrared absorbing ability, it is particularly useful for near-infrared and infrared light sensors, etc.

Claims

1. The present invention includes a squarylium dye containing a heteroatom and a liquid crystal compound that transmits visible light, The dichroic dye composition, wherein the squarylium dye has a maximum absorption wavelength in a wavelength region of 700 nm or more and is a compound represented by any one of the following formulas (II), (III), (V), and (VI): 【Chemistry 1】 [The symbols in the above formula are as follows: Each ring Z2 is independently a 5- or 6-membered ring having 0 to 3 heteroatoms in the ring, and the hydrogen atom in ring Z2 may be substituted. R 12 and R 22 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an unsaturated bond between carbon atoms, a heteroatom, or a saturated or unsaturated ring structure and which may have a substituent. R 32 and R 42 each independently represent a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 8 carbon atoms which may contain a heteroatom between the carbon atoms and which may have a substituent. R 12 and R 22 , R 12 and R 42 , and R 22 and the carbon atoms or heteroatoms constituting ring Z2 may be bonded to each other to form, together with the nitrogen atom, a 4- to 6-membered heterocycle A2, a 5- to 7-membered heterocycle B2, and a 5- to 7-membered heterocycle C2, respectively. 【Chemistry 2】 [The symbols in the above formula are as follows: R 13 and R 23 each independently represent an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a heteroatom, an alicyclic ring or an aromatic ring. R 33 is an organic group R 33A which does not necessarily have an unsaturated bond, or an organic group R 33B which necessarily has an unsaturated bond. X 31 is CR 43 or N. X 32 is S, NR 53 or O. X 33 is S, NR 63 or O. R 43 is a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carbonyl structure-containing monovalent organic group, a phosphate group, a silyl group, a thiol group, a sulfide group, an amide structure-containing monovalent organic group, a sulfonamide group, a urea group, a urethane structure-containing monovalent organic group, an alkyl group having 1 to 9 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, an alkynyl group having 2 to 9 carbon atoms which may have a substituent, an aryl group having 6 to 9 carbon atoms which may have a substituent, a heteroaryl group having 3 to 9 carbon atoms which may have a substituent, an alkoxy group having 1 to 9 carbon atoms which may have a substituent, an acyloxy group having 2 to 9 carbon atoms which may have a substituent, or -N(R 43g ) 2 (R 43g is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent). R 53 and R 63 each independently represent a hydrogen atom, a carbonyl structure-containing monovalent organic group, a sulfo group, or an alkyl group having 1 to 9 carbon atoms which may have a substituent. R 13 may be linked with R 23 , R 33 , X 31 , X 32 or X 33 to form a 3-6 membered ring. R 23 may be linked with R 13 , R 33 , X 31 , X 32 or X 33 to form a 3-6 membered ring. R 33 may be linked with X 31 , X 32 , or X 33 to form a 5- to 7-membered ring.] 【Chemistry 3】 [The symbols in the above formula are as follows: R 15 and R 25 each independently represent an alkyl group having 1 to 20 carbon atoms, which may have a substituent, and which may contain an unsaturated bond or a heteroatom between the carbon atoms, or an araryl group having 4 to 20 carbon atoms. R 35 , R 45 , R 55 and R 65 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aryl group having 4 to 9 carbon atoms which may have a substituent, or an araryl group having 5 to 9 carbon atoms which may have a substituent. R 35 and R 45 , R 45 and R 55 , and R 55 and R 65 may be linked to each other to form a monocycle or a polycycle having 2 to 4 condensed rings. R 15 and R 25 may be linked to each other to form a 4-10 membered heterocycle together with the nitrogen atom.] 【Chemistry 4】 [The symbols in the above formula are as follows: R 16 and R 26 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent and which may contain an unsaturated bond between carbon atoms, a heteroatom, an alicyclic ring or an aromatic ring. R 36 is a monovalent organic group having 9 or less carbon atoms which contains an atom having an unshared electron pair. R 46 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. R 56 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. X 61 is C═O, C═S, or SO 2 . R 16 and R 26 , R 16 and R 46 , and R 36 and R 46 may be bonded to each other to form a ring having 3 to 6 members.]

2. The dichroic dye composition according to claim 1 , wherein the squarylium dye is a compound represented by formula (II).

3. The dichroic dye composition according to claim 1 , wherein the squarylium dye is a compound represented by formula (III).

4. The dichroic dye composition according to claim 1 , wherein the squarylium dye is a compound represented by formula (V).

5. The dichroic dye composition according to claim 1 , wherein the squarylium dye is a compound represented by formula (VI).

6. 6. The dichroic dye composition according to claim 1, wherein the content of the liquid crystal compound is 50% by mass or more.

7. A liquid crystal element comprising a pair of electrode substrates and a liquid crystalline layer formed between the pair of electrode substrates, A liquid crystal device, wherein the liquid crystal layer is formed from the dichroic dye composition according to any one of claims 1 to 6.

8. A retardation plate comprising a substrate and a refractive index anisotropic film formed on at least one of the main surfaces of the substrate; or A retardation plate comprising a pair of substrates and a refractive index anisotropic film formed between the pair of substrates, 7. A retardation plate, comprising the refractive index anisotropic film formed from the dichroic dye composition according to claim 1.

9. A polarizer comprising a substrate and a light absorbing anisotropic film formed on at least one main surface of the substrate; or A polarizer comprising a pair of substrates and a light absorbing anisotropic film formed between the pair of substrates, A polarizer, wherein the optically absorptive anisotropic film is formed from the dichroic dye composition according to any one of claims 1 to 6.

10. 7. An imaging device, an optical distance measuring device, a virtual reality device, or a solar radiation control member comprising an optical element formed from the dichroic dye composition according to claim 1.

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